CN105732705B - 一种含磷氮阻燃单体及其制备方法 - Google Patents
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- 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 39
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 39
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- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 14
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
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- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
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- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
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- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- 229910052736 halogen Inorganic materials 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 239000003610 charcoal Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- SULWMEGSVQCTSK-UHFFFAOYSA-N diethyl hydrogen phosphite Chemical compound CCOP(O)OCC SULWMEGSVQCTSK-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
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- 239000004698 Polyethylene Substances 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
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Classifications
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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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种含磷氮阻燃单体及其制备方法,涉及阻燃材料。制备方法:取对苯二胺加入到装有溶剂的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳和缚酸剂;将亚磷酸二乙酯用溶剂溶解,再将亚磷酸二乙酯加入容器中反应,反应液过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得反应中间体化合物;将反应中间体化合物溶于溶剂中,加入缚酸剂,水浴,再加入甲基丙烯酰氯反应,过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得含磷氮阻燃单体。反应在室温便可进行,易于控制,操作简单。含磷氮阻燃单体可均聚为大分子阻燃剂,可与其他单体共聚为大分子阻燃剂,可作为反应物进行双键的加成反应。可用于聚烯烃类和环氧树脂材料的阻燃。
Description
技术领域
本发明涉及阻燃材料,尤其是涉及一种含磷氮阻燃单体及其制备方法。
背景技术
高分子材料易于加工、品种多、性能优越、价格便宜,其制品广泛运用于生产、生活的各个方面。但大部分材料阻燃性能较差,危害人们的生命及财产安全。高分子制品的阻燃成为亟需解决的问题。
传统卤素阻燃剂在燃烧时生成较多的烟和释放有刺激性和腐蚀性气体,污染环境,危害人体健康。欧盟已于2006年禁止使用卤素阻燃剂。阻燃剂朝着无卤化、抑烟化、无毒气体化、协同阻燃等方向发展。
磷系阻燃剂阻燃过程中可产生如下过程,如火焰的抑制、熔滴导致的热量损失、含磷酸引起的表面阻断、酸催化炭层的累积和积炭防止炭的进一步氧化等。其分解产物和燃烧产物中腐蚀性、有毒物很少。
氮系阻燃剂燃烧时受热分解后释放出氮气、氨气、二氧化碳、深度氮氧化物等不燃性气体,这些不易燃烧气体阻断了氧的供应,同时带走大部分热量,极大地降低材料的表面温度,从而达到阻燃效果。
提高高分子材料阻燃性能,磷氮协同阻燃受到研究者的重视。中国专利CN104592300A公开了一种磷氮阻燃剂及其制备方法,该磷氮阻燃剂为添加型小分子阻燃剂,其制备过程会伴有部分副反应,致使产品纯度下降。中国专利CN104311818A公开了一种含磷、氮聚合型阻燃剂及其制备方法,该阻燃剂为两官能度的含磷化合物与三官能度的含氮化合物缩聚而成,制备过程产生较多的小分子化合物。中国专利CN104262553A公开一种含磷氮阻燃嵌段共聚物及其制备方法,通过两次聚合将磷、氮元素引入阻燃剂,该方法可调节磷氮含量比。但现有的含磷氮阻燃剂,关于含磷氮阻燃单体的报道较少。
发明内容
本发明的目的在于提供一种含磷氮阻燃单体及其制备方法。
所述含磷氮阻燃单体的化学结构式如下:
所述含磷氮阻燃单体的制备路线如下:
所述含磷氮阻燃单体的制备方法,包括以下步骤:
1)取对苯二胺加入到装有溶剂的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳和缚酸剂;将亚磷酸二乙酯用溶剂溶解,再将亚磷酸二乙酯加入容器中反应,反应液过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得反应中间体化合物;
2)将步骤1)得到的反应中间体化合物溶于溶剂中,加入缚酸剂,水浴,再加入甲基丙烯酰氯反应,过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得含磷氮阻燃单体。
在步骤1)中,所述溶剂可选自N,N-二甲基甲酰胺、四氢呋喃、二氯甲烷、乙腈、氯仿等中的一种;所述缚酸剂可选自三乙胺、吡啶、碳酸氢钠、碳酸钾等中的一种;所述反应的时间可为10~24h;所述对苯二胺、四氯化碳、缚酸剂、亚磷酸二乙酯的摩尔比可为1∶(1~3)∶(1~3)∶(1~1.5);所述将亚磷酸二乙酯加入容器中反应可用恒压滴液漏斗将亚磷酸二乙酯加入容器中。
在步骤2)中,所述溶剂可选自乙酸乙酯、乙腈、N,N-二甲基甲酰胺、二氯甲烷、氯仿、甲苯等中的一种;所述缚酸剂可选自三乙胺、吡啶、碳酸氢钠、碳酸钾等中的一种;所述反应的时间可为8~16h;所述中间体化合物、缚酸剂、甲基丙烯酰氯的摩尔比可为1∶(1~3)∶(1~1.5)。
本发明所述含磷氮阻燃单体可溶于多种溶剂,选择性大,反应条件温和,无需升温反应。该单体含有磷和氮元素,通过协同阻燃作用提高高分子材料的阻燃能力。该单体为可均聚为大分子阻燃剂,可与丙烯酸类、甲基丙烯酸类、甲基丙烯酰胺类等单体共聚为大分子阻燃剂,所含的双键可与其它小分子化合物发生加成反应,拓展其使用范围。
本发明所述含磷氮阻燃单体均聚或共聚所得的大分子阻燃剂可添加到环氧树脂、聚丙烯、聚乙烯等聚合物,在提高材料的阻燃性能的同时,也可改善阻燃剂与基体相容性。
本发明的反应在室温便可进行,易于控制,操作简单。该含磷氮阻燃单体适用范围广,可均聚为大分子阻燃剂,可以与其他单体共聚为大分子阻燃剂,可作为反应物进行双键的加成反应。可用于聚烯烃类和环氧树脂材料的阻燃。
附图说明
图1为实施例1所得到的含磷氮阻燃单体的1H NMR核磁谱图。
图2为实施例1所得到的含磷氮阻燃单体的31P NMR核磁谱图。
具体实施方式
下面通过实施例和附图对本发明作进一步的说明。
实施例1
1)取对苯二胺1.08g(0.01mol),加入到装有N,N-二甲基甲酰胺的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳1.54g(0.01mol)和三乙胺1.01g(0.01mol)。称取亚磷酸二乙酯1.38g(0.01mol),用少量N,N-二甲基甲酰胺溶解,用恒压滴液漏斗将亚磷酸二乙酯滴入容器中。常温反应16h。过滤将三乙胺盐酸盐分离。萃洗、旋转蒸发后,提纯、干燥即得反应中间体化合物。
2)将反应中间体化合物1.22g(0.005mol)溶于乙酸乙酯中,加入三乙胺1.01g(0.01mol),水浴,滴入甲基丙烯酰氯0.5225g(0.005mol),反应8h。过滤将三乙胺盐酸盐分离。萃洗、旋转蒸发后,提纯、干燥后即得该含磷氮阻燃单体。将所得含磷氮阻燃单体进行核磁共振氢谱(图1)与磷谱(图2)的表征。
图1为含磷氮阻燃单体的1H NMR核磁谱图,化学位移5.45ppm和5.76ppm为双键质子峰,化学位移6.93ppm和7.47ppm为苯环质子峰,化学位移5.45ppm和5.76ppm为—NH质子峰,化学位移3.99ppm为—OCH2质子峰,化学位移1.94ppm为与双键相连甲基质子峰,化学位移1.18ppm为与亚甲基相连的甲基质子峰,化学位移2.5ppm为核磁试剂DMSO溶剂峰。且各个位置积分面积比与实际所含氢的个数比一致。图2为含磷氮阻燃单体的31P NMR核磁谱图,磷谱为单峰。氢谱与磷谱说明本发明所述含磷氮阻燃单体成功合成。
实施例2
1)取对苯二胺1.62g(0.015mol),加入到装有四氢呋喃的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳4.62g(0.03mol)和吡啶2.37g(0.01mol)。称取亚磷酸二乙酯2.07g(0.015mol),用少量四氢呋喃溶解,用恒压滴液漏斗将亚磷酸二乙酯滴入容器中。常温反应12h。过滤将吡啶盐酸盐分离。萃洗、旋转蒸发后。提纯、干燥即得反应中间体化合物。
2)将反应中间体化合物2.44g(0.01mol)溶于二氯甲烷中,加入三乙胺2.02g(0.02mol),水浴,滴入甲基丙烯酰氯1.045g(0.01mol),反应10h。过滤将三乙胺盐酸盐分离。萃洗、旋转蒸发后,提纯、干燥后即得该含磷氮阻燃单体。
实施例3
1)取对苯二胺0.54g(0.005mol),加入到装有氯仿的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳2.31g(0.015mol)和碳酸氢钠1.68g(0.01mol)。称取亚磷酸二乙酯0.69g(0.005mol),用少量氯仿溶解,用恒压滴液漏斗将亚磷酸二乙酯滴入容器中。常温反应20h。过滤将氯化钠分离。萃洗、旋转蒸发后,提纯、干燥即得反应中间体化合物。
2)将反应中间体化合物1.22g(0.005mol)溶于乙腈中,加入吡啶0.79g(0.01mol),水浴,滴入甲基丙烯酰氯0.627g(0.006mol),反应12h。过滤将吡啶盐酸盐分离。萃洗、旋转蒸发后,提纯、干燥后即得该含磷氮阻燃单体。
Claims (10)
1.一种含磷氮阻燃单体,其特征在于其化学结构式如下:
2.如权利要求1所述一种含磷氮阻燃单体的制备路线如下:
3.如权利要求1所述一种含磷氮阻燃单体的制备方法,其特征在于包括以下步骤:
1)取对苯二胺加入到装有溶剂的容器中,磁力搅拌至对苯二胺溶解,加入四氯化碳和缚酸剂;将亚磷酸二乙酯用溶剂溶解,再将亚磷酸二乙酯加入容器中反应,反应液过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得反应中间体化合物;
2)将步骤1)得到的反应中间体化合物溶于溶剂中,加入缚酸剂,水浴,再加入甲基丙烯酰氯反应,过滤后将缚酸剂盐酸盐分离,萃洗、旋转蒸发,提纯、干燥后即得含磷氮阻燃单体。
4.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤1)中,所述溶剂选自N,N-二甲基甲酰胺、四氢呋喃、二氯甲烷、乙腈、氯仿中的一种。
5.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤1)中,所述缚酸剂选自三乙胺、吡啶、碳酸氢钠、碳酸钾中的一种。
6.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤1)中,所述反应的时间为10~24h。
7.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤1)中,所述对苯二胺、四氯化碳、缚酸剂、亚磷酸二乙酯的摩尔比为1∶(1~3)∶(1~3)∶(1~1.5);所述将亚磷酸二乙酯加入容器中反应可用恒压滴液漏斗将亚磷酸二乙酯加入容器中。
8.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤2)中,所述溶剂选自乙酸乙酯、乙腈、N,N-二甲基甲酰胺、二氯甲烷、氯仿、甲苯中的一种。
9.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤2)中,所述缚酸剂选自三乙胺、吡啶、碳酸氢钠、碳酸钾中的一种;所述反应的时间可为8~16h。
10.如权利要求3所述一种含磷氮阻燃单体的制备方法,其特征在于在步骤2)中,所述中间体化合物、缚酸剂、甲基丙烯酰氯的摩尔比为1∶(1~3)∶(1~1.5)。
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