CN113929717A - 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof - Google Patents
2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN113929717A CN113929717A CN202111200799.5A CN202111200799A CN113929717A CN 113929717 A CN113929717 A CN 113929717A CN 202111200799 A CN202111200799 A CN 202111200799A CN 113929717 A CN113929717 A CN 113929717A
- Authority
- CN
- China
- Prior art keywords
- flame
- compound
- epoxy resin
- aminopyrimidine
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 94
- 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 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 61
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- -1 tetraphenyl glycidyl Chemical group 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- JLBSVDZUWJLOCF-GTWSWNCMSA-N DDM-838 Chemical compound C1CCCNC(=O)C1NC(=O)CC(C)OC(=O)C(CCCCNC(=O)\C=C/CCCCCCCCCCCCCCCCC)NC(=O)C(N=1)(C)COC=1C1=CC=CC=C1O JLBSVDZUWJLOCF-GTWSWNCMSA-N 0.000 description 12
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- 238000005498 polishing Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YTLIXUAGIGBJAF-UHFFFAOYSA-N 6-hydroxybenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound C1=CC=C2P(O)(=O)OC3=CC=CC=C3C2=C1 YTLIXUAGIGBJAF-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Images
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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- 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
- C08K5/5333—Esters of phosphonic acids
- C08K5/5357—Esters of phosphonic acids cyclic
-
- 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
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)
- Epoxy Resins (AREA)
Abstract
The invention relates to a compound based on 2-aminopyrimidine, a flame-retardant epoxy resin material, and a preparation method and application thereof. The compound provided by the invention is shown as a formula (I):
the compound has high flame-retardant efficiency, can endow epoxy resin with excellent flame-retardant performance by low addition amount, and when the addition amount is 3-9 wt%, the UL94 combustion grade of the flame-retardant epoxy resin material is V-0, the limited oxygen index is more than 27.4%, and the flame-retardant performance is good. The compound is synthesized by reacting DOPO-OH and 2-aminopyrimidine, and its useThe raw materials of the preparation method are halogen-free and have small influence on the environment, the whole preparation process does not need a catalyst, and the preparation method is simple and easy to implement, low in toxicity and pollution and easy to industrialize.
Description
Technical Field
The invention belongs to the field of flame retardants, and more particularly relates to a compound based on 2-aminopyrimidine, a flame-retardant epoxy resin material, and a preparation method and application thereof.
Background
The epoxy resin is a three-dimensional cross-linked network-shaped cured product formed by an epoxy-containing oligomer and a curing agent, and contains a large number of polar groups, so that the resin has many excellent service properties such as adhesive property, solvent resistance, strength, corrosion resistance, dielectric property and the like, and is widely applied to the fields of functional coatings, automobiles, adhesives, printed circuit boards, electronic packaging, building materials, aerospace and the like. However, epoxy resin is easy to burn, releases a large amount of heat, smoke and harmful substances during burning, easily causes secondary combustion, brings great fire hazard to life and property safety, and limits popularization and use of epoxy resin. Therefore, the development of flame retardant epoxy resins is an effective means for solving the above problems, and has important practical significance.
There are generally two methods for imparting flame retardant properties to epoxy resins: firstly, the additive flame retardant is introduced into the epoxy resin through physical blending to realize the flame retardant property of the epoxy resin; and secondly, the reactive flame retardant is introduced into the epoxy resin through chemical bonds to realize the flame retardant property of the epoxy resin. Compared with the flame-retardant epoxy resin obtained by the former method, the flame-retardant epoxy resin obtained by the latter method has the advantages of stable performance, higher flame-retardant efficiency, smaller negative influence on the performance of the epoxy resin, and the like. In order to avoid harm to human health and ecological environment in the use process of the flame retardant, the development trend is to use the halogen-free environment-friendly flame retardant in the epoxy resin. In recent years, many studies on halogen-free environment-friendly flame retardants are made, including organic phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, phosphorus-nitrogen synergistic flame retardants, multi-element synergistic flame retardants, nano composite flame retardants, and the like. The phosphorus-nitrogen synergistic flame retardant is greatly researched due to good synergistic flame retardant effect and flexible diversity of structural design. The flame retardant can simultaneously play a flame retardant role in a gas phase and a condensed phase.
The existing flame retardant applied to epoxy resin has the problems of large addition amount and low flame retardant efficiency. For part of flame retardants, the problems of use of harmful raw materials, solvents and catalysts, high synthesis difficulty, complex synthesis process and the like exist. If environment-friendly raw materials, solvents and catalysts can be adopted and a simple synthesis process is adopted, a high-efficiency halogen-free environment-friendly flame retardant is developed, so that the flame retardant can be better applied to epoxy resin.
The 2-aminopyrimidine is a water-soluble compound with high nitrogen content. Patent CN109467574A discloses a vanillin-based reactive flame retardant, and preparation and application thereof, and specifically relates to a flame retardant formed by covalent bonds by utilizing the reactivity of primary amino groups on 2-aminopyrimidine, but the addition amount of the flame retardant needs to reach 12%, and the flame retardant level of epoxy resin can reach UL-94V-0. 10-hydroxy-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH) is a water-soluble organic phosphonic acid, and the molecule of the organic phosphonic acid contains DOPO (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) flame retardant groups with higher flame retardant efficiency. Regarding the research on the application of the DOPO derivative in the flame retardant, the patent CN110590849A discloses a phosphorus-nitrogen-containing DOPO derivative flame retardant, and a preparation method and application thereof, and specifically, the flame retardant utilizes the flame retardant property of the DOPO group and the synergistic flame retardant effect of phosphorus and nitrogen, but the DOPO group and the phosphorus and nitrogen are added into a polymer, the oxygen index of the obtained polymer is 23-25%, and the flame retardant property is general.
Therefore, it is important to develop a flame retardant for epoxy resin applications, which has high flame retardant efficiency and can impart excellent flame retardant properties to epoxy resins with a low addition amount.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of low flame-retardant efficiency and high addition amount of the existing epoxy resin flame retardant, and provides a compound based on 2-aminopyrimidine. The compound has high flame-retardant efficiency, and can endow epoxy resin with excellent flame-retardant performance by low addition amount.
The invention also aims to provide a preparation method of the compound, the compound is synthesized by reacting DOPO-OH and 2-aminopyrimidine, and the preparation method has the characteristics of environment-friendly raw materials and simple synthesis process.
The invention also aims to provide the application of the compound as a flame retardant in preparing resin materials.
Another object of the present invention is to provide a flame retardant epoxy resin material.
The invention also aims to provide a preparation method of the flame-retardant epoxy resin material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a 2-aminopyrimidine-based compound having the structure shown in formula (i):
in the compound, a DOPO group and 2-aminopyrimidine are combined in an ionic bond mode, an O atom of a P ═ O bond in the DOPO group and a primary amino group in the 2-aminopyrimidine are combined in a hydrogen bond mode, the compound has a good synergistic flame retardant effect of phosphorus and nitrogen, and simultaneously the compound plays a flame retardant role when the gas phase and the condensation are the same, so that the compound has high flame retardant efficiency, and the epoxy resin can be endowed with excellent flame retardant performance by low addition amount.
Specifically, the compound is crystal, the microscopic melting point of the compound is 130-135 ℃, and the primary amino group and the charged group of the compound can participate in the curing of the epoxy resin.
The preparation method of the compound is also within the protection scope of the invention, and comprises the following steps: dissolving DOPO-OH and 2-aminopyrimidine, stirring for reaction at 20-35 ℃, and then stirring for reaction at 50-100 ℃ to obtain the compound. Wherein the stirring reaction at 20-35 ℃ is to avoid the reaction from being too violent in the initial stage of the reaction, and the stirring reaction at 50-100 ℃ is to ensure the reaction to be complete. The raw materials used in the method are halogen-free and have small influence on the environment, the whole preparation process does not need a catalyst, and the method is simple and easy to implement, low in toxicity and pollution and easy to industrialize.
Preferably, the molar ratio of DOPO-OH to 2-aminopyrimidine is 1 (0.9-1.1).
Preferably, the stirring reaction time at 20-35 ℃ is 1-4 h.
Preferably, the stirring reaction time at 50-100 ℃ is 4-10 h.
Preferably, after the reaction is completed, the method further comprises the steps of spin-drying the solvent and then recrystallizing to obtain the compound.
Specifically, the DOPO-OH and the 2-aminopyrimidine are dissolved in deionized water, stirred and reacted for 1-4 hours at the temperature of 20-35 ℃, then stirred and reacted for 4-10 hours at the temperature of 50-100 ℃, and then the reaction liquid is rotated to a non-flowing state through rotary evaporation. Then adding ethyl acetate and absolute ethyl alcohol respectively at 80 ℃ to enable the ethyl acetate and the absolute ethyl alcohol to be just dissolved, cooling and standing, separating out crystals, filtering to obtain light yellow crystals, and drying in vacuum to obtain the product.
The application of the compound as a flame retardant in the preparation of resin materials is also within the protection scope of the invention.
The flame-retardant epoxy resin material comprises the following components in parts by weight:
74-80 parts of epoxy monomer,
3 to 9 parts of the above-mentioned compound,
16-21 parts of a co-curing agent.
The weight percentage of the compound in the flame-retardant epoxy resin material is 3-9%, and the epoxy resin material can have excellent flame-retardant performance by adding the compound. The flame-retardant epoxy resin material has a UL94 combustion rating of V-0 and a limited oxygen index of more than 27.4%.
Epoxy monomers and co-curing agents conventional in the art may be used in the present invention.
Preferably, the epoxy monomer is one or more of bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A glycidyl ether, tetraphenyl glycidyl ether ethane or phenol novolac polyglycidyl ether; the co-curing agent is one or more of 4,4 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone, m-phenylenediamine, diethylenetriamine or triethylene tetramine.
The preparation method of the flame-retardant epoxy resin material is also within the protection scope of the invention and comprises the following steps: and mixing and dissolving the 2-aminopyrimidine-based compound, the epoxy monomer and the co-curing agent, and thermally curing to obtain the flame-retardant epoxy resin material.
Preferably, the dissolving temperature is 120-150 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the compound, a DOPO group and 2-aminopyrimidine are combined in an ionic bond form, so that the compound has a good synergistic flame retardant effect of phosphorus and nitrogen, and simultaneously plays a flame retardant role when the gas phase and the condensation are the same, so that the compound has high flame retardant efficiency, and can endow epoxy resin with excellent flame retardant performance by low addition amount.
(2) The raw materials for preparing the compound are halogen-free and have small influence on the environment, the whole preparation process does not need a catalyst, and the compound is simple and easy to implement, low in toxicity and pollution and easy to industrialize.
(3) The compound is added into an epoxy resin material as a flame retardant, the addition amount of the compound is 3-9 wt%, the UL94 combustion grade of the obtained flame-retardant epoxy resin material is V-0, the limited oxygen index is more than 27.4%, and the flame-retardant performance is good.
Drawings
FIG. 1 is a structural diagram of an X-ray single crystal of a compound provided in example 1 of the present invention.
FIG. 2 is a high resolution mass spectrum of the compound provided in example 1 of the present invention.
FIG. 3 is a drawing of a compound provided in example 1 of the present invention31P NMR spectrum.
Detailed Description
The present invention will be further described with reference to examples and comparative examples. These examples are merely representative descriptions of the present invention, but the present invention is not limited thereto. The test methods used in the following examples and comparative examples are, unless otherwise specified, conventional methods, and the raw materials, reagents and the like used are, unless otherwise specified, commercially available raw materials and reagents.
Example 1
This example provides a 2-aminopyrimidine based compound. The preparation method of the compound comprises the following steps: adding 0.06mol of DOPO-OH and 0.06mol of 2-aminopyrimidine into a 250mL single-neck round-bottom flask, adding 100mL of deionized water, stirring until the solid is dissolved, stirring at room temperature for reaction for 2h, heating to 100 ℃, and stirring for reaction for 9 h. After the reaction solution was spun to a non-flowable state by rotary evaporation, 50mL of ethyl acetate was added to the flask at 80 ℃ and then absolute ethanol was gradually added until the solution became just clear. The solution is cooled and kept stand, crystals are separated out, filtered, dried in vacuum for 24 hours at 65 ℃ and ground to obtain the compound powder based on the 2-aminopyrimidine. The synthetic route is as follows:
the structure of an X-ray single crystal of the 2-aminopyrimidine-based compound prepared in this example is shown in FIG. 1, confirming that the structure is shown below:
main crystal data: molecular formula C32H28N6O6P2(ii) a Molecular weight, 654.54; crystal system, triclinic system; space group, P-1;
α＝105.1700(10)°,β＝99.1110(10)°,γ＝100.8820(10)°；
Z＝2；ρcalc＝1.470g/cm3；Index ranges,-7≤h≤8,-15≤k≤13,-24≤l≤21；μ＝1.829mm-1；Crystal size,0.2×0.15×0.05mm3；Radiation,CuKα(λ＝1.54184)；F(000)＝680.0；2θrange for data collection,7.424-148.472°；Goodness-of-fit on F2＝1.058；Reflections collected,14621；Independent reflections,5787[Rint＝0.0273,Rsigma＝0.0251；Data/restraints/parameters,5787/0/423；Final R indexes(all data),R1＝0.0390,wR2＝0.1067；Final R indexes[I>2σ(I)],R1＝0.0378,wR2＝0.1055；Largest diff.peak and hole,
0.42,-0.54。
2-Ammonia-based catalyst prepared in this exampleThe high resolution mass spectrum of the pyrimidine-based compound is shown in FIG. 2, which shows [ M + H ] at 328.0850]+Molecular ion peak, which is consistent with the theoretical molecular weight of the compound, 327.0773.
Preparation of 2-aminopyrimidine-based Compounds prepared in this example31The P NMR spectrum is shown in fig. 3, with a single signal peak at +5.40ppm, indicating that the target compound was successfully prepared and has a higher purity.
Example 2
The embodiment provides a flame-retardant epoxy resin material, which consists of the following components: the weight percentage of 2-aminopyrimidine based compound, DDM and bisphenol a glycidyl ether resin was 3: 18.15:78.15, at 140 ℃, putting the compound into bisphenol A glycidyl ether resin, stirring until the compound is dissolved, then adding DDM, stirring until the DDM is dissolved, pouring into a mold, curing for 2h at 80 ℃ and curing for 4h at 150 ℃, cooling, demolding and polishing to obtain the flame-retardant epoxy resin. The flame-retardant epoxy resin had a UL94 flame rating of V-0(130 mm. times.13 mm. times.3.2 mm) and a limiting oxygen index of 27.4% (150 mm. times.6.5 mm. times.3 mm).
Example 3
The embodiment provides a flame-retardant epoxy resin material, which consists of the following components: the weight percentage of 2-aminopyrimidine based compound, DDM and bisphenol a glycidyl ether resin was 6: and 17.52:76.48, at the temperature of 140 ℃, putting the compound into bisphenol A glycidyl ether resin, stirring until the compound is dissolved, then adding DDM, stirring until the DDM is dissolved, pouring into a mold, curing at the temperature of 80 ℃ for 2 hours, curing at the temperature of 150 ℃ for 4 hours, cooling, demolding, and polishing to obtain the flame-retardant epoxy resin. The flame-retardant epoxy resin had a UL94 flame rating of V-0(130 mm. times.13 mm. times.3.2 mm) and a limiting oxygen index of 31.9% (150 mm. times.6.5 mm. times.3 mm).
Example 4
The embodiment provides a flame-retardant epoxy resin material, which consists of the following components: the weight percentage of 2-aminopyrimidine based compound, DDM and bisphenol a glycidyl ether resin was 9: 16.19:74.81, at 140 ℃, putting the compound into bisphenol A glycidyl ether resin, stirring until the compound is dissolved, then adding DDM, stirring until the DDM is dissolved, pouring into a mould, curing for 2h at 80 ℃ and curing for 4h at 150 ℃, cooling, demoulding and polishing to obtain the flame-retardant epoxy resin. The flame-retardant epoxy resin had a UL94 flame rating of V-0(130 mm. times.13 mm. times.3.2 mm) and a limiting oxygen index of 33.9% (150 mm. times.6.5 mm. times.3 mm).
Comparative example 1
The embodiment provides an epoxy resin material, which consists of the following components: the weight percentage of DDM and bisphenol A glycidyl ether resin is 20.18:79.82, the DDM is put into the bisphenol A glycidyl ether resin at 140 ℃, stirred until the DDM is dissolved, poured into a mould, cured for 2h at 80 ℃ and cured for 4h at 150 ℃, cooled, demoulded and polished to obtain the epoxy resin. The epoxy resin was extremely flammable, had no UL94 flame rating (130 mm. times.13 mm. times.3.2 mm) and had a limiting oxygen index of 22.8% (150 mm. times.6.5 mm. times.3 mm).
As can be seen from the comparative analysis of examples 2-4 and comparative example 1 above, the epoxy resin was extremely flammable without the addition of a flame retardant. When a 2-aminopyrimidine-based compound is added as a flame retardant to an epoxy resin, the epoxy resin can achieve the highest UL94 burning rating when the 2-aminopyrimidine-based compound is added in an amount of 3%, the UL94 burning rating is V-0(130 mm. times.13 mm. times.3.2 mm), the limiting oxygen index is 27.4% (150 mm. times.6.5 mm. times.3 mm), and the limiting oxygen index of the epoxy resin is further increased with the increase of the 2-aminopyrimidine-based compound. Therefore, the 2-aminopyrimidine is used as a flame retardant to be added into an epoxy resin material, so that the flame retardant efficiency is high, and the epoxy resin can be endowed with excellent flame retardant performance by a low addition amount.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A 2-aminopyrimidine-based compound having the structure shown in formula (i):
2. a process for the preparation of a compound according to claim 1, comprising the steps of: dissolving DOPO-OH and 2-aminopyrimidine, stirring for reaction at 20-35 ℃, and then stirring for reaction at 50-100 ℃ to obtain the compound.
3. The method according to claim 2, wherein the molar ratio of DOPO-OH to 2-aminopyrimidine is 1 (0.9 to 1.1).
4. The preparation method of claim 2, wherein the stirring reaction at 20-35 ℃ is carried out for 1-4 h.
5. The preparation method according to claim 2, wherein the reaction time at 50-100 ℃ is 4-10 h.
6. The method according to claim 2, further comprising a step of spin-drying the solvent and then recrystallizing to obtain the compound after completion of the reaction.
7. Use of the compound of claim 1 as a flame retardant in the preparation of a resin material.
8. The flame-retardant epoxy resin material is characterized by comprising the following components in parts by weight:
74-80 parts of epoxy monomer,
3 to 9 parts of the compound according to claim 1,
16-21 parts of a co-curing agent.
9. The flame retardant epoxy resin material according to claim 8, wherein the epoxy monomer is one or more of bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A glycidyl ether, tetraphenyl glycidyl ether ethane or phenol novolac polyglycidyl ether; the co-curing agent is one or more of 4,4 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone, m-phenylenediamine, diethylenetriamine or triethylene tetramine.
10. The method for preparing the flame-retardant epoxy resin material as claimed in any one of claims 8 to 9, which is characterized by comprising the following steps: and (2) mixing and dissolving a compound based on 2-aminopyrimidine, an epoxy monomer and a co-curing agent, and thermally curing to obtain the flame-retardant epoxy resin material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200799.5A CN113929717A (en) | 2021-10-14 | 2021-10-14 | 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111200799.5A CN113929717A (en) | 2021-10-14 | 2021-10-14 | 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113929717A true CN113929717A (en) | 2022-01-14 |
Family
ID=79279594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111200799.5A Pending CN113929717A (en) | 2021-10-14 | 2021-10-14 | 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113929717A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116903546A (en) * | 2023-09-13 | 2023-10-20 | 浙江华宇钠电新能源科技有限公司 | Sodium ion battery pack with fire extinguishing function and vehicle |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467926A (en) * | 2013-09-24 | 2013-12-25 | 北京工商大学 | Phosphor-nitrogen halogen-free flame-retardant epoxy resin |
| CN104812838A (en) * | 2012-11-28 | 2015-07-29 | 胜技高分子株式会社 | Flame-retardant polybutylene terephthalate resin composition, and molded product thereof |
| US20190382427A1 (en) * | 2016-11-23 | 2019-12-19 | Xiamen University | Preparation method of phosphaphenanthrene-structure reactive flame retardant and application thereof |
-
2021
- 2021-10-14 CN CN202111200799.5A patent/CN113929717A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104812838A (en) * | 2012-11-28 | 2015-07-29 | 胜技高分子株式会社 | Flame-retardant polybutylene terephthalate resin composition, and molded product thereof |
| CN103467926A (en) * | 2013-09-24 | 2013-12-25 | 北京工商大学 | Phosphor-nitrogen halogen-free flame-retardant epoxy resin |
| US20190382427A1 (en) * | 2016-11-23 | 2019-12-19 | Xiamen University | Preparation method of phosphaphenanthrene-structure reactive flame retardant and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116903546A (en) * | 2023-09-13 | 2023-10-20 | 浙江华宇钠电新能源科技有限公司 | Sodium ion battery pack with fire extinguishing function and vehicle |
| CN116903546B (en) * | 2023-09-13 | 2023-12-15 | 浙江华宇钠电新能源科技有限公司 | Sodium ion battery pack with fire extinguishing function and vehicle |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101597308B (en) | Preparation method of hexaaniline cyclotriphosphazene and non-halogen flame retardant epoxy resin composition | |
| CN110510605B (en) | Nitrogen-rich group functionalized graphene, and preparation method and application thereof | |
| CN113234103B (en) | Phosphazene flame retardant, preparation method and application thereof | |
| Zhang et al. | Environment-friendly synthesis and performance of a novel hyperbranched epoxy resin with a silicone skeleton | |
| US20090258997A1 (en) | Novel phosphorus-containing compounds and their preparing process and use | |
| CN102838778A (en) | Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof | |
| CN105255109A (en) | Phthalonitrile modified benzoxazine and epoxy resin composite material, preparation and application | |
| CN104086751A (en) | DOPO-based symtriazine ring hydrogenated benzimidazole epoxy curing agent and preparation method thereof | |
| TW200936602A (en) | Manufacture of advanced epoxy resins and their high Tg thermosets for electronic applications | |
| CN109467574B (en) | Reactive flame retardant based on vanillin as well as preparation and application thereof | |
| TWI460186B (en) | Phosphinated amino and phenolic-containing multifunctional epoxy curing agents and their preparation and use | |
| CN103044708A (en) | High-efficiency N/P flame retardant, as well as preparation method and application thereof | |
| EP0099268B1 (en) | Process for producing polymaleimide | |
| CN109651825A (en) | A kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen and the preparation method and application thereof | |
| CN112210191B (en) | Method for modifying epoxy resin through phosphorus/nitrogen/silicon synergistic flame retardation | |
| CN103012847A (en) | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant | |
| CN113929717A (en) | 2-aminopyrimidine-based compound, flame-retardant epoxy resin material, and preparation method and application thereof | |
| CN113248789B (en) | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin | |
| CN107663278B (en) | A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof | |
| CN111560112B (en) | Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin | |
| Liu et al. | Preparation and characterization of phosphorus‐containing Mannich‐type bases as curing agents for epoxy resin | |
| CN105295092B (en) | A kind of phosphorous, nitrogen luxuriant molysite fire retardant and its preparation method and application | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN103421192B (en) | Phosphorous benzoxazine colophony and composition | |
| CN113429629B (en) | Schiff-HCCP flame retardant, preparation method thereof and modified epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |