CN114539316B - Phosphorus-containing imidazole compound, and preparation method and application thereof - Google Patents
Phosphorus-containing imidazole compound, and preparation method and application thereof Download PDFInfo
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- CN114539316B CN114539316B CN202210084549.8A CN202210084549A CN114539316B CN 114539316 B CN114539316 B CN 114539316B CN 202210084549 A CN202210084549 A CN 202210084549A CN 114539316 B CN114539316 B CN 114539316B
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 154
- -1 imidazole compound Chemical class 0.000 title claims abstract description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 52
- 239000011574 phosphorus Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 8
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 6
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 claims description 3
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 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 abstract description 17
- 239000003063 flame retardant Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000000903 blocking effect Effects 0.000 abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000001307 helium Substances 0.000 description 5
- 229910052734 helium Inorganic materials 0.000 description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 4
- 239000010410 layer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The invention discloses a phosphorus-containing imidazole compound, and a preparation method and application thereof. The invention relates to a phosphorus-containing microphoneThe structural formula of the azole compound is as follows:wherein R is 1 And R is 2 Are all independently selected from One of them. The preparation method of the phosphorus-containing imidazole compound comprises the following steps: 1) Performing a reaction between imidazole and p-hydroxybenzyl alcohol to obtain an intermediate; 2) And (3) carrying out a reaction between the intermediate and the organophosphorus compound to obtain the phosphorus-containing imidazole compound. The phosphorus-containing imidazole compound has good compatibility with epoxy resin, and can be used as an epoxy resin curing agent to not only have excellent curing performance, but also endow the epoxy resin with excellent flame retardant property, water blocking property and thermal stability on the premise of not affecting the mechanical property of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of epoxy resin curing agents, in particular to a phosphorus-containing imidazole compound, a preparation method and application thereof.
Background
The high polymer material has the advantages of light weight, low cost, good performance and the like, and is widely concerned, and plastic steel is considered as a future development trend. However, the polymer material has the inherent inflammable characteristic, and has great fire hazard, and the economic loss and casualties caused by fire disaster are not small, so that the flame retardant treatment of the polymer material is necessary.
Epoxy resin is an application type thermosetting resin, has unique advantages in mechanical property, adhesive property, corrosion resistance, processability and the like, has low shrinkage rate and small dimensional change in the curing process, and is widely applied in recent years. However, the epoxy resin also has the inflammable characteristic of the polymer material, and one of the most effective means for improving the flame retardant property of the epoxy resin is to add a flame retardant, but the currently used additive flame retardant can influence the mechanical property of the epoxy resin product to a certain extent, and the influence can be further increased along with the increase of the adding amount of the flame retardant, so that the actual use effect is not ideal, and the increasing actual application requirement is difficult to meet.
Therefore, it is of great importance to develop a flame retardant curing agent (i.e., an intrinsic type flame retardant) that can react with an epoxy resin matrix.
Disclosure of Invention
The invention aims to provide a phosphorus-containing imidazole compound, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a phosphorus-containing imidazole compound has the following structural formula:
wherein R is 1 And R is 2 Are all independently selected from-> One of them.
Preferably, the phosphorus-containing imidazole compound has the structural formula of One of them.
The preparation method of the phosphorus-containing imidazole compound comprises the following steps:
1) Performing a reaction between imidazole and p-hydroxybenzyl alcohol to obtain an intermediate;
2) And (3) carrying out a reaction between the intermediate and the organophosphorus compound to obtain the phosphorus-containing imidazole compound.
Preferably, the preparation method of the phosphorus-containing imidazole compound comprises the following steps:
1) Mixing imidazole and p-hydroxybenzyl alcohol for reaction, and separating and purifying the product to obtain an intermediate;
2) Dispersing the intermediate, the organic phosphorus compound, the acid binding agent and the catalyst in a solvent for reaction, and then separating and purifying the product to obtain the phosphorus-containing imidazole compound.
Preferably, the molar ratio of the imidazole to the p-hydroxybenzyl alcohol in the step 1) is 1-2:1.
Preferably, the reaction in the step 1) is carried out at the temperature of 90-120 ℃ for 2-6 hours.
Preferably, the reaction of step 1) is carried out in a protective atmosphere.
It is further preferred that the reaction of step 1) is carried out in a nitrogen atmosphere or a helium atmosphere.
Preferably, the molar ratio of the intermediate to the organic phosphorus compound in the step 2) is 1-3:1.
Preferably, the organic phosphorus compound in the step 2) is one of diphenyl chlorophosphate, diphenyl phosphinic chloride and phenylphosphonic dichloride.
Preferably, the acid binding agent in the step 2) is at least one of pyridine, sodium hydroxide, sodium bicarbonate and triethylamine.
Preferably, the catalyst in the step 2) is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP).
Preferably, the solvent in the step 2) is at least one of methanol, ethanol, ethyl acetate, dichloromethane, chloroform, diethyl ether and water.
Preferably, the reaction in the step 2) is carried out at room temperature (15-25 ℃) for 4-14 hours.
Preferably, the reaction of step 2) is carried out in a protective atmosphere.
It is further preferred that the reaction of step 2) is carried out in a nitrogen atmosphere or in a helium atmosphere.
An epoxy resin curing agent comprises the phosphorus-containing imidazole compound.
An epoxy resin material, which comprises the phosphorus-containing imidazole compound.
The beneficial effects of the invention are as follows: the phosphorus-containing imidazole compound has good compatibility with epoxy resin, and can be used as an epoxy resin curing agent to not only have excellent curing performance, but also endow the epoxy resin with excellent flame retardant property, water blocking property and thermal stability on the premise of not affecting the mechanical property of the epoxy resin.
Specifically:
1) The phosphorus-containing imidazole compound has a long-chain large steric hindrance structure with rigidity as a main part and flexibility as an auxiliary part, can be used as an epoxy resin curing agent to greatly improve the gas phase and solid phase flame retardant effect of epoxy resin, and can also ensure that the epoxy resin still maintains good thermal stability (T) 5％ The temperature is higher than 340 ℃ and the mechanical property, and the water blocking property of the epoxy resin can be improved;
2) The preparation raw material p-hydroxybenzyl alcohol adopted by the invention is from natural biological extract, has wide sources and low price, and is beneficial to reducing the production cost;
3) The preparation process of the phosphorus-containing imidazole compound is simple, the first step is free of solvent, the activity of the generated intermediate is high, the second step can be performed at room temperature, byproducts are easy to remove, the product purity is high, the product stability is good, and the phosphorus-containing imidazole compound is suitable for large-scale industrial production.
Drawings
FIG. 1 shows the results of water absorption test of epoxy samples prepared with the phosphorus-containing imidazole compound and imidazole of example 1 as curing agents, respectively.
FIG. 2 is a Mass diagram of an epoxy sample prepared using the phosphorus-containing imidazole compound and imidazole of example 3 as curing agents, respectively.
FIG. 3 is a combustion cross-sectional view of an epoxy sample prepared using the phosphorus-containing imidazole compound and imidazole of example 3 as curing agents, respectively.
Fig. 4 is a graph showing thermal weight loss of epoxy samples prepared using the phosphorus-containing imidazole compound and imidazole of example 3 as curing agents, respectively.
Detailed Description
The invention is further illustrated and described below in connection with specific examples.
Example 1:
the preparation method of the phosphorus-containing imidazole compound comprises the following steps:
1) Adding 0.1mol of imidazole and 0.1mol of p-hydroxybenzyl alcohol into a reaction vessel, filling helium for protection, stirring for 4 hours at 90 ℃, naturally cooling to room temperature, adding boiling water to convert the product into white precipitate for precipitation, filtering, and drying the filtered solid to obtain an intermediate (yield: 87%);
2) Adding 0.1mol of intermediate, 0.25mol of triethylamine, 0.005mol of DMAP and 500mL of dichloromethane into a reaction vessel, filling nitrogen for protection, dropwise adding 500mL of a phenylphosphonic dichloride dissolved dichloromethane solution (containing 0.05mol of phenylphosphonic dichloride) at room temperature under stirring, continuing stirring for 12 hours after the addition is finished, filtering, extracting filtrate with brine, taking a lower organic layer for rotary evaporation, and drying to obtain a phosphorus-containing imidazole compound (melting point: 154 ℃, yield: 91%).
The nmr hydrogen spectrum, nmr carbon spectrum and ir spectrum data of the phosphorus-containing imidazole compound of this embodiment are as follows:
1 H NMR(500MHz,DMSO)：δ7.92(dd,J＝13.9,7.2Hz,2H),7.76-7.65(m,3H),7.65-7.52(m,2H),7.25(d,J＝8.6Hz,4H),7.16(dd,J＝20.0,13.7Hz,6H),6.90(s,2H),5.15(s,4H)；
13 C NMR(126MHz,DMSO)：δ149.68(d,J＝7.2Hz),137.82(s),135.44(s),134.28(s),132.52(d,J＝10.7Hz),129.58(d,J＝13.2Hz),129.20(s),121.06(d,J＝4.4Hz),119.95(s),49.14(s)；
IR：1300cm -1 (P＝O),1430cm -1 ,1492cm -1 (-CH 2 ),1050cm -1 ,1150cm -1 (P-O),1250cm -1 (C-N)。
in summary, the structural formula of the phosphorus-containing imidazole compound in this embodiment is as follows:
example 2:
the preparation method of the phosphorus-containing imidazole compound comprises the following steps:
1) Adding 0.1mol of imidazole and 0.1mol of p-hydroxybenzyl alcohol into a reaction vessel, filling helium for protection, stirring for 4 hours at 90 ℃, naturally cooling to room temperature, adding boiling water to convert the product into white precipitate for precipitation, filtering, and drying the filtered solid to obtain an intermediate (yield: 87%);
2) Adding 0.1mol of intermediate, 0.25mol of triethylamine, 0.005mol of DMAP and 500mL of ethyl acetate into a reaction vessel, filling nitrogen for protection, dropwise adding 500mL of ethyl acetate solution (containing 0.1mol of diphenyl chlorophosphate) dissolved by phenylphosphonic dichloride while stirring at room temperature, continuing stirring for 12 hours after the addition, filtering, extracting filtrate with brine, taking a lower organic layer for rotary evaporation, and drying to obtain the phosphorus-containing imidazole compound (melting point: 65 ℃, yield: 85%).
The nmr hydrogen spectrum, nmr carbon spectrum and ir spectrum data of the phosphorus-containing imidazole compound of this embodiment are as follows:
1 H NMR(500MHz,CDCl 3 )：δ7.54(s,1H),7.35(t,J＝7.8Hz,4H),7.25-7.18(m,8H),7.15-7.10(m,2H),7.09(s,1H),6.87(d,J＝6.8Hz,1H),5.09(s,2H)；
13 C NMR(126MHz,CDCl 3 )：δ150.34(d,J＝7.4Hz),137.33(s),133.58(s),129.91(d,J＝7.9Hz),128.84(s),125.77(s),120.75(d,J＝4.8Hz),120.08(d,J＝5.2Hz),119.23(s),50.08(s)；
IR：1310cm -1 (P＝O),1435cm -1 ,1490cm -1 (-CH 2 ),1035cm -1 ,1155cm -1 (P-O),1230cm -1 (C-N)。
in summary, the structural formula of the phosphorus-containing imidazole compound in this embodiment is as follows:
example 3:
the preparation method of the phosphorus-containing imidazole compound comprises the following steps:
1) Adding 0.1mol of imidazole and 0.1mol of p-hydroxybenzyl alcohol into a reaction vessel, filling helium for protection, stirring for 4 hours at 90 ℃, naturally cooling to room temperature, adding boiling water to convert the product into white precipitate for precipitation, filtering, and drying the filtered solid to obtain an intermediate (yield: 87%);
2) Adding 0.1mol of intermediate, 0.25mol of triethylamine, 0.005mol of DMAP and 600mL of ethyl acetate into a reaction vessel, filling nitrogen for protection, dropwise adding 500mL of ethyl acetate solution (containing 0.1mol of diphenylphosphinoyl chloride) dissolved by phenylphosphonic dichloride while stirring at room temperature, continuing stirring for 12 hours after the addition, filtering, extracting filtrate with brine, taking a lower organic layer for rotary evaporation, and drying to obtain the phosphorus-containing imidazole compound (melting point: 125 ℃, yield: 92%).
The nmr hydrogen spectrum, nmr carbon spectrum and ir spectrum data of the phosphorus-containing imidazole compound of this embodiment are as follows:
1 H NMR(500MHz,CDCl 3 )：δ7.80(dd,J＝12.6,7.7Hz,4H),7.47(t,J＝7.4Hz,2H),7.42-7.35(m,5H),7.10(d,J＝8.3Hz,2H),6.95(dd,J＝17.8,9.4Hz,3H),6.76(s,1H),4.93(s,2H)；
13 C NMR(126MHz,CDCl 3 )：δ150.77(d,J＝8.2Hz),137.28(s),132.64(d,J＝2.7Hz),132.40(s),131.76(d,J＝10.6Hz),131.22(s),130.12(s),129.69(s),128.97(s),128.82-128.54(m),121.29(d,J＝4.7Hz),119.25(s),116.16(s),50.11(s)；
IR：1305cm -1 (P＝O),1420cm -1 ,1491cm -1 (-CH 2 ),1050cm -1 ,1150cm -1 (P-O),1248cm -1 (C-N)。
in summary, the structural formula of the phosphorus-containing imidazole compound in this embodiment is as follows:
performance test:
1) The phosphorus-containing imidazole compounds and imidazole (epoxy curing agents commonly used in the market) of examples 1 to 3 were applied as curing agents to epoxy resins, respectively, and the specific operations were as follows: mixing bisphenol A epoxy resin (E-44) and a curing agent (dissolved by methylene dichloride firstly) according to a mass ratio of 100:18, degassing for 15min at normal temperature, pouring into a preheated mold, curing for 2h at 70 ℃ and 3h at 170 ℃, cooling, demolding to obtain an epoxy sample, and performing performance test, wherein the test results are shown in the following table:
TABLE 1 Performance test results of epoxy samples
Note that:
tensile strength and tensile modulus: carrying out tensile test by adopting a universal material tester, wherein the tensile rate is 2mm/min;
limiting Oxygen Index (LOI): measurement is performed with reference to ASTM D2863;
vertical burn test (UL-94): the measurement was performed with reference to UL94 flame retardant test methods and standards.
As can be seen from table 1: the phosphorus-containing imidazole compound is added into the epoxy resin as a curing agent, so that the flame retardant property of the epoxy sample can be obviously improved on the premise of not affecting the mechanical property of the epoxy sample.
2) The phosphorus-containing imidazole compound and imidazole of example 1 were applied as curing agents to epoxy resins, respectively, to prepare epoxy samples (the specific operations are the same as above), and then immersed in boiling distilled water to conduct a water absorption test, and the obtained water absorption test results are shown in fig. 1 (note: the water absorption is the weight increase rate of the epoxy sample).
As can be seen from fig. 1: the two epoxy samples can absorb water rapidly at the beginning, the quality is kept constant after 40 hours, and the water absorption rate of the epoxy sample prepared by taking the phosphorus imidazole compound as a curing agent is lower finally, which indicates that the phosphorus imidazole compound obtained by adjusting and controlling the steric hindrance design can endow the epoxy resin with excellent water blocking performance.
3) The phosphorus-containing imidazole compound and imidazole of example 3 were applied as curing agents to epoxy resins to prepare epoxy samples (the specific operations are the same as above), and cone calorimetric test was performed, and the Mass chart (the change curve of Mass with combustion time in the combustion process) and the combustion section chart obtained are shown in fig. 2 and 3, respectively.
As can be seen from fig. 2 and 3: the epoxy sample prepared by taking the phosphorus-containing imidazole compound as a curing agent has slower weight loss, larger residual mass and high carbon residue height of 3cm, which indicates that the phosphorus-containing imidazole compound can simultaneously flame retardant from a gas phase layer and a solid phase layer, and is different from a halogen flame retardant and a nitrogen flame retardant which only flame retardant at the gas phase layer and an inorganic flame retardant which only flame retardant at the solid phase layer.
4) The phosphorus-containing imidazole compound and imidazole of example 3 were applied as curing agents to epoxy resins, respectively, to prepare epoxy samples (the specific operations were the same as above), and then subjected to thermal weight loss test (nitrogen atmosphere, heating rate of 10 ℃/min), and the obtained thermal weight loss curves are shown in fig. 4.
As can be seen from fig. 4: the initial decomposition temperature (5%) of the epoxy sample prepared by taking the phosphorus-containing imidazole compound as a curing agent is not much different from that of the epoxy sample prepared by taking imidazole as the curing agent, and exceeds 340 ℃ (which is far higher than the normal use temperature of epoxy resin), and the maximum decomposition temperature is higher than 410 ℃, so that the phosphorus-containing imidazole compound obtained by converting the design thought has the effect of protecting and improving the intolerance of phosphoryl groups, and finally has good thermal stability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. The phosphorus-containing imidazole compound is characterized by having the following structural formula:
wherein R is 1 And R is 2 Are all independently selected from-> One of them.
2. The phosphorus-containing imidazole compound according to claim 1, wherein the structural formula is
One of them.
3. The process for producing a phosphorus-containing imidazole compound according to claim 1 or 2, comprising the steps of:
1) Performing a reaction between imidazole and p-hydroxybenzyl alcohol to obtain an intermediate;
2) Carrying out a reaction between the intermediate and an organic phosphorus compound to obtain a phosphorus-containing imidazole compound;
the molar ratio of the imidazole to the p-hydroxybenzyl alcohol in the step 1) is 1-2:1;
the reaction in the step 1) is carried out at the temperature of 90-120 ℃ for 2-6 h;
the molar ratio of the intermediate to the organic phosphorus compound in the step 2) is 1-3:1;
step 2) the organic phosphorus compound is one of diphenyl chlorophosphate, diphenyl phosphinyl chloride and phenylphosphonyl dichloride;
the reaction in the step 2) is carried out at room temperature, and the reaction time is 4-14 h.
4. An epoxy resin curing agent, characterized in that the composition comprises the phosphorus-containing imidazole compound according to claim 1 or 2.
5. An epoxy resin material characterized by comprising the phosphorus-containing imidazole compound according to claim 1 or 2.
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| JP2013124265A (en) * | 2011-12-13 | 2013-06-24 | Nippon Synthetic Chem Ind Co Ltd:The | Curing agent for epoxy resin |
| CN110746579A (en) * | 2019-11-20 | 2020-02-04 | 武汉理工大学 | Liquid-state phosphorus-containing imidazole flame-retardant latent curing agent and preparation method and application thereof |
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| JP2013124265A (en) * | 2011-12-13 | 2013-06-24 | Nippon Synthetic Chem Ind Co Ltd:The | Curing agent for epoxy resin |
| CN110746579A (en) * | 2019-11-20 | 2020-02-04 | 武汉理工大学 | Liquid-state phosphorus-containing imidazole flame-retardant latent curing agent and preparation method and application thereof |
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