CN110229190A - 一种含多价态磷元素的阻燃剂及其制备方法 - Google Patents
一种含多价态磷元素的阻燃剂及其制备方法 Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
- 239000011574 phosphorus Substances 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims description 3
- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 claims description 3
- CVNMBKFJYRAHPO-UHFFFAOYSA-N [chloro(methyl)phosphoryl]methane Chemical compound CP(C)(Cl)=O CVNMBKFJYRAHPO-UHFFFAOYSA-N 0.000 claims description 3
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical group C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- UGOLAPHJCTVIEW-UHFFFAOYSA-N chloro-dimethyl-sulfanylidene-$l^{5}-phosphane Chemical compound CP(C)(Cl)=S UGOLAPHJCTVIEW-UHFFFAOYSA-N 0.000 claims description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical group C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
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- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 abstract description 23
- 229920000647 polyepoxide Polymers 0.000 abstract description 23
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000979 retarding effect Effects 0.000 abstract description 15
- 238000002485 combustion reaction Methods 0.000 abstract description 13
- 230000007246 mechanism Effects 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000003610 charcoal Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 3
- 238000002390 rotary evaporation Methods 0.000 description 14
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 5
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000781 heat-release-rate curve Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical class C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
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- 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)
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Abstract
本发明公开了一种含多价态磷元素的阻燃剂及其制备方法,其中含多价态磷元素的阻燃剂的化学结构如式(I)所示:其中R1和R2分别为不同价态的含磷结构。本发明含多价态磷元素的阻燃剂化学结构中同时含有多种不同价态的磷原子,既可以发挥凝聚相阻燃机理促进燃烧过程中聚合物的成炭,又可以发挥气相阻燃机理捕捉燃烧过程中活性自由基;且磷含量和芳环数量可调节,适用于不同聚合物基体的阻燃处理。本发明所述的阻燃剂处理环氧树脂的极限氧指数有明显提高,垂直燃烧等级达V‑0级,具有良好的成炭性、阻燃效率高等优点。
Description
技术领域
本发明属于含磷阻燃剂技术领域,具体涉及一种含多价态磷元素的阻燃剂及其制备方法。
背景技术
磷系阻燃剂作为一种高效、低烟、低毒的阻燃剂,近年来成为无卤阻燃技术领域研究的热点之一。磷系阻燃剂的阻燃机理主要包括凝聚相和气相阻燃机理。在凝聚相中,磷系阻燃剂受热分解形成聚偏磷酸等酸性化合物,催化聚合物脱水、环化、成炭,在聚合物表面形成阻隔性炭层,阻止热量和物质交换;在气相中,磷系阻燃剂受热分解形成挥发性PO自由基,能够捕获活性氢原子,阻止燃烧链式反应(Polymer Degradation and Stability2014,105,248-256;Fire and Materials 2016,40,826-835)。磷系阻燃剂的阻燃机理与其化学结构中磷元素的价态密切相关。据文献报道,含低价态磷元素的化合物以气相阻燃机理为主,而含高价态磷元素的化合物则以凝聚相阻燃机理为主(Polymer 2006,47,8495-8508;Polymer Degradation and Stability 2011,96,1455-1461)。目前,磷系阻燃剂的制备主要集中在含单一价态磷元素的化合物,同时含多价态磷元素的阻燃剂鲜有报道。中国科学技术大学胡源课题组在同一阻燃剂结构中引入不同价态磷元素,能够同时发挥凝聚相和气相阻燃机理,具有协同阻燃效应(Industrial&Engineering Chemistry Research2017,56,1245-1255),然而该阻燃剂的添加量在5.7%以上时,才能通过UL-94垂直燃烧试验V-0级别,其阻燃效率有待于进一步提高。因此,开发无卤环保、安全高效的新型磷系阻燃剂,已成为阻燃聚合物技术领域的迫切需求。
发明内容
本发明旨在提供一种含多价态磷元素的阻燃剂及其制备方法。本发明阻燃剂的化学结构中同时含有多种不同价态的磷原子,既可以发挥凝聚相阻燃机理促进燃烧过程中聚合物的成炭,又可以发挥气相阻燃机理捕捉燃烧过程中活性自由基,而且结构中的磷含量和芳环数量可调节,适用于不同聚合物基体的阻燃处理。
本发明含多价态磷元素的阻燃剂,其化学结构如下式(I)所示:
式(I)中,R1的化学结构为以下结构中的任一种:
式(I)中,R2的化学结构为以下结构中的任一种:
本发明含多价态磷元素的阻燃剂的制备方法,包括以下步骤:
①将含磷化合物A与对苯二甲醛混合于溶剂甲苯中,在惰性气体的保护下,加热至回流温度反应3~6小时,旋转蒸发除去溶剂,得到含磷二元醇,其化学结构如下式(II)所示:
所述含磷化合物A为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、二苯基磷氧、亚磷酸二苯酯、亚磷酸二乙酯、亚磷酸二甲酯中的任一种。
②步骤①获得的含磷二元醇、三乙胺以及含磷化合物B混合于溶剂甲苯中,加热至60~100℃反应6~24小时,过滤,旋转蒸发除去溶剂,得到目标产物。
所述含磷化合物B为氯代磷酸二苯酯、二苯基次膦酰氯、氯代二苯基膦、二乙基亚磷酰氯、O,O-二甲基磷酰氯、二甲基硫代磷酰氯中的任一种。
步骤①中,对苯二甲醛与含磷化合物A的摩尔比为1:2~2.2。
步骤①中,所述惰性气体为氮气、氩气或氦气中的任一种。
步骤②中,所述含磷二元醇与三乙胺的摩尔比为1:2~2.2,所述含磷二元醇与含磷化合物B的摩尔比为1:2~2.2。
与现有技术相比,本发明的有益效果是:
1、本发明提供的含多价态磷元素的阻燃剂,化学结构中同时含有多种不同价态的磷原子,既可以发挥凝聚相阻燃机理促进燃烧过程中聚合物的成炭,又可以发挥气相阻燃机理捕捉燃烧过程中活性自由基,具有协同阻燃效应,阻燃效率高。
2、本发明提供的含多价态磷元素的阻燃剂,化学结构中的磷含量和芳环数量可调节,适用于不同聚合物基体的阻燃处理。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明实施例7中各样品的热重分析曲线。
图2为本发明实施例7中采用微型燃烧量热仪对各样品表征的热释放速率曲线。
具体实施方式
为了进一步说明本发明的技术方案,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1-7中的原材料及测试为国家自然科学基金青年科学基金项目(21604081)资助。
实施例1:
①将对苯二甲醛与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,按摩尔比1:2在氮气保护下,在甲苯溶剂中加热至回流温度反应3小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、氯代磷酸二苯酯按反应摩尔比1:2:2在甲苯溶剂中加热至60℃,反应24小时,过滤,旋转蒸发除去溶剂,得到目标产物a,其化学结构如下所示:
目标产物a经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):754,934(P-O-C),1226-1201(P=O),1589(P-O-Ph).1H-NMR(400MHz,DMSO-d6,ppm):5.40–5.13(m,2H,(P-CH-O)2),8.27-8.13,(m,4H),8.02-7.91,(m,2H),7.82-7.08(m,34H).
实施例2:
①将对苯二甲醛与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,按摩尔比1:2.2在氩气保护下,在甲苯溶剂中加热至回流温度反应6小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、二苯基次膦酰氯按反应摩尔比1:2.2:2.2在甲苯溶剂中加热至100℃,反应6小时,过滤,旋转蒸发除去溶剂,得到目标产物b,其化学结构如下所示:
目标产物b经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):932(P-O-C),1192(P=O),1589(P-Ar).1H-NMR(400MHz,DMSO-d6,ppm):5.41–5.16(m,2H,(P-CH-O)2),8.26-8.13(m,4H),8.05-7.93(m,2H),7.82-7.08(m,34H).
实施例3:
①将对苯二甲醛与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,按摩尔比1:2.1在氦气保护下,在甲苯溶剂中加热至回流温度反应4小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、氯代二苯基膦按反应摩尔比1:2.1:2.1在甲苯溶剂中加热至80℃,反应12小时,过滤,旋转蒸发除去溶剂,得到目标产物c,其化学结构如下所示:
目标产物c经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):932(P-O-C),1231(P=O),1592cm-1(P-Ar).1H-NMR(400MHz,DMSO-d6,ppm):5.51–5.19(m,2H,(P-CH-O)2),8.25-8.13(m,4H),8.04-7.90(m,2H),7.83-7.04(m,34H).
实施例4:
①将对苯二甲醛与二苯基磷氧,按摩尔比1:2在氮气保护下,在甲苯溶剂中加热至回流温度反应4小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、二乙基亚磷酰氯按反应摩尔比1:2.1:2.1在甲苯溶剂中加热至80℃,反应12小时,过滤,旋转蒸发除去溶剂,得到目标产物d,其化学结构如下所示:
目标产物d经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):932(P-O-C),1202(P=O),1589(P-Ph),3240(P-CH-OH);1H-NMR(400MHz,DMSO-d6,ppm):1.29(t,J=8.2Hz,12H,-CH3),3.79(q,J=8.2Hz,8H,O-CH2-),5.25-5.10(m,2H,(P-CH-O)2),7.36(s,4H,Ar-H),7.52-7.61(m,12H,Ar-H),7.77-7.89(m,8H,Ar-H).
实施例5:
①将对苯二甲醛与亚磷酸二苯酯,按摩尔比1:2.1在氮气保护下,在甲苯溶剂中加热至回流温度反应4小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、O,O-二甲基磷酰氯按反应摩尔比1:2.1:2.1在甲苯溶剂中加热至80℃,反应12小时,过滤,旋转蒸发除去溶剂,得到目标产物e,其化学结构如下所示:
目标产物e经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):931(P-O-C),940(P-O-Ph),1204(P=O),3241(P-CH-OH);1H-NMR(400MHz,DMSO-d6,ppm):3.92(d,J=9.4Hz,12H,-OCH3),5.28-5.12(m,2H,(P-CH-O)2),7.86-7.38(m,24H,Ar-H).
实施例6:
①将对苯二甲醛与亚磷酸二甲酯,按摩尔比1:2.1在氮气保护下,在甲苯溶剂中加热至回流温度反应4小时,旋转蒸发除去溶剂,得到含磷二元醇。
②将上述含磷二元醇、三乙胺、二甲基硫代磷酰氯按反应摩尔比1:2.1:2.1在甲苯溶剂中加热至100℃,反应6小时,过滤,旋转蒸发除去溶剂,得到目标产物f,其化学结构如下所示:
目标产物f经傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H-NMR)表征,确认其化学结构如下:FT-IR(KBr,cm-1):654(P=S),732(P-C),935(P-O-C),1206(P=O),3238(P-CH-OH).1H-NMR(400MHz,DMSO-d6,ppm):1.38(s,J=6.2Hz,12H,P-CH3),3.95(d,J=9.3Hz,12H,-OCH3),5.32-5.15(m,2H,(P-CH-O)2),7.38(s,4H,Ar-H).
实施例7:阻燃环氧树脂的制备及其氧指数、垂直燃烧试验结果
本实施例按照表1配方制备阻燃环氧树脂:
表1阻燃环氧树脂配方
注:环氧树脂为N,N,N,N-四环氧丙基-4,4-二氨基二苯甲烷,固化剂为4,4’-二氨基二苯砜,含磷阻燃剂1是9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,含磷阻燃剂2是亚磷酸二苯酯。
准确称量环氧树脂、固化剂、阻燃剂,先将环氧树脂与阻燃剂在烧杯里80℃混合1小时,然后加入固化剂,继续混合30分钟,立即倒入模具中,固化条件为100℃/2小时+150℃/2小时+180℃/2小时。自然冷却至室温,得到阻燃环氧树脂样品,按照测试氧指数及垂直燃烧试验,结果如表2所示:
表2阻燃环氧树脂的氧指数及垂直燃烧试验结果
氧指数(%) | UL-94垂直燃烧试验结果 | |
环氧树脂 | 25.0 | 无级别 |
阻燃环氧树脂-1 | 29.0 | V-0级 |
阻燃环氧树脂-2 | 30.0 | V-0级 |
阻燃环氧树脂-3 | 30.0 | V-0级 |
阻燃环氧树脂-4 | 29.0 | V-1级 |
阻燃环氧树脂-5 | 28.5 | V-1级 |
从表2各样品的阻燃测试结果表明,未处理环氧树脂的氧指数为25.0%,UL-94垂直燃烧试验无级别。分别添加2wt%含磷阻燃剂1和含磷阻燃剂2的环氧树脂能通过UL-94垂直燃烧试验V-1级别。相比之下,分别添加2wt%阻燃剂a、阻燃剂b和阻燃剂c的环氧树脂的氧指数上升到29.0%、30.0%和30.0%,同时均能通过UL-94垂直燃烧试验V-0级别,体现出阻燃效率高的优势。
各样品的热重分析曲线如图1所示。可以看出,阻燃剂a、阻燃剂b和阻燃剂c能够明显提升环氧树脂的成炭性能。未处理环氧树脂在800℃时几乎分解殆尽,而阻燃环氧树脂的残炭率均在10%以上,表明阻燃剂a、阻燃剂b和阻燃剂c具有良好的催化成炭能力。
图2是采用微型燃烧量热仪对各样品表征的热释放速率曲线。未处理环氧树脂的热释放速率峰值约为198W/g。分别添加2wt%阻燃剂a、阻燃剂b和阻燃剂c的环氧树脂的热释放速率峰值降幅均在20%以上,表明阻燃剂a、阻燃剂b和阻燃剂c具有良好的阻燃性能。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (7)
1.一种含多价态磷元素的阻燃剂,其特征在于其化学结构如下式(I)所示:
式(I)中,R1的化学结构为以下结构中的任一种:
式(I)中,R2的化学结构为以下结构中的任一种:
2.权利要求1所述的含多价态磷元素的阻燃剂的制备方法,其特征在于包括以下步骤:
①将含磷化合物A与对苯二甲醛混合于溶剂甲苯中,在惰性气体的保护下反应得到含磷二元醇,其化学结构如下式(II)所示:
所述含磷化合物A为9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、二苯基磷氧、亚磷酸二苯酯、亚磷酸二乙酯、亚磷酸二甲酯中的任一种;
②步骤①获得的含磷二元醇、三乙胺以及含磷化合物B混合于溶剂甲苯中,加热反应得到目标产物;
所述含磷化合物B为氯代磷酸二苯酯、二苯基次膦酰氯、氯代二苯基膦、二乙基亚磷酰氯、O,O-二甲基磷酰氯、二甲基硫代磷酰氯中的任一种。
3.根据权利要求2所述的制备方法,其特征在于:
步骤①中,对苯二甲醛与含磷化合物A的摩尔比为1:2~2.2。
4.根据权利要求2所述的制备方法,其特征在于:
步骤①中,所述惰性气体为氮气、氩气或氦气中的任一种。
5.根据权利要求2所述的制备方法,其特征在于:
步骤①中,反应温度为回流温度,反应时间为3~6小时。
6.根据权利要求2所述的制备方法,其特征在于:
步骤②中,所述含磷二元醇与三乙胺的摩尔比为1:2~2.2,所述含磷二元醇与含磷化合物B的摩尔比为1:2~2.2。
7.根据权利要求2所述的制备方法,其特征在于:
步骤②中,反应温度为60~100℃,反应时间为6~24小时。
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