CN115340574A - 一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 - Google Patents
一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 Download PDFInfo
- Publication number
- CN115340574A CN115340574A CN202211057311.2A CN202211057311A CN115340574A CN 115340574 A CN115340574 A CN 115340574A CN 202211057311 A CN202211057311 A CN 202211057311A CN 115340574 A CN115340574 A CN 115340574A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- epoxy resin
- retardant
- reactive flame
- flame
- 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 91
- 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 87
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 26
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- 238000000576 coating method Methods 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004100 electronic packaging Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000004786 cone calorimetry Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 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
- 239000001301 oxygen Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 101000869866 Emys orbicularis Beta-defensin 1 Proteins 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- C07F9/657172—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 one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
-
- 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
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- 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
- C08G59/68—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 catalysts used
- C08G59/688—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 catalysts used containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用。反应型阻燃剂的制备包括如下步骤：将2,4,6‑三氨基嘧啶和苯甲醛溶解在有机溶剂中，在80～100℃下反应，得到均匀淡黄色液体；反应体系冷却至室温后，加入DOPO并升温至120～140℃搅拌反应3～5h，得到均匀橘红色液体；将得到的橘红色液体减压蒸馏，得到淡黄色粉末固体；将淡黄色粉末真空干燥，除去剩余的有机溶剂，即得到所述反应型阻燃剂(记为TBD)。本发明提供的反应型阻燃剂与环氧树脂有很好的相容性，能赋予环氧树脂优异的阻燃性能，环氧树脂的阻燃性能与力学性能均有较大的提升。无需催化剂，原料简单，工艺简单易行，低毒低污染，易于工业化。
Description
技术领域
本发明属于环氧树脂阻燃技术领域，尤其涉及一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用。
背景技术
限制环氧树脂在实际应用中使用的主要因素之一是其高可燃性，然而，随着人们对环保问题的日益重视，含卤阻燃剂的弊端已得到深刻认识。有机卤素化合物在高温下可转化为有毒的二恶英。同时，这些有毒有害物质不能被生物降解，会导致它们暴露在环境中并在生物体内蓄积，对环境和健康造成极大危害。因此，为适应环保要求，无卤阻燃剂相关研究的重要性日益凸显。
近年来，DOPO的研究在环氧树脂无卤阻燃剂的研究中最为突出，由于其特殊的磷杂菲DOPO的结构赋予环氧树脂良好的耐热性和阻燃性。同时，分子中的活性P-H键可以参与反应获得含有不同官能团的衍生物。然而，单一的仅含磷元素的基于DOPO的阻燃剂需要大量添加以确保优异的阻燃性。因此，其他元素已被引入磷化合物的分子结构中以提高阻燃性能，包括氮、硫、硅、硼。DOPO及相关衍生物与其他元素具有令人满意的相互促进作用，在保证阻燃性能的前提下减少了阻燃添加剂的用量。
然而，在大多数情况下，阻燃剂的加入带来了优异的阻燃效果，同时对其他性能产生了不利影响，如机械性能急剧恶化和耐热性下降，这将限制材料的应用范围。因此，合成一种高效的环氧树脂阻燃剂对于在保持环氧树脂优良的机械性能的同时提高阻燃性具有重要意义。
发明内容
针对上述现有技术问题，本发明的目的在于提供一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用。本发明提供了一种基于2,4,6-三氨基嘧啶的反应型阻燃剂及其在环氧树脂中的应用，本发明阻燃剂具有原料毒性小、价格便宜、合成单体来源广泛、阻燃效率高，本发明制备方法简单易行，便于工业化生产，同时制备过程中使用的溶剂无毒，气味小，可回收利用。阻燃剂能使环氧树脂达到很好的阻燃性能，且能降低环氧树脂燃烧过程中的热释放速率，并能增强环氧树脂的力学性能。
本发明的目的通过以下技术方案实现：
一种反应型阻燃剂，其化学结构式如下：
上述反应型阻燃剂的制备方法，包括如下步骤：
(1)将2,4,6-三氨基嘧啶和苯甲醛溶解在有机溶剂中，在80～100℃下搅拌反应4～6h，得到均匀淡黄色液体；
(2)待步骤(1)反应体系冷却至室温后，加入DOPO并升温至120～140℃搅拌反应3～5h，得到均匀橘红色液体；
(3)将步骤(2)中得到的橘红色液体减压蒸馏，得到淡黄色粉末固体；
(4)将步骤(3)中淡黄色粉末真空干燥，除去剩余的有机溶剂，即得到所述反应型阻燃剂。
优选的，步骤(1)所述2,4,6-三氨基嘧啶和苯甲醛与步骤(2)所述DOPO的摩尔比为1:(2.8～3.2):(2.9～3.1)。
优选的，步骤(1)所述有机溶剂为DMF、四氢呋喃、二氧六环和丙酮中的至少一种。
优选的，步骤(3)所述减压蒸馏的方式为：采用旋转蒸发仪，在125℃下以80rpm的旋转速度蒸发。
优选的，步骤(3)所述减压蒸馏的时间为1～2h。
优选的，步骤(4)所述真空干燥的温度为100～110℃，真空干燥的时间为10～12h。
一种阻燃环氧树脂，其由包含如下质量份的组分制备得到：100份双酚F环氧树脂、8～10份所述反应型阻燃剂和29～31份固化剂。
优选的，所述双酚F环氧树脂的环氧值为0.58～0.6。
优选的，所述固化剂为4.4'-二氨基二苯基甲烷(DDM)、DDS(二氨基二苯基砜)、2-甲基咪唑和双氰胺中的至少一种。
所述阻燃环氧树脂的制备方法，包括如下步骤：先将环氧树脂加热至120～150℃，再加入上述反应型阻燃剂，并混合均匀，然后冷却至温度为70～90℃，再加入固化剂，混合均匀后真空脱泡，再依次进行浇注模具，先在80～90℃下保温2-3h，再在120～130℃下保温2-3h，最后在150～160℃下保温5-6h，自然冷却后，制得所述阻燃环氧树脂。
上述阻燃环氧树脂在装饰涂料、轨道交通和电子封装方面的应用。
本发明的反应原理为：反应的第一步是通过2,4,6-三氨基嘧啶的氨基和苯甲醛中的活性羰基缩合生成含有-C＝N-双键的席夫碱，第二部是用第一步得到的席夫碱和DOPO中的活泼-P-H-键发生加成反应，最后得到目标产物。选择2,4,6-三氨基嘧啶的原因有两点：1.最后得到的目标产物是一种对称结构，具有较好的热稳定性；2.作为一种富氮杂环，可以有效降低产物中磷的含量，进一步提高热稳定性。
与现有技术相比，本发明的有益效果包括：
(1)本发明合成的一种基于2,4,6-三氨基嘧啶的阻燃剂比传统卤素阻燃剂环保，无污染，无腐蚀性气体产生，反应条件易控制，反应过程无危险产物生成，阻燃效率更高。
(2)本发明的阻燃环氧树脂可根据阻燃要求的不同，通过改变阻燃剂添加量，制备得到不同情况下使用的阻燃环氧树脂，有利于节省成本。
(3)本发明的阻燃剂包含的-NH-化学键能与环氧树脂的环氧基反应，与环氧树脂有很好的结合性，且阻燃剂的结构中有较高的磷含量和较多的芳构型碳，阻燃剂的对称结构使其具有更高的热稳定性。
(4)本发明合成的阻燃环氧树脂过程设备简单，步骤简单，无高温高压，制备过程安全，原料无有害物质，工业化生产价值高。
(5)本发明合成的阻燃环氧树脂由于具有多苯环的刚性结构，其力学性能相较于纯树脂有很大提高。在低添加量下，TBD可以催化环氧树脂的固化反应，从而提高交联密度，提高环氧树脂的力学性能。
附图说明
图1为对比例1制备所得的纯环氧树脂EP锥形量热后的残碳拉曼光谱图。
图2为实施例4制备的阻燃环氧树脂EP/TBD锥形量热后的残碳拉曼光谱图。
图3为对比例1制备所得的纯环氧树脂EP锥形量热测试后的数码照片图。
图4为实施例4制备的阻燃环氧树脂EP/TBD锥形量热测试后的数码照片图。
图5为对比例1制备所得的纯环氧树脂EP锥形量热测试后的残碳扫描电镜图。
图6为实施例4制备的阻燃环氧树脂EP/TBD锥形量热测试后的残碳扫描电镜图。
图7为实施例1的目标产物的元素含量与计算含量对比数据。
图8为实施例2的目标产物的元素含量与计算含量对比数据。
图9为实施例3的目标产物的元素含量与计算含量对比数据。
图10为实施例1制备的产物TBD、苯甲醛、2,4,6-三氨基嘧啶和DOPO的红外光谱图对比图。
图11为本发明实施例的化学反应式示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例所述的双酚F环氧树脂购买于荷兰皇家壳牌集团，环氧当量为158～172g/mol。
所述旋转蒸发仪购买于郑州长城科工贸有限公司，型号为R-1001VN。
实施例1
一种反应型阻燃剂的制备方法，步骤如下：
(1)将0.05mol 2,4,6-三氨基嘧啶和0.15mol苯甲醛加入到250mL三颈烧瓶中，再加入70mL DMF溶剂，搅拌至固体溶解后，升温至100℃搅拌反应6h，得到均匀淡黄色液体。
(2)待反应体系冷却至室温后，加入0.15mol DOPO升温至120℃搅拌反应3h，得到均匀橘红色液体；
(3)液体在旋转蒸发仪中减压蒸馏1h，得到淡黄色粉末固体；
(4)将淡黄色粉末放置于真空烘箱中除去剩余的DMF溶剂，温度调节为100℃，设定10h，即得到所述阻燃剂，记为TBD。
实施例2
一种反应型阻燃剂的制备方法，步骤如下：
(1)将0.05mol 2,4,6-三氨基嘧啶和0.14mol苯甲醛加入到250mL三颈烧瓶中，再加入70mL DMF溶剂，搅拌至固体溶解后，升温至100℃搅拌反应6h，得到均匀淡黄色液体。
(2)待反应体系冷却至室温后，加入0.145mol DOPO升温至120℃搅拌反应3h，得到均匀橘红色液体；
(3)液体在旋转蒸发仪中减压蒸馏1h，得到淡黄色粉末固体；
(4)将淡黄色粉末放置于真空烘箱中除去剩余的DMF溶剂，温度调节为100℃，设定10h，即得到所述阻燃剂。
实施例3
一种反应型阻燃剂的制备方法，步骤如下：
(1)将0.05mol 2,4,6-三氨基嘧啶和0.16mol苯甲醛加入到250mL三颈烧瓶中，再加入70mL DMF溶剂，搅拌至固体溶解后，升温至100℃搅拌反应6h，得到均匀淡黄色液体。
(2)待反应体系冷却至室温后，加入0.155mol DOPO升温至120℃搅拌反应3h，得到均匀橘红色液体；
(3)液体在旋转蒸发仪中减压蒸馏1h，得到淡黄色粉末固体；
(4)将淡黄色粉末放置于真空烘箱中除去剩余的DMF溶剂，温度调节为100℃，设定10h，即得到所述阻燃剂。
实施例4
一种阻燃环氧树脂的制备方法，步骤如下：
原料组成为：双酚F环氧树脂、实施例1制备的阻燃剂和固化剂DDM的质量比为100:10:29。
先将双酚F环氧树脂加热至140℃，再加入上述反应型阻燃剂，并混合均匀，然后冷却至温度为80℃，再加入固化剂，混合均匀后真空脱泡10min，再依次进行浇注模具，先在90℃下保温2h，再在120℃下保温2h，最后在150℃下保温6h，自然冷却后，制得所述阻燃环氧树脂，样品记为EP/TBD。
实施例5
一种阻燃环氧树脂的制备方法，步骤如下：
原料组成为：双酚F环氧树脂、实施例2制备的阻燃剂和固化剂DDM的质量比为100:8:30。
先将双酚F环氧树脂加热至140℃，再加入上述反应型阻燃剂，并混合均匀，然后冷却至温度为80℃，再加入固化剂，混合均匀后真空脱泡10min，再依次进行浇注模具，先在90℃下保温2h，再在120℃下保温2h，最后在150℃下保温6h，自然冷却后，制得所述阻燃环氧树脂，样品记为EP/TBD-1。
实施例6
一种阻燃环氧树脂的制备方法，步骤如下：
原料组成为：双酚F环氧树脂、实施例3制备的阻燃剂和固化剂DDM的质量比为100:9:31。
先将双酚F环氧树脂加热至140℃，再加入上述反应型阻燃剂，并混合均匀，然后冷却至温度为80℃，再加入固化剂，混合均匀后真空脱泡10min，再依次进行浇注模具，先在90℃下保温2h，再在120℃下保温2h，最后在150℃下保温6h，自然冷却后，制得所述阻燃环氧树脂，样品记为EP/TBD-2。
对比例1
纯环氧树脂的制备方法，步骤如下：
向100g的双酚F环氧树脂中加入29g的固化剂DDM，机械搅拌均匀后在真空下脱泡10min，最后将其倒入模具中，先在90℃下保温2h，再在120℃下保温2h，最后在150℃下保温6h，自然冷却后，样品记为EP。
图1为对比例1制备所得的纯环氧树脂EP锥形量热后的残碳拉曼光谱图。图2为实施例4制备的阻燃环氧树脂EP/TBD锥形量热后的残碳拉曼光谱图。
采用拉曼光谱仪表征碳质材料的石墨化程度，可以看到两个光谱图均在1360cm-1和1590cm-1处出现峰形，分别为D带和G带。D带和G带分别为无定形碳的振动和有序碳的振动。而残炭的石墨化程度可以通过两个谱带的积分强度比(R＝ID/IG)来进行评估。很明显R值越高，残炭的石墨化程度也就越低。D和G是先确定EP曲线的峰值，然后用origin对两个峰值进行匹配分峰拟合操作得到的，fitting曲线是拟合后的EP曲线，和曲线EP几乎重合。
两个谱带的积分强度比(ID/IG)可以表征炭层的石墨化程度，较低的ID/IG值表示较高的石墨化程度。EP/TBD试样残炭的ID/IG值(2.09)比纯EP试样残炭的ID/IG值(2.52)低得多，这表明TBD的添加提高了炭层的石墨化程度。这意味着阻燃环氧树脂在燃烧过程中能形成更加热稳定的炭层。
图3为对比例1制备所得的纯环氧树脂EP锥形量热测试后的数码照片图。图4为实施例4制备的阻燃环氧树脂EP/TBD锥形量热测试后的数码照片图。从图3～4可以看出，纯环氧树脂EP基本已经燃烧殆尽，只有极小的残炭残留。而EP/TBD的残炭是蓬松的，有利于阻碍燃烧。
图5为对比例1制备所得的纯环氧树脂EP锥形量热测试后的残碳扫描电镜图。图6为实施例4制备的阻燃环氧树脂EP/TBD锥形量热测试后的残碳扫描电镜图。在图5中纯EP的SEM图像中可以清楚地观察到断裂、穿孔和沟槽表面。残炭表面的缺陷降低了炭层的稳定性，导致阻燃性能下降。随着TBD的加入，从图6可以看出残渣表面变得致密和完整，这对阻碍环氧树脂燃烧起到了重要作用。
表1为对比例1和实施例4～6制备得到的产物的锥形量热(采用英国FTT公司，型号0007锥形量热仪)的数据，从表1可以看出：EP的点火时间(TTI)为28s，而EP/TBD的TTI增加到66s，表明TBD阻燃剂改性树脂后可以增加环氧树脂的点燃时间。此外，峰值放热率(PHRR)从EP的1395.6kW/m2降低到EP/TBD的1063.2kW/m2。同样，总放热量(THR)从EP的75.0MJ/m2下降到EP/TBD的50.7MJ/m2，降低了33％，平均有效燃烧热(av-EHC)也从22.6MJ/kg下降至17.7MJ/kg。这些参数都表明改性环氧树脂的阻燃性得到了很大的提高。
表1锥形量热数据
表2为对比例1和实施例4～6制备得到的产物的极限氧指数(LOI)统计数据，从表2可以看到，TBD改性后，LOI有大幅度提高，表明环氧树脂的阻燃性变好。
表2极限氧指数(LOI)数据
表3为对比例1和实施例4～6制备得到的产物的力学性能数据，弯曲强度和模量参考GB/T 2567-1995。从表3可以发现：EP/TBD的弯曲强度和模量，分别比EP高102.1％和3.4％，这表明磷/氮协同(2,4,6-三氨基嘧啶中含有N元素)也可以提高环氧树脂的韧性。
元素分析计算值是通过实施例1的化学反应方程式比例计算各种元素相对原子质量得到的，实验室是通过以下仪器对实施例进行测试得到的：
Vario EL cube Elemental Analyzer(Elementar,德国)用于分析实施例制备的产物TBD中的元素含量(C,H,N,P)。在该测试中使用了20mg TBD粉末。
为了确认TBD的化学结构，对元素含量进行了分析。结果如图7所示：C，70.13％；H，4.41％；N，6.78％；P，9.41％。计算值：C，70.59％；H，4.44％；N，6.75％；P，9.35％。它清楚地表明TBD的元素含量分析值与计算值基本一致。这也证明TBD的成功合成。
同样的方法对实施例2制备的产物的化学结构进行元素分析，其结果见图8：C，70.08％；H，4.11％；N，6.44％；P，9.03％。计算值：C，70.59％；H，4.44％；N，6.75％；P，9.35％。它清楚地表明样品的元素含量分析值与计算值基本一致。这也证明目标产物的成功合成。
同样的方法对实施例3制备的产物的化学结构进行元素分析，其结果见图9：C，70.65％；H，4.48％；N，6.82％；P，9.67％。计算值：C，70.59％；H，4.44％；N，6.75％；P，9.35％。它清楚地表明样品的元素含量分析值与计算值基本一致。这也证明目标产物的成功合成。
图10为实施例1制备的产物TBD、苯甲醛、2,4,6-三氨基嘧啶和DOPO的红外光谱图对比图。从图10可以看出：苯甲醛中对应C＝O的吸收峰1700cm-1和DOPO中对应的P-H的2430cm-1吸收峰在TBD的谱图中消失，表明苯甲醛与DOPO均参与了反应，此外，DOPO中的主要特征吸收峰1230cm-1(P＝O)和754cm-1(P-C)依旧出现在TBD谱图中。此外，2,4,6-三氨基嘧啶中对应的嘧啶环特征吸收峰1500cm-1仍在TBD曲线中保留下来。这些都表明了TBD的成功合成。
以上所述本发明的具体实施方式，并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形，均应包含在本发明权利要求的保护范围内。
Claims (10)
1.一种反应型阻燃剂，其特征在于，具有如下的化学结构式：
2.权利要求1所述一种反应型阻燃剂的制备方法，其特征在于，包括如下步骤：
(1)将2,4,6-三氨基嘧啶和苯甲醛溶解在有机溶剂中，在80～100℃下搅拌反应4～6h，得到均匀淡黄色液体；
(2)待步骤(1)反应体系冷却至室温后，加入DOPO并升温至120～140℃搅拌反应3～5h，得到均匀橘红色液体；
(3)将步骤(2)中得到的橘红色液体减压蒸馏，得到淡黄色粉末固体；
(4)将步骤(3)中淡黄色粉末真空干燥，除去剩余的有机溶剂，即得到所述反应型阻燃剂。
3.根据权利要求2所述的一种反应型阻燃剂的制备方法，其特征在于，步骤(1)所述2,4,6-三氨基嘧啶和苯甲醛与步骤(2)所述DOPO的摩尔比为1:2.8～3.2:2.9～3.1。
4.根据权利要求2或3所述的一种反应型阻燃剂的制备方法，其特征在于，步骤(4)所述真空干燥的温度为100～110℃，真空干燥的时间为10～12h。
5.根据权利要求4所述的种反应型阻燃剂的制备方法，其特征在于，步骤(3)所述减压蒸馏的方式为：采用旋转蒸发仪，在125℃下以80rpm的旋转速度蒸发。
6.根据权利要求5所述的种反应型阻燃剂的制备方法，其特征在于，步骤(1)所述有机溶剂为DMF、四氢呋喃、二氧六环和丙酮中的至少一种；
步骤(3)所述减压蒸馏的时间为1～2h。
7.一种阻燃环氧树脂，其特征在于，其由包含如下质量份的组分制备得到：100份双酚F环氧树脂、8～10份权利要求1所述的反应型阻燃剂和29～31份固化剂。
8.根据权利要求7所述一种阻燃环氧树脂，其特征在于，所述双酚F环氧树脂的环氧值为0.58～0.6；
所述固化剂为4.4'-二氨基二苯基甲烷、(二氨基二苯基砜)、2-甲基咪唑和双氰胺中的至少一种。
9.权利要求7～8任一项所述一种阻燃环氧树脂的制备方法，其特征在于，包括如下步骤：先将双酚F环氧树脂加热至120～150℃，再加入反应型阻燃剂，并混合均匀，然后冷却至温度为70～90℃，再加入固化剂，混合均匀后真空脱泡，再依次进行浇注模具，先在80～90℃下保温2-3h，再在120～130℃下保温2-3h，最后在150～160℃下保温5～6h，自然冷却后，制得所述阻燃环氧树脂。
10.权利要求7～8任一项所述一种阻燃环氧树脂在装饰涂料、轨道交通和电子封装方面的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211057311.2A CN115340574A (zh) | 2022-08-31 | 2022-08-31 | 一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211057311.2A CN115340574A (zh) | 2022-08-31 | 2022-08-31 | 一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115340574A true CN115340574A (zh) | 2022-11-15 |
Family
ID=83955885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211057311.2A Pending CN115340574A (zh) | 2022-08-31 | 2022-08-31 | 一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340574A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116355284A (zh) * | 2023-03-28 | 2023-06-30 | 福州大学 | 一种用于阻燃环氧树脂的dopo基反应型阻燃剂及其制备方法 |
-
2022
- 2022-08-31 CN CN202211057311.2A patent/CN115340574A/zh active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116355284A (zh) * | 2023-03-28 | 2023-06-30 | 福州大学 | 一种用于阻燃环氧树脂的dopo基反应型阻燃剂及其制备方法 |
| CN116355284B (zh) * | 2023-03-28 | 2024-06-07 | 福州大学 | 一种用于阻燃环氧树脂的dopo基反应型阻燃剂及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qian et al. | Organic/inorganic flame retardants containing phosphorus, nitrogen and silicon: Preparation and their performance on the flame retardancy of epoxy resins as a novel intumescent flame retardant system | |
| Chen et al. | Synthesis of chitosan-based flame retardant and its fire resistance in epoxy resin | |
| Cheng et al. | Aminobenzothiazole-substituted cyclotriphosphazene derivative as reactive flame retardant for epoxy resin | |
| Zhu et al. | Influence of a novel P/N-containing oligomer on flame retardancy and thermal degradation of intumescent flame-retardant epoxy resin | |
| Zhang et al. | Facile construction of one-component intrinsic flame-retardant epoxy resin system with fast curing ability using imidazole-blocked bismaleimide | |
| Sun et al. | Effect of additive phosphorus-nitrogen containing flame retardant on char formation and flame retardancy of epoxy resin | |
| Huo et al. | Flame‐retardant performance and mechanism of epoxy thermosets modified with a novel reactive flame retardant containing phosphorus, nitrogen, and sulfur | |
| Huo et al. | Thermal properties and flame retardancy of an intumescent flame-retarded epoxy system containing phosphaphenanthrene, triazine-trione and piperidine | |
| Liu | Epoxy resins from novel monomers with a bis‐(9, 10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl‐) substituent | |
| Jin et al. | Epoxy thermoset with enhanced flame retardancy and physical-mechanical properties based on reactive phosphaphenanthrene compound | |
| Yi et al. | Effects of common synergistic agents on intumescent flame retardant polypropylene with a novel charring agent | |
| Peng et al. | A bio-based phosphaphenanthrene-containing derivative modified epoxy thermosets with good flame retardancy, high mechanical properties and transparency | |
| Xu et al. | Small change, big impact: Simply changing the substitute on Si atom towards significant improvement of flame retardancy and toughness of epoxy resins | |
| Qian et al. | Novel DOPO-based epoxy curing agents: synthesis and the structure–property relationships of the curing agents on the fire safety of epoxy resins | |
| CN113968878B (zh) | 超支化硼酸改性的酞腈单体及其制备方法与应用 | |
| Zhou et al. | High residue bio-based structural–functional integration epoxy and intrinsic flame retardant mechanism study | |
| Niu et al. | A furan-based phosphaphenanthrene-containing derivative as a highly efficient flame-retardant agent for epoxy thermosets without deteriorating thermomechanical performances | |
| Qi et al. | Facile and scalable fabrication of bioderived flame retardant based on adenine for enhancing fire safety of fully biodegradable PLA/PBAT/TPS ternary blends | |
| Nabipour et al. | Improvement of the flame retardant and thermomechanical properties of epoxy resins by a vanillin-derived cyclotriphosphazene-cored triazole compound | |
| CN111303483A (zh) | 含对羟基苯甲醛和色胺结构的氮-磷系高效阻燃剂、制备方法及应用 | |
| CN115340574A (zh) | 一种反应型阻燃剂、阻燃环氧树脂及其制备方法和应用 | |
| Chen et al. | Preparation of flame-retardant cyanate ester with low dielectric constants and dissipation factors modified with novel phosphorus-contained Schiff base | |
| CN110563944B (zh) | 一种聚磷腈共价三嗪聚合物及其制备方法和应用 | |
| CN113234228B (zh) | 一种高效阻燃抑烟的含硼聚磷酰胺阻燃剂及其制备方法和应用 | |
| CN110746577A (zh) | 一种本征阻燃的结构阻尼一体化树脂及其制备方法 |
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 |