CN113333019A - 一种路易斯酸离子液体催化合成有机磷阻燃剂的方法 - Google Patents
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法 Download PDFInfo
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- 239000002841 Lewis acid Substances 0.000 title claims abstract description 64
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 64
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003063 flame retardant Substances 0.000 title claims abstract description 34
- 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 27
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 5
- 239000011574 phosphorus Substances 0.000 title claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000007787 solid Substances 0.000 claims abstract description 47
- 239000000047 product Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
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- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- -1 aryl ethylene oxide Chemical compound 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 claims description 2
- 125000005667 alkyl propylene group Chemical group 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 238000007036 catalytic synthesis reaction Methods 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 24
- 238000001514 detection method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- 229910021485 fumed silica Inorganic materials 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 5
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 3
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridine hydrochloride Substances [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- DMUDPMBKQJNINF-UHFFFAOYSA-N tris(1-chloroethyl) phosphate Chemical compound CC(Cl)OP(=O)(OC(C)Cl)OC(C)Cl DMUDPMBKQJNINF-UHFFFAOYSA-N 0.000 description 1
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
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- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
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Abstract
本发明公开了一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括如下步骤:固体负载催化剂的制备:在有机溶剂中,将路易斯酸离子液体与载体混合,将路易斯酸离子液体负载在载体上,最后干燥即可;催化反应:采用固体负载催化剂催化三氯氧磷或三氯化磷与环氧化合物进行开环反应后获得反应产物;分离纯化:对反应产物进行减压蒸馏除去未反应的物质,抽滤即得目标产物。本发明不仅仅能有效将路易斯酸离子液体催化剂回收利用,并且,在反应后即使不进行后续碱洗、分液、水洗步骤,也能有效避免合成的有机磷阻燃剂在存储过程中容易出现返酸、返浊的缺陷,操作更简单。
Description
技术领域
本发明涉及阻燃剂制备领域,具体涉及一种路易斯酸离子液体催化合成有机磷阻燃剂的方法。
背景技术
多氯联苯和多溴二苯醚虽然作为性能良好的阻燃剂,但因其生物蓄积性、毒性以及难降解而带来的持久性有机污染,已对人类的健康、生命安全和生存环境带来了巨大的威胁,因此已经逐渐在阻燃剂行业中被暂停或禁止。有机磷阻燃剂大都具有热稳定性好、低烟、无毒、效果持久等优点,近年来作为替代多氯联苯和多溴二苯醚的阻燃剂,已被广泛应用于塑料、泡沫、涂料、家具、建筑材料、电子产品等领域。
有机磷阻燃剂中,应用最广的是磷酸酯和亚磷酸酯阻燃剂。其中,磷酸酯或亚磷酸酯的一种制备方法是三氯氧磷或三氯化磷与环氧化合物在催化剂的作用下经过开环反应得到磷酸三酯或亚磷酸三酯。以磷酸三(β-氯丙基)酯(TCPP)制备为例:TCPP是以三氯氧磷在不同种类的催化剂催化下将环氧丙烷开环制备得到粗品。
现有公开的文献中,大多采用路易酸催化剂(无水三氯化铝、氯化镁、四氯化钛、三氯化铁、三氟化硼等),但这些路易斯酸催化剂在空气中极易水解,因此对反应条件要求较为苛刻,同时反应结束后无法回收这些催化剂。并且,利用该方法生产的TCPP粗品一般需要经过碱洗、分液、水洗、蒸馏等后处理才能得到成品,如果不进行后续碱洗、分液、水洗步骤,则会导致产品在50℃稳定性测试中更容易出现返酸、返浊现象;产品的酸值变大将直接导致产品质量不合格,若将其应用在材料中,将直接影响材料性能。
发明内容
因此,本发明要解决的技术问题在于克服现有路易斯酸离子液体催化剂不能回收利用且合成的有机磷阻燃剂在存储过程中容易出现返酸、返浊的缺陷,从而提供一种催化剂可回收利用,且在反应完成后无需碱洗、分液、水洗也可避免产物返酸、返浊的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法。
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括如下步骤:
固体负载催化剂的制备:在有机溶剂中,将路易斯酸离子液体与载体混合,将路易斯酸离子液体负载在载体上,最后干燥即可;
催化反应:采用固体负载催化剂催化三氯氧磷或三氯化磷与环氧化合物进行开环反应后获得反应产物;
分离纯化:对反应产物进行减压蒸馏除去未反应的物质,抽滤即得目标产物。
所述固体负载催化剂中路易斯酸离子液体占固体负载催化剂总质量的1%-90%;优选为10%-70%。
所述路易斯酸离子液体采用常温浸渍或高温回流的方式处理后负载在载体上;所述浸渍或所述回流的处理时间为1-120h,优选为6-72h;
所述干燥的温度不高于100℃,优选为30℃-80℃。
在固体负载催化剂的制备步骤中,所述有机溶剂选自二氯甲烷、二氯乙烷和环己烷;载体选自二氧化硅、氧化铝和分子筛SBA-15;路易斯酸离子液体为[X]-n[路易斯酸],其中,X选自胺、咪唑、吡啶和其衍生物,路易斯酸选自三氯化铝、三氯化铁、氯化镁、氯化亚锡和四氯化钛;n是路易斯酸的摩尔百分数,n为30%~90%。
胺及其衍生物为三烷基胺或三烷基胺盐酸盐。其中,三烷基胺中烷基为乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、异丙基、异丁基、异戊基或异辛基。
咪唑及其衍生物为咪唑、N-烷基咪唑或1,3-二烷基-咪唑或烷基咪唑盐酸盐,其中烷基为甲基、乙基、丙基或丁基。
吡啶及其衍生物为吡啶、烷基吡啶、卤代烷基吡啶或烷基吡啶盐酸盐,其中烷基为甲基、乙基、丙基或丁基,卤代基为氯基或溴基。
所述固体负载催化剂的用量为反应原料总重量的0.001%-2.0%。
所述环氧化合物与三氯氧磷或三氯化磷的摩尔比为(0.5-5):1,优选为(3-4):1。
所述催化反应的过程为:先将固体负载催化剂与三氯氧磷或三氯化磷混合,预加热获得预热反应液,然后将环氧化合物滴加到三氯氧磷或三氯化磷中,滴加时的反应温度为50℃-130℃,优选为60℃-90℃。
环氧化合物加入前,控制三氯氧磷或三氯化磷的温度为35℃-100℃,优选45℃-75℃。
所述减压蒸馏的条件为:在反应温度下,利用真空油泵在0.01-0.1mbar下进行减压蒸馏除去未反应的物质,直至体系内无气泡产生。
所述环氧化合物为环氧乙烷、环氧丙烷、环氧氯丙烷、烷基环氧乙烷、芳基环氧乙烷、烷基环氧丙烷、芳基环氧丙烷、一卤代环氧乙烷、一卤代环氧丙烷、二卤代环氧乙烷或二卤代环氧丙烷,其中烷基为甲基、乙基、丙基或丁基,卤代基为氯基或溴基。
本发明技术方案,具有如下优点:
1、本发明提供的方法,以路易斯酸离子液体负载在载体上作为非均相催化剂,酯化反应结束后催化剂与产品容易分离回收,降低了生产成本;并且,通过该方法制备得到的产物可以直接采用减压蒸馏除去未反应的物质,然后通过抽滤分离即可得到产物,该产物无需进行后续碱洗、分液、水洗步骤,操作更加简单,产物在50℃稳定性测试中不会出现返酸、返浊现象,产品质量稳定。
2、本发明方法回收的催化剂可循环使用至少5次,仍然具有较好的催化效果,效果十分显著。
3、本发明的工艺简单、原料丰富易得,有较好的工业化前景。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
实施例1
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[三乙胺盐酸盐]-50%[三氯化铝]负载在气相二氧化硅上作为固体负载催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。
具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[三乙胺盐酸盐]-50%[三氯化铝];然后采用二氯甲烷50mL作为有机溶剂,将1g路易斯酸离子液体添加到有机溶剂,再将9g气相二氧化硅添加到有机溶剂中,常温浸渍,浸渍48h后,进行真空干燥获得负载量为10%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.6g三氯氧磷和0.20g固体负载催化剂,加热到50±2℃,滴加18.8g环氧丙烷,保持反应温度在70±2℃。滴加完后,继续保温反应2h,在70℃下,利用真空油泵,在0.1mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCPP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为95%,酸值<0.1mgKOH/g。
实施例2
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,本实施例中采用的是实施例1中回收的催化剂进行反应,具体如下:
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.9g三氯氧磷和0.18g实施例1中回收的催化剂,加热到38±2℃,滴加19.3g环氧丙烷,保持反应温度在75±2℃。滴加完后,继续保温反应2h,在75℃下,利用真空油泵,在0.01mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即TCPP产品。
经过检测并计算得到,该产品的产率94%,酸值<0.1mgKOH/g。
实施例3
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[1-丁基吡啶盐酸盐]-60%[三氯化铝]负载在SBA-15分子筛上作为固体负载催化剂,进行酯化反应制得磷酸三(α-氯乙基)酯(TCEP)。具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[1-丁基吡啶盐酸盐]-60%[三氯化铝];然后采用环己烷30mL作为有机溶剂,将1g路易斯酸离子液体添加到有机溶剂中,再将4g SBA-15分子筛添加到有机溶剂中,高温回流,回流温度为100℃,回流时间为12h,回流后进行真空干燥获得负载量为20%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.6g三氯氧磷和上述0.20g固体负载催化剂,加热到50±2℃,滴加14.3g环氧乙烷,保持反应温度在60±2℃。滴加完后,继续保温反应2h,在60℃下,利用真空油泵,在0.1mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCEP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为93%,酸值<0.1mgKOH/g。
实施例4
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[1-丁基-3-甲基咪唑盐酸盐]-50%[三氯化铝]负载在氧化铝上作为固体负载催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[1-丁基-3-甲基咪唑盐酸盐]-50%[三氯化铝];然后采用二氯乙烷60mL作为有机溶剂,将1g路易斯酸离子液体添加到有机溶剂中,再将9g氧化铝添加到有机溶剂中,常温浸渍,浸渍6h后,进行真空干燥获得负载量为10%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.7g三氯氧磷和上述0.20g固体负载催化剂,加热到50±2℃,滴加18.6g环氧丙烷,保持反应温度在80±2℃。滴加完后,继续保温反应2h,在80℃下,利用真空油泵,在0.01mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCPP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为95%,酸值<0.1mgKOH/g。
实施例5
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[1-丁基-3-甲基咪唑盐酸盐]-50%[三氯化铁]负载在气相二氧化硅上作为固体负载催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[1-丁基-3-甲基咪唑盐酸盐]-50%[三氯化铁];然后采用二氯甲烷30mL作为有机溶剂,将0.5g路易斯酸离子液体添加到有机溶剂中,再将4.5g气相二氧化硅添加到有机溶剂中,常温浸渍,浸渍24h后,进行真空干燥获得负载量为10%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.7g三氯氧磷和上述0.20g固体负载催化剂,加热到50±2℃,滴加18.6g环氧丙烷,保持反应温度在80±2℃。滴加完后,继续保温反应2h,在80℃下,利用真空油泵,在0.01mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCPP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为93%,酸值<0.1mgKOH/g。
实施例6
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[三乙胺盐酸盐]-50%[三氯化铁]负载在气相二氧化硅上作为固体负载催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。
具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[三乙胺盐酸盐]-50%[三氯化铁];然后采用二氯甲烷80mL作为有机溶剂,将0.5g路易斯酸离子液体添加到有机溶剂中,再将9.5g气相二氧化硅添加到有机溶剂中,常温浸渍,浸渍24h后,进行真空干燥获得负载量为5%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.7g三氯氧磷和上述0.40g固体负载催化剂,加热到50±2℃,滴加18.6g环氧丙烷,保持反应温度在75±2℃。滴加完后,继续保温反应2h,在75℃下,利用真空油泵,在0.1mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCPP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为86%,酸值<0.1mgKOH/g。
实施例7
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,[三乙胺]-50%[三氯化铝]负载在气相二氧化硅上作为固体负载催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。具体过程如下:
固体负载催化剂的制备:采用CN102807581A中相同的制备方法,制备出路易斯酸离子液体,该路易斯酸离子液体为[三乙胺]-50%[三氯化铝];然后采用二氯甲烷40mL作为有机溶剂,将5g路易斯酸离子液体添加到有机溶剂,再将5g气相二氧化硅添加到有机溶剂中,常温浸渍,浸渍24h后,进行真空干燥获得负载量为50%的固体负载催化剂。
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.6g三氯氧磷和0.10g固体负载催化剂,加热到50±2℃,滴加18.8g环氧丙烷,保持反应温度在75±2℃。滴加完后,继续保温反应2h,在75℃下,利用真空油泵,在0.1mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,趁热抽滤得到无色透明的液体,即为TCPP产品;抽滤获得的固体物质即为回收的催化剂。
经过检测并计算得到,该产品的产率为94%,酸值<0.1mgKOH/g。
对比例1
一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,包括以三氯氧磷和环氧丙烷为原料,采用实施例1中制备得到的[三乙胺盐酸盐]-50%[三氯化铝]作为催化剂,进行酯化反应制得磷酸三(β-氯丙基)酯(TCPP)。具体过程如下:
在配有磁力搅拌子、磨口温度计、回流冷凝管和恒压滴液漏斗的三颈烧瓶(250mL)中加入15.6g三氯氧磷和0.020g固体负载催化剂,加热到50±2℃,滴加18.8g环氧丙烷,保持反应温度在70±2℃。滴加完后,继续保温反应2h,在70℃下,利用真空油泵,在0.1mbar的条件下减压蒸馏除未反应的物质,至无气泡产生,减压蒸馏后得到产物TCPP。
经过检测并计算得到,该产物TCPP的产率为95%,酸值<0.1mgKOH/g。
采用实施例和对比例的产物在50℃进行稳定性测试,稳定性测试方法如下:取500g样品于样品瓶,放于恒温50℃烘箱内,放置7天后,取出进行检测。试验结果如下表1所示。
表1
通过上述检测结果可知:本发明的方法,不仅仅能够实现路易斯酸离子液体催化剂的回收利用,降低制备成本,并且,还能简化操作步骤,即使不进行反应后的后续碱洗、分液、水洗步骤,也能避免合成的有机磷阻燃剂在存储过程中不会出现返酸、返浊的问题,操作更加简单。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
1.一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,包括如下步骤:
固体负载催化剂的制备:在有机溶剂中,将路易斯酸离子液体与载体混合,将路易斯酸离子液体负载在载体上,最后干燥即可;
催化反应:采用固体负载催化剂催化三氯氧磷或三氯化磷与环氧化合物进行开环反应后获得反应产物;
分离纯化:对反应产物进行减压蒸馏除去未反应的物质,抽滤即得目标产物。
2.根据权利要求1所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述固体负载催化剂中路易斯酸离子液体占固体负载催化剂总质量的1%-90%;优选为10%-70%。
3.根据权利要求1或2所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述路易斯酸离子液体采用常温浸渍或高温回流的方式处理后负载在载体上;所述浸渍或所述回流的处理时间为1-120h,优选为6-72h;
所述干燥的温度不高于100℃,优选为30℃-80℃。
4.根据权利要求1-3任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,在固体负载催化剂的制备步骤中,所述有机溶剂选自二氯甲烷、二氯乙烷和环己烷;载体选自二氧化硅、氧化铝和分子筛SBA-15;路易斯酸离子液体为[X]-n[路易斯酸],其中,X选自胺、咪唑、吡啶和其衍生物,路易斯酸选自三氯化铝、三氯化铁、氯化镁、氯化亚锡和四氯化钛;n是路易斯酸的摩尔百分数,n为30%~90%。
5.根据权利要求1-4任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述固体负载催化剂的用量为反应原料总重量的0.001%-2.0%。
6.根据权利要求1-5任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述环氧化合物与三氯氧磷或三氯化磷的摩尔比为(0.5-5):1,优选为(3-4):1。
7.根据权利要求1-6任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述催化反应的过程为:先将固体负载催化剂与三氯氧磷或三氯化磷混合,预加热获得预热反应液,然后将环氧化合物滴加到三氯氧磷或三氯化磷中,滴加时的反应温度为50℃-130℃,优选为60℃-90℃。
8.根据权利要求1-7任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,环氧化合物加入前,控制三氯氧磷或三氯化磷的温度为35℃-100℃,优选45℃-75℃。
9.根据权利要求1-8任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述减压蒸馏的条件为:在反应温度下,在0.01-0.1mbar下进行减压蒸馏至体系内无气泡产生。
10.根据权利要求1-8任一项所述的一种路易斯酸离子液体催化合成有机磷阻燃剂的方法,其特征在于,所述环氧化合物为环氧乙烷、环氧丙烷、环氧氯丙烷、烷基环氧乙烷、芳基环氧乙烷、烷基环氧丙烷、芳基环氧丙烷、一卤代环氧乙烷、一卤代环氧丙烷、二卤代环氧乙烷或二卤代环氧丙烷,其中烷基为甲基、乙基、丙基或丁基,卤代基为氯基或溴基。
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