CN109608499A - 含哌嗪环磷氮系无卤阻燃剂及其制备方法和用途 - Google Patents
含哌嗪环磷氮系无卤阻燃剂及其制备方法和用途 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- 125000004193 piperazinyl group Chemical group 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 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 claims abstract description 30
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract description 19
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims abstract description 15
- RAOZVFGTRXLBTA-UHFFFAOYSA-N 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane Chemical compound CC1(C)COP(Cl)OC1 RAOZVFGTRXLBTA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011938 amidation process Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims abstract description 3
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
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- 239000012452 mother liquor Substances 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
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- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 claims description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
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- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
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- 239000000047 product Substances 0.000 description 15
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000002027 dichloromethane extract Substances 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
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- -1 inorganic acid ester Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
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- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
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- 238000002485 combustion reaction Methods 0.000 description 3
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- 239000012973 diazabicyclooctane Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960004279 formaldehyde Drugs 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
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- 239000000779 smoke Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
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- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- HWSUUGHIDOOOOJ-UHFFFAOYSA-N dioxaphosphinane Chemical compound C1COOPC1 HWSUUGHIDOOOOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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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
- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K5/5398—Phosphorus bound to sulfur
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
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- C08J2301/02—Cellulose; Modified cellulose
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Abstract
本发明提供了一种含哌嗪环磷氮系无卤阻燃剂及其制备方法和用途;该阻燃剂的分子式为C10H21N2O2PS,结构式为:由2‑硫代‑2‑氯‑5,5‑二甲基‑1,3,2‑二氧磷杂环己烷与N‑甲基哌嗪经过酰胺化反应制得;其能作为纤维素、聚酯、聚氨酯和聚烯烃的纤维或薄膜阻燃用的原料添加物,或作为阻燃涂层的主要功能物。该阻燃剂是含有氮、磷阻燃成分的添加型阻燃剂,不含卤素;制备方法采用两步法合成工艺,反应条件温和,制备工艺简单,适宜于工业化大规模生产。
Description
技术领域
本发明涉及阻燃材料领域,具体涉及一种含哌嗪环磷氮系无卤阻燃剂及其制备方法和用途。
背景技术
火给人类带来光明与温暖,可是在它不受控制的时候也会给人类带来灾难。社会在进步,人民生活水平日益提高,人口越来越密集,火灾发生的危害愈来愈大,因此,材料阻燃开始变得势在必行。随着中国高分子材料工业的发展和应用领域的拓展,阻燃材料在化学建材、电子电器、交通运输、航空航天、日用家居等各个领域中具有广泛的应用。
阻燃材料是指与普通材料相比,在相同着火条件下具有更难点燃,且点然后易于熄灭或者不易蔓延,具有热量、烟气释放量低等优良性能的材料。阻燃剂则是使易燃材料具有阻燃特性的助剂。应用于阻燃材料的阻燃剂大致可以分为添加型阻燃剂和反应型阻燃剂两大类。本发明所述阻燃剂系添加型阻燃剂。
近年来,十溴二苯醚和六溴环十二烷被列入持久性有机污染类阻燃剂,卤素阻燃剂的发展受到限制,商业化阻燃剂如四径甲基氯化磷(THPC)等含有卤素或者有甲醛释放等问题而达不到环保要求。开发环保绿色无卤阻燃剂成为研究热点,磷氮系阻燃剂因其无与伦比的优点受到越来越多的重视。
在磷-氮协同阻燃剂中,含磷组分和含氮组分按照一定的比例配合使用,其中磷和氮起主要阻燃作用。两者共同使用时,阻燃剂的阻燃效果得到加强,而且磷-氮阻燃剂的毒性较低,燃烧过程中发烟量小,与材料的相容性好,在高聚物的阻燃应用中得到了广泛的应用。
磷-氮膨胀阻燃剂的作用机理通常可用“三源一体”表述,三源即“炭源”、“酸源”和“气源”。其中炭源是指含多羟基的碳氢化合物(如多元醇),多羟基化合物可被酸源夺走水分,脱水成炭,阻隔热源。酸源在阻燃剂中占比最大,多为无机酸和无机酸酯类化合物,它们是炭源的脱水剂,是阻燃剂发挥作用的主要原因。气源则是在受热过程中,分解出大量无毒且可起到灭火作用的气体的化合物,这些不可燃性气体与含磷组分分解形成的保护层经过发泡作用形成隔热层,这层隔热层由磷-碳组成,呈泡沫状,从而使高聚物变得膨胀,导热性能大大降低。选择气源的关键是使其分解温度适宜,过低会导致炭层无法起到作用,过高则会吹走炭层。这三源组成了一体,具有较高的阻燃效率,使得膨胀型阻燃剂在阻燃市场发展前景一片光明。
发明内容
针对现有阻燃剂含卤素及甲醛释放等不环保等问题,本发明提供了一种含哌嗪环磷氮系无卤阻燃剂及其制备方法和用途;该阻燃剂是含有氮、磷阻燃成分的添加型阻燃剂,不含卤素。该制备方法采用两步法合成工艺,反应条件温和,制备工艺简单,适宜于工业化大规模生产。
一种含哌嗪环磷氮系无卤阻燃剂,分子式为C10H21N2O2PS,结构式为:中文名称为5,5-二甲基-2-硫代-2-(4-甲基哌嗪)-1,3,2-二氧磷杂环己烷,英文名称为5,5-dimethyl-2-(4-methylpiperazin-1-yl)-1,3,2-dioxaphosphinane-2-sulfide,结构特点是含有哌嗪环的硫代膦酰胺体系。
进一步,所述含哌嗪环磷氮系无卤阻燃剂由2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷与N-甲基哌嗪经过酰胺化反应制得;优选2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷与N-甲基哌嗪物质的量配比为1:0.2-3.0。
进一步,所述中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷由新戊二醇与三氯硫磷经酯化反应制得。
进一步,所述酰胺化反应包括如下步骤:
1)向反应容器中加入溶剂、缚酸剂和反应物中的一种,在-20℃~室温条件下,将反应物中的另外一种以滴加的方式加入反应容器;优选,反应容器中还加入有催化剂;2)待滴加完成后,在0℃-80℃下继续反应2小时以上;
3)反应完成后,过滤,在母液中加入蒸馏水,再用萃取剂萃取,收集有机相干燥;去除萃取剂,得到粗产物;
4)将所述粗产物重结晶,得到所述含哌嗪环磷氮系无卤阻燃剂;
所述反应物为:2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和N-甲基哌嗪。
更进一步,步骤1)中所述溶剂为:1,2-二氯乙烷、二氯甲烷、四氢呋喃、甲苯或乙腈;所述催化剂为4-二甲氨基吡啶(DMAP)、三乙烯二胺(DABCO);所述缚酸剂为:三乙胺或吡啶。
更进一步,步骤1)中所述缚酸剂用量为反应物摩尔量的1~5倍;
更近一步,步骤3)中萃取剂为:二氯甲烷、1,2-二氯乙烷、乙酸乙酯或乙醚。
更进一步,步骤4)中重结晶使用的溶剂为:二氯甲烷、乙醇、甲苯、乙腈、乙酸乙酯或其混合物。
上述含哌嗪环磷氮系无卤阻燃剂能作为纤维素、聚酯、聚氨酯和聚烯烃纤维或薄膜制备过程的原料添加物,或作为阻燃涂层的主要功能物。
与现有技术相比,本发明提供的技术方案具有如下优点:
1)含哌嗪环磷氮系无卤阻燃剂是一种无卤的环保膨胀型阻燃剂,分解时释放不燃性气体使体系膨胀。含阻燃元素氮、磷、硫的含量相比单一阻燃元素阻燃剂的含量更高,同时,各元素中间具有多元协效阻燃作用,本发明集“酸源”、“碳源”、“气源”于一体,相互协同,阻燃性能高,且符合绿色环保要求。
2)本发明提供的磷氮系阻燃剂的制备方法采用两步法合成工艺,反应温度在0℃~80℃之间,采用缚酸剂为有机碱类促进反应的进行,反应条件温和,制备工艺简单,适宜于工业化大规模生产。
3)由于P-N键的存在,化合物水溶性显著降低,在应用于阻燃材料过程中稳定性好,不易受损,阻燃性能持久。
附图说明
图1为本发明提供的含哌嗪环磷氮系无卤阻燃剂的合成流程;
图2为实施例1制得产品的红外光谱图。
图3为实施例1制得产品的核磁共振(1HNMR)谱图;
图4为实施例1制得产品的核磁共振(13CNMR)谱图;
图5为实施例1制得产品的核磁共振(31PNMR)谱图;
图6为实施例1制得产品在空气中的热重(TG-DTG)分析图;
图7为实施例1制得产品在氩气中的热重(TG-DTG)分析图。
具体实施方式
以下通过实施例对本发明做进一步详细说明。
本发明各实施例中制备中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷的步骤为:
①将1.0mol三氯硫磷溶于100mL 1,2-二氯乙烷中,配置溶液A;
②向一装有恒压滴液漏斗、电动搅拌器、回流冷凝管的三口烧瓶里加入1.0mol新戊二醇、1.5mol缚酸剂三乙胺、及500mL溶剂1,2-二氯乙烷,搅拌,待新戊二醇完全溶解后,将所述溶液A在1-2s/滴的速度下滴入三口烧瓶;滴加完毕后回流反应3小时,得到反应液B;
③将所述反应液B加入100mL蒸馏水中淬灭,之后用200mL乙酸乙酯萃取液萃取三次,合并有机相,干燥,再用摩尔比为1:1的乙酸乙酯与石油醚重结晶,得到白色固体,即为中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷。
实施例1:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂二氯甲烷、3mol缚酸剂三乙胺和1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷,在0℃条件下,将1.0molN-甲基哌嗪/100mL溶剂二氯甲烷的溶液,以滴加的方式加入反应容器;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在室温条件(25℃)下继续反应24小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例2:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂1,2-二氯乙烷、4mol缚酸剂三乙胺、1.0mol甲基哌嗪和75mmol催化剂4-二甲氨基吡啶,在0℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂1,2-二氯乙烷构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在80℃下继续反应4小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例3:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂甲苯、2mol缚酸剂三乙胺、1.0mol甲基哌嗪和75mmol催化剂4-二甲氨基吡啶,在0℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂甲苯构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在50℃下继续反应6小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例4:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂乙腈、5mol缚酸剂吡啶、1.0mol甲基哌嗪和75mmol催化剂4-二甲氨基吡啶,在-10℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂乙腈构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在室温下下继续反应3小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例5:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂乙腈、6mol缚酸剂吡啶、1.0mol甲基哌嗪和75mmol催化剂4-二甲氨基吡啶,在-10℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂乙腈构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在室温下继续反应6小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例6:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂乙腈、7mol缚酸剂吡啶、1.0mol甲基哌嗪和75mmol催化剂4-二甲氨基吡啶,在0℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂乙腈构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在40℃继续反应8小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例7:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂乙腈、8mol缚酸剂吡啶、1.0mol甲基哌嗪和75mmol催化剂三乙烯二胺(DABCO),在0℃条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂乙腈构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在35℃继续反应3小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
实施例8:
一种含哌嗪环磷氮系无卤阻燃剂的制备方法,包括如下步骤:
1)向反应容器中加入500mL溶剂乙腈、7mol缚酸剂吡啶、1.0mol甲基哌嗪和75mmol催化剂DABCO,在室温条件下,将中间体溶液以滴加的方式加入反应容器;所述中间体溶液由1.0mol中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和200mL溶剂乙腈构成;
该反应容器为:装有搅拌机、回流冷凝管的1L三颈烧瓶;
2)待滴加完成后,在室温继续反应8小时;
3)反应完成后,过滤,在母液中加入150mL蒸馏水,再用200mL二氯甲烷萃取液萃取三次,收集有机相,干燥;去除萃取剂,得到粗、产物;
4)将粗产物利用乙酸乙酯重结晶,得到含哌嗪环磷氮系无卤阻燃剂。
各实施例制得的含哌嗪环磷氮系无卤阻燃剂结构相同,仅因反应条件的差异对产率有影响。附图2-7给出了利用实施例1制得的含哌嗪环磷氮系无卤阻燃剂的分析结果,具体如下:
图2为本发明磷氮系阻燃剂的红外光谱图,IR(KBr,cm-1):ν790是P=S伸缩振动吸收峰,ν970为P-N伸缩振动吸收峰,ν1099和ν1037的吸收峰是P-O-C骨架伸缩振动吸收峰,ν1280~1285为C-N伸缩振动吸收峰,ν1470和1360是CH2,CH3的C-H变形振动吸收峰,ν2971为CH2,CH3的C-H伸缩振动吸收峰。
图3为本发明磷氮系阻燃剂的核磁共振氢谱,1H NMR(400MHz,CDCl3)δ0.87(3H)和δ1.23(3H)为六元磷酸酯季碳上连接的两个-CH3的核磁信号峰,δ2.29(3H)为连接氮原子的-CH3上的氢原子的核磁信号峰;δ2.39(4H)为连接甲基的氮原子相邻-CH2-上的氢的核磁信号峰;δ3.44(4H)为连接磷原子的氮原子相邻2个-CH2-上的氢原子的核磁信号峰;δ3.75(2H)和δ4.39(2H)分别为与氧原子连接2个-CH2-上的氢原子的核磁信号峰。
图4为本发明磷氮系阻燃剂的核磁共振碳谱,13C NMR(100MHz,CDCl3)δ76.1两个峰分别为与氧原子连接2个-CH2-上的碳原子的核磁信号峰;δ55.2两个峰分别为连接磷原子的氮原子相邻2个-CH2-上的碳原子的核磁信号峰;δ46.3为连接氮原子的-CH3的碳原子的核磁信号峰;δ45.0和44.9为连接甲基的氮原子相邻-CH2-上的碳原子的核磁信号峰;δ32.3为连接两个甲基的季碳原子的核磁信号峰;δ22.9和20.8为连接季碳原子的两个-CH3的碳原子的核磁信号峰;
图5为本发明磷氮系阻燃剂的核磁共振磷谱,31P NMR(162MHz,CDCl3)δ71.8为磷原子核磁信号。
图6为本发明磷氮系阻燃剂在空气中的热重(TG-DTG)曲线图,该磷氮系阻燃剂初始失重温度为130℃,130℃~250℃时阻燃剂的分解速度较快,成炭迅速,最大失重速率出现在235℃。250℃以后,阻燃剂失重率基本达到稳定,残炭量为5%。该阻燃剂在受热过程中会分解出水、碳氮化合物及磷化物,随着温度的不断升高,水、碳氮化合物都会形成气态,最后残余的固体主要是磷化物。
图7为本发明磷氮系阻燃剂在氩气中的热重(TG-DTG)曲线图,该磷氮系阻燃剂初始失重温度为150℃,150℃~235℃时阻燃剂的分解速度较快,最大失重速率出现在225℃,与空气中测得数据相接近。235℃以后,阻燃剂失重率基本达到稳定,残炭量为4%。
综上分析,采用两步法制备方法得到的白色固体(Mp:71-72℃)产品为所述磷氮系阻燃剂:该产品在后续的阻燃试验中表现出了优异的阻燃性能,较以往已知阻燃剂具有更大的优势。
Claims (10)
1.一种含哌嗪环磷氮系无卤阻燃剂,其特征在于:分子式为C10H21N2O2PS,结构式为:
2.一种含哌嗪环磷氮系无卤阻燃剂的制备方法,其特征在于:由中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷与N-甲基哌嗪经过酰胺化反应制得。
3.如权利要求2所述的制备方法,其特征在于:2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷与N-甲基哌嗪物质的量配比为1:0.2~3.0。
4.如权利要求2所述的制备方法,其特征在于:所述中间体2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷由新戊二醇与三氯硫磷经酯化反应制得。
5.如权利要求2所述的制备方法,其特征在于:所述酰胺化反应包括如下步骤:
1)向反应容器中加入溶剂、缚酸剂和反应物中的一种,在-20℃~室温条件下,将反应物中的另外一种以滴加的方式加入反应容器;优选,反应容器中还加入有催化剂;
2)待滴加完成后,在0℃-80℃下继续反应2小时以上;
3)反应完成后,过滤,在母液中加入蒸馏水,再用萃取剂萃取,收集有机相干燥;去除萃取剂,得到粗产物;
4)将所述粗产物重结晶,得到所述含哌嗪环磷氮系无卤阻燃剂;
所述反应物为:2-硫代-2-氯-5,5-二甲基-1,3,2-二氧磷杂环己烷和N-甲基哌嗪。
6.如权利要求5所述的制备方法,其特征在于:步骤1)中所述溶剂为:1,2-二氯乙烷、二氯甲烷、四氢呋喃、甲苯或乙腈;所述催化剂为4-二甲氨基吡啶、三乙烯二胺;所述缚酸剂为:三乙胺或吡啶。
7.如权利要求5所述的制备方法,其特征在于:步骤1)中所述缚酸剂用量为反应物摩尔量的1~5倍。
8.如权利要求5所述的制备方法,其特征在于:步骤3)中萃取剂为:二氯甲烷、1,2-二氯乙烷、乙酸乙酯或乙醚。
9.如权利要求5所述的制备方法,其特征在于:步骤4)中重结晶使用的溶剂为:二氯甲烷、乙醇、甲苯、乙腈、乙酸乙酯或其混合物。
10.一种含哌嗪环磷氮系无卤阻燃剂的用途,其特征在于:其能作为纤维素、聚酯、聚氨酯和聚烯烃的纤维或薄膜阻燃用的原料添加物,或作为阻燃涂层的主要功能物。
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