CN106543473B - 一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂及其制备方法 - Google Patents
一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂及其制备方法 Download PDFInfo
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- CN106543473B CN106543473B CN201610898889.9A CN201610898889A CN106543473B CN 106543473 B CN106543473 B CN 106543473B CN 201610898889 A CN201610898889 A CN 201610898889A CN 106543473 B CN106543473 B CN 106543473B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 17
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002444 silanisation Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 24
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical group NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 13
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
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- -1 Nitrile compound Chemical class 0.000 claims description 3
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
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- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
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- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 2
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- 229910000859 α-Fe Inorganic materials 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 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 group 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 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract description 7
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- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
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- 239000007795 chemical reaction product Substances 0.000 description 6
- 150000002171 ethylene diamines Chemical class 0.000 description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
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- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08K5/5399—Phosphorus bound to nitrogen
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- 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
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- 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
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- 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
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- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2255—Oxides; Hydroxides of metals of molybdenum
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- 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
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
本发明公开了一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂,其制备方法是将六氯环三磷腈中的六个氯原子用乙二胺取代,再将具有成炭作用的三嗪基团引入其每条侧链,得到一种同时含有磷腈和三嗪基团的双基分子,继而将γ‑氨丙基三乙氧基硅烷(KH550)引入至该双基分子的侧链,并进一步将纳米金属化合物Me加入到反应体系中进行硅烷化反应,制备获得阻燃剂。该阻燃剂由于磷腈基团和三嗪基团的基团协同效应、双基化合物和纳米金属化合物间的协同效应及纳米金属化合物良好的催化成炭作用,具有热稳定性好、阻燃效率高、成炭率高、加工性能优越等优点,可广泛应用于各种高分子材料的阻燃改性中。
Description
技术领域
本发明涉及高分子材料技术领域,具体涉及一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂及其制备方法。
背景技术
近年来,在添加型阻燃剂领域中,研究者们致力于寻求、设计并开发阻燃效率、阻燃效果好的阻燃剂,力求在添加量较低的情况下基材能获得较好的阻燃效果。其中,双基协同阻燃剂受到了研究者们的广泛关注,并在Polymer、Polymer Degradation andStability、Journal of Applied Polymer Science、化工新型材料、工程塑料应用等诸多期刊上均可见到相关双基协同阻燃的研究成果的发表。
具体来讲,常见的双基协同阻燃剂主要包括磷杂菲基团和磷腈基团、三嗪基团和磷腈基团、三嗪基团和磷杂菲基团、三嗪三酮和磷杂菲基团、磷腈和三嗪基团等。文献Journal of Applied Polymer Science,43241-49,2016及专利104403128A中分别公开报道了基于三嗪和磷杂菲以及基于磷腈与磷杂菲基团的双基化合物及它们在环氧树脂中的应用。在公开专利104262399A中,报道还指出,含磷杂菲及磷腈基团的双基化合物阻燃剂可用于树脂、聚酯、聚烯烃阻燃中。
常用的金属化合物阻燃剂有氢氧化铝、氢氧化镁、镍化物、锌化物、铁化物、钼化物、钙化物等。然而,为了达到满意的阻燃效果,金属化合物阻燃剂的添加量通常比较大,导致树脂在混炼、成型时的流动性变差和成型品的物性降低。
发明内容
本发明的一个目的是提供一种热稳定性好、阻燃效率高、成炭率高的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂。
本发明提供了一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂,该类阻燃剂的化学结构式为:
本发明的另一目的是提供一种制备上述基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的方法。
该制备方法包括如下具体步骤:
步骤(1)将六氯环三磷腈的非质子有机溶剂加入到乙二胺的非质子有机溶剂中,体系中加入缚酸剂,在惰性气体氛围中,-5~30℃下搅拌3~6小时,得到6-(乙二氨基)环三磷腈化合物;
所述的6-(乙二氨基)环三磷腈化合物的分子结构式为:
六氯环三磷腈的非质子性有机溶剂中六氯环三磷腈的浓度为0.1~2mol/L,乙二胺的非质子性有机溶剂中乙二胺的浓度为0.15~3mol/L,加入的六氯环三磷腈、乙二胺、缚酸剂的摩尔比例为1∶6∶6~1∶12∶12;
所述的惰性气体通常为氮气或氩气;
所述的缚酸剂通常为三乙胺、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、吡啶、4-二甲氨基吡啶、N,N-二异丙基乙胺中的一种;
所述的非质子性有机溶剂通常为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二氧六环、甲苯、丙酮、丁酮、乙酸乙酯中的一种;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入三聚氯氰的非质子性有机溶剂,并加入缚酸剂,-10~10℃搅拌条件下反应2~8小时;所述的非质子性有机溶剂与步骤(1)采用同种非质子性有机溶剂;
三聚氯氰的非质子性有机溶剂中三聚氯氰的浓度为0.35~1.22mol/L,6-(乙二氨基)环三磷腈化合物与三聚氯氰的摩尔比例为1∶6~1∶12;
所述的缚酸剂采用与步骤(1)同种缚酸剂,缚酸剂与三聚氯氰的摩尔比例为1∶1~2∶1;
步骤(3).向反应溶液中加入γ-氨丙基三乙氧基硅烷(即硅烷偶联剂KH550)的非质子性有机溶剂;升高温度至40~70℃,搅拌、冷凝条件下反应3~15小时,继续升高温度至80~120℃,搅拌、冷凝条件下反应3~15小时;
所述的非质子性有机溶剂与步骤(2)采用同种非质子性有机溶剂;
所述的γ-氨丙基三乙氧基硅烷(KH550)的非质子性有机溶剂中KH550的浓度为1.15~3.89mol/L,KH550与三聚氯氰的摩尔比例为2∶1~4∶1;
步骤(4).将步骤(3)得到的产物经过抽滤将缚酸剂生成的盐除去,得到反应中间产物;
步骤(5).将纳米金属化合物Me和蒸馏水加入到步骤(4)所得的反应中间产物中,在40℃~100℃下搅拌或超声1~8小时进行硅烷化反应;
所述的纳米金属化合物Me优选纳米二氧化钛、纳米氧化锌、纳米氧化铝、纳米氧化锆、纳米氧化镧、纳米氧化铈、纳米三氧化钼、纳米氧化镍、纳米硫化镍、纳米磷酸镍、纳米氧化铁、纳米氢氧化铝、纳米氢氧化镁、纳米金属铁酸盐、或者纳米金属铝酸盐;
所述的纳米金属化合物Me、蒸馏水和γ-氨丙基三乙氧基硅烷(KH550)的摩尔比例为0.5∶1∶1~3∶6∶1;
步骤(6).反应结束后,经过旋蒸、干燥,得到基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂。
本发明中的六氯环三磷腈、乙二胺、缚酸剂、三聚氯氰、γ-氨丙基三乙氧基硅烷(KH550)、纳米金属化合物Me均为成熟产品,可以通过市场购买取得。
本发明将具有本质阻燃特性的六氯环三磷腈中的六个氯原子用乙二胺取代,得到一种环三磷腈衍生物,再将具有成炭作用的三嗪基团引入其每条侧链,得到一种同时含有磷腈和三嗪基团的双基分子,继而将γ-氨丙基三乙氧基硅烷(KH550)引入至该双基分子的侧链,并进一步将纳米金属化合物Me加入到反应体系中进行硅烷化反应,最终制备出一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂。该阻燃剂因同时含有磷腈和三嗪基团以及纳米金属化合物,富含N、P、Si、金属元素,在燃烧过程中,该阻燃剂通过磷腈基团和三嗪基团的基团协同效应及双基化合物和纳米金属化合物间的协同效应以及P、N、Si、金属元素四种元素之间的协同阻燃效果,发挥气相阻燃和凝聚相机理的阻燃作用;另外,纳米金属化合物具有良好的催化成炭作用,促使生成更多更稳定的炭层,这些炭层能够隔热、抑氧,从而起到提高阻燃剂阻燃效率的作用;该阻燃剂的热稳定性好、阻燃效率高、成炭率高、加工性能优越,可广泛应用于各种高分子材料的阻燃改性中。
具体实施方式
下面通过实施例进一步描述本发明。
实施例1.
步骤(1).将8.35g六氯环三磷腈溶于120ml二氧六环溶液,加入到48ml溶有8.64g乙二胺的二氧六环溶液中,加入无水碳酸钾20g,在N2氛围中,-5℃下搅拌6小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入200ml含25.6g三聚氯氰的二氧六环溶液,加入碳酸钾20g,-10℃搅拌条件下反应8小时;
步骤(3).向反应溶液中加入80ml含63.6g KH550的二氧六环溶液;升高温度至50℃,搅拌、冷凝条件下反应6小时,继续升高温度至100℃,搅拌、冷凝条件下反应6小时;
步骤(4).将步骤(3)得到的产物经过抽滤将碳酸钾生成的盐除去,得到反应中间产物;
步骤(5).将12.3g纳米氧化锌和5.8g蒸馏水加入到步骤(4)所得的反应中间产物中,50℃超声条件下反应6小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到基于原位掺杂纳米氧化锌的磷腈/三嗪双基分子阻燃剂。
实施例2.
步骤(1).将4.18g六氯环三磷腈溶于120ml二氧六环溶液,加入到48ml溶有4.32g乙二胺的二氧六环溶液中,加入无水碳酸钠9g,在N2氛围中,0℃下搅拌5小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入200ml含12.86g三聚氯氰的二氧六环溶液,加入碳酸钠9g,-5℃搅拌条件下反应7小时;
步骤(3).向反应溶液中加入50ml含32.8g KH550的二氧六环溶液;升高温度至55℃,搅拌、冷凝条件下反应7小时,继续升高温度至90℃,搅拌、冷凝条件下反应7小时;
步骤(4).将步骤(3)得到的产物经过抽滤将碳酸钠生成的盐除去,得到反应中间产物;
步骤(5).将45.6g纳米氧化锆和13.5g蒸馏水加入到步骤(4)所得的反应中间产物中,40℃超声条件下反应8小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到基于原位掺杂纳米氧化锆的磷腈/三嗪双基分子阻燃剂。
实施例3.
步骤(1).将0.835g六氯环三磷腈溶于15ml四氢呋喃溶液,加入到50ml溶有0.86g乙二胺的四氢呋喃溶液中,加入碳酸氢钾1.5g,在N2氛围中,5℃下搅拌4小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入20ml含2.56g三聚氯氰的四氢呋喃溶液,加入碳酸氢钾1.5g,0℃搅拌条件下反应6小时;
步骤(3).向反应溶液中加入16ml含6.36g KH550的二氧六环溶液;升高温度至40℃,搅拌、冷凝条件下反应9小时,继续升高温度至80℃,搅拌、冷凝条件下反应9小时;
步骤(4).将步骤(3)得到的产物经过抽滤将碳酸氢钾生成的盐除去,得到反应中间产物;
步骤(5).将28.1g纳米氧化镧和3.5g蒸馏水加入到步骤(4)所得的反应中间产物中,60℃超声条件下反应5小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到基于原位掺杂纳米氧化镧的磷腈/三嗪双基分子阻燃剂。
实施例4.
步骤(1).将1.69g六氯环三磷腈溶于30ml丙酮溶液,加入到20ml溶有1.72g乙二胺的丙酮溶液中,加入碳酸氢钠2.5g,在N2氛围中,10℃下搅拌4.5小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入40ml含3.15g三聚氯氰的丙酮溶液,加入碳酸氢钠2.5g,5℃搅拌条件下反应5.5小时;
步骤(3).向反应溶液中加入50ml含12.73g KH550的丙酮溶液;升高温度至50℃,搅拌、冷凝条件下反应3小时,继续升高温度至85℃,搅拌、冷凝条件下反应3小时;
步骤(4).将步骤(3)得到的产物经过抽滤将碳酸氢钠生成的盐除去,得到反应中间产物;
步骤(5).将20.74g纳米三氧化钼和5.2g蒸馏水加入到步骤(4)所得的反应中间产物中,60℃条件下搅拌、冷凝回流4小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到原位掺杂纳米三氧化钼的磷腈/三嗪双基分子阻燃剂。
实施例5.
步骤(1).将2.51g六氯环三磷腈溶于45ml N,N-二甲基甲酰胺溶液,加入到50ml溶有3.34g乙二胺的N,N-二甲基甲酰胺溶液中,加入三乙胺6.75g,在N2氛围中,15℃下搅拌4小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入90ml含11.48g三聚氯氰的N,N-二甲基甲酰胺溶液,加入三乙胺6.75g,6℃搅拌条件下反应4.5小时;
步骤(3).向反应溶液中加入70ml含42.66g KH550的N,N-二甲基甲酰胺溶液;升高温度至65℃,搅拌、冷凝条件下反应15小时,继续升高温度至95℃,搅拌、冷凝条件下反应15小时;
步骤(4).将步骤(3)得到的产物经过抽滤将三乙胺生成的盐除去,得到反应中间产物;
步骤(5).将90g纳米氧化镧和10.4g蒸馏水加入到步骤(4)所得的反应中间产物中,70℃超声条件下反应5小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到原位掺杂纳米氧化镧的磷腈/三嗪双基分子阻燃剂。
实施例6.
步骤(1).将3.69g六氯环三磷腈溶于60ml N-甲基吡咯烷酮溶液,加入到40ml溶有3.45g乙二胺的丙酮溶液中,加入三乙胺9.03g,在N2氛围中,20℃下搅拌3.5小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入40ml含6.25g三聚氯氰的N-甲基吡咯烷酮溶液,加入三乙胺9.03g,10℃搅拌条件下反应2小时;
步骤(3).向反应溶液中加入60ml含51.06g KH550的N-甲基吡咯烷酮溶液;升高温度至70℃,搅拌、冷凝条件下反应12小时,继续升高温度至120℃,搅拌、冷凝条件下反应12小时;
步骤(4).将步骤(3)得到的产物经过抽滤将三乙胺生成的盐除去,得到反应中间产物;
步骤(5).将4.67g纳米氧化镁和4.2g蒸馏水加入到步骤(4)所得的反应中间产物中,100℃条件下搅拌、冷凝回流1小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到原位掺杂纳米氧化镁的磷腈/三嗪双基分子阻燃剂。
实施例7.
步骤(1).将7.48g六氯环三磷腈溶于80ml N,N-二甲基乙酰胺溶液,加入到40ml溶有6.92g乙二胺的N,N-二甲基乙酰胺中,加入吡啶9.13g,在N2氛围中,30℃下搅拌3小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入70ml含12.65g三聚氯氰的N-N二甲基乙酰胺溶液,加入吡啶9.13g,-6℃搅拌条件下反应5小时;
步骤(3).向反应溶液中加入80ml含50.53g KH550的N,N-二甲基乙酰胺溶液;升高温度至61℃,搅拌、冷凝条件下反应6小时,继续升高温度至88℃,搅拌、冷凝条件下反应9小时;
步骤(4).将步骤(3)得到的产物经过抽滤将吡啶生成的盐除去,得到反应中间产物;
步骤(5).将6.7g纳米氢氧化镁和5g蒸馏水加入到步骤(4)所得的反应中间产物中,75℃条件下搅拌、冷凝回流2.5小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到原位掺杂纳米氢氧化镁的磷腈/三嗪双基分子阻燃剂。
实施例8.
步骤(1).将5.21g六氯环三磷腈溶于95ml二氧六环溶液,加入到60ml溶有10.32g乙二胺的二氧六环溶液中,加入碳酸钾24g,在N2氛围中,20℃下搅拌4小时,得到6-(乙二氨基)环三磷腈化合物;
步骤(2).6-(乙二氨基)环三磷腈化合物中加入120ml含27.12g三聚氯氰的二氧六环溶液,加入碳酸钾24g,3℃搅拌条件下反应5小时;
步骤(3).向反应溶液中加入200ml含74.22g KH550的二氧六环溶液;升高温度至55℃,搅拌、冷凝条件下反应7.5小时,继续升高温度至90℃,搅拌、冷凝条件下反应7.5小时;
步骤(4).将步骤(3)得到的产物经过水洗将碳酸钾生成的盐除去,得到反应中间产物;
步骤(5).将39.3g纳米氢氧化铝和36g蒸馏水加入到步骤(4)所得的反应中间产物中,90℃超声条件下反应2小时,制备得目标产物;
步骤(6).反应结束后,经过旋蒸、干燥,得到原位掺杂纳米氢氧化铝的磷腈/三嗪双基分子阻燃剂。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明,不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说,在不脱离本发明构思的前提下,做出若干等同替代或明显变型,而且性能或用途相同,都应当视为属于本发明的保护范围。
Claims (6)
1.一种基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂,其特征在于,该阻燃剂的化学结构式为:
2.制备如权利要求1所述的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的方法,其特征在于,包括以下步骤:
步骤(1)将六氯环三磷腈的非质子有机溶剂加入到乙二胺的非质子有机溶剂中,体系中加入缚酸剂,在惰性气体氛围中,-5~30℃下搅拌3~6小时,得到6-(乙二氨基)环三磷腈化合物;
其中,所述的六氯环三磷腈的非质子性有机溶剂中六氯环三磷腈的浓度为0.1~2mol/L,乙二胺的非质子性有机溶剂中乙二胺的浓度为0.15~3mol/L,加入的六氯环三磷腈、乙二胺、缚酸剂的摩尔比例为1∶6∶6~1∶12∶12;
步骤(2)向上述6-(乙二氨基)环三磷腈化合物中加入三聚氯氰的非质子性有机溶剂,并加入缚酸剂,-10~10℃搅拌条件下反应2~8小时;
其中,所述的三聚氯氰的非质子性有机溶剂中三聚氯氰的浓度为0.35~1.22mol/L,6-(乙二氨基)环三磷腈化合物与三聚氯氰的摩尔比例为1∶6~1∶12;缚酸剂与三聚氯氰的摩尔比例为1∶1~2∶1;
步骤(3)向上述反应溶液中加入硅烷偶联剂KH550的非质子性有机溶剂;升高温度至40~70℃,搅拌、冷凝条件下反应3~15小时,继续升高温度至80~120℃,搅拌、冷凝条件下反应3~15小时;
其中,所述的硅烷偶联剂KH550的非质子性有机溶剂中KH550的浓度为1.15~3.89mol/L,KH550与三聚氯氰的摩尔比例为2∶1~4∶1;
步骤(4)将步骤(3)得到的产物经过抽滤将缚酸剂生成的盐除去,得到反应中间产物;
步骤(5)将纳米金属化合物Me和蒸馏水加入到上述反应中间产物中,在40℃~100℃下搅拌或超声1~8小时进行硅烷化反应;
其中,所述的纳米金属化合物Me、蒸馏水与步骤(3)所加入的硅烷偶联剂KH550的摩尔比例为0.5∶1∶1~3∶6∶1;
步骤(6)反应结束后,经过旋蒸、干燥,得到基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂;
上述所有的非质子性有机溶剂均采用同一种非质子性有机溶剂;上述所有的缚酸剂均采用同一种缚酸剂。
3.根据权利要求2所述的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的制备方法,其特征在于,所述的惰性气体为氩气。
4.根据权利要求2所述的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的制备方法,其特征在于,所述的缚酸剂为三乙胺、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾、吡啶、4-二甲氨基吡啶、N,N-二异丙基乙胺中的一种。
5.根据权利要求2所述的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的制备方法,其特征在于,所述的非质子性有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、四氢呋喃、二氧六环、甲苯、丙酮、丁酮、乙酸乙酯中的一种。
6.根据权利要求2所述的基于原位掺杂纳米级金属化合物的磷腈/三嗪双基分子阻燃剂的制备方法,其特征在于,所述的纳米金属化合物Me为纳米二氧化钛、纳米氧化锌、纳米氧化铝、纳米氧化锆、纳米氧化镧、纳米氧化铈、纳米三氧化钼、纳米氧化镍、纳米硫化镍、纳米磷酸镍、纳米氧化铁、纳米氢氧化铝、纳米氢氧化镁、纳米金属铁酸盐、或者纳米金属铝酸盐。
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