CN1174199A - 2,2′,2″-次氮基[三乙基-三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]的制备方法 - Google Patents
2,2′,2″-次氮基[三乙基-三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]的制备方法 Download PDFInfo
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- CN1174199A CN1174199A CN97112792A CN97112792A CN1174199A CN 1174199 A CN1174199 A CN 1174199A CN 97112792 A CN97112792 A CN 97112792A CN 97112792 A CN97112792 A CN 97112792A CN 1174199 A CN1174199 A CN 1174199A
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- tertiary amine
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- acid ester
- phosphorous acid
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- -1 3, 3', 5, 5' -tetra -tert -butyl -1, 1' -biphenyl -2, 2' -diyl Chemical group 0.000 title claims abstract description 14
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title abstract 2
- 239000007983 Tris buffer Substances 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229960004418 trolamine Drugs 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- DQTRYXANLKJLPK-UHFFFAOYSA-N chlorophosphonous acid Chemical compound OP(O)Cl DQTRYXANLKJLPK-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- MUMQYXACQUZOFP-UHFFFAOYSA-N Dialifor Chemical compound C1=CC=C2C(=O)N(C(CCl)SP(=S)(OCC)OCC)C(=O)C2=C1 MUMQYXACQUZOFP-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- GJXAPHONGGLIOM-UHFFFAOYSA-N oxaphosphepine Chemical compound O1C=CC=CC=P1 GJXAPHONGGLIOM-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
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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)
Abstract
本发明涉及缩写为NTTBP的式Ⅰ2,2’,2”-次氮基[三乙基-三(3,3’,5,5’-四叔丁基-1,1’-联苯-2,2’－二基)亚磷酸酯]的制备方法,其中以氯－亚磷酸酯∶叔胺∶三乙醇胺为3.3—2.9∶3.3—2.9∶1的摩尔比将式Ⅱ的氯-亚磷酸酯加入三乙醇胺和叔胺的溶液中,继续搅拌并且在反应结束之后分离叔胺的盐酸盐。NTTBP是有价值的聚合物稳定剂。
Description
2，2’，2”-次氮基[三乙基-三(3，3’，5，5’-四叔丁基-1，1’-联苯-2，2’-二基)亚磷酸酯](缩写为NTTBP)是有价值的聚合物稳定剂(见US4,318,845和US4,374,219)，并且除了无定形固相变体外(US5,276,076和US5,373,040)，还以三种不同的结晶变体存在(α变体：WO94/12509，β变体：WO94/12508和γ变体：WO95/03587)。
按照US4,318,845(实施例4)，目前NTTBP的制备方式如下，在第一方法步骤中，以三氯化磷和2，2’，4，4’-四叔丁基-O，O’-双酚为原料，制备于溶液中的6-氯-2，4，8，10-四叔丁基苯并〔d，f〕〔1，3，2〕二氧杂phosphepin(缩写为氯-亚磷酸酯)并向溶液中滴加三乙醇胺和三乙胺的混合物。反应结束后，吸滤出三乙胺盐酸盐，蒸馏去除溶剂。作为粗产物留下无定形固相变体的NTTBP。从乙腈/甲苯中二次重结晶后得到白色粉末状的NTTBP，其熔点为121-134℃，产率仅略大于70％，并不令人满意。
因此需要提供一种方法，由该方法可以以工艺简单方式以高产率获得NTTBP。
我们出乎预料地发现，当首先引入三乙醇胺/叔胺溶液而不是氯亚磷酸酯溶液，然后向其中加入氯亚磷酸酯溶液，则能以直至94％的产率获得NTBBP。
因此本发明涉及式I的2，2’，2”-次氮基[三乙基-三(3，3’，5，5’-四叔丁基-1，1’-联苯-2，2’-二基)亚磷酸酯]的制备方法，
其中以氯-亚磷酸酯∶叔胺∶三乙醇胺为3.3-2.9∶3.3-2.9∶1，优选3∶3∶1的摩尔比将式II的氯-亚磷酸酯加入三乙醇胺和叔胺的溶液中，并且在反应结束之后分离叔胺的盐酸盐。
合适的叔胺例如有三甲胺、三乙胺、三正丙基胺、二异丙基甲基胺、二异丙基乙基胺或三正丁基胺。尤其优选三乙胺。
式II的氯-亚磷酸酯可按US4,318,845和US4,374,219的实施例A或实施例1制备。但其制备优选按Helv.-Chim.Acta76，900(1993)进行，该文献结合入本文以作参考。
本发明方法如下进行，将三乙醇胺和叔胺溶于一种合适的溶剂中。合适的溶剂例如有二氯甲烷、甲苯、二甲苯如邻二甲苯、四氢呋喃、乙腈或这些溶剂的混合物。然而在充分搅拌下向该溶液中加入于上述溶剂中的氯-亚磷酸酯。其中反应温度宜在-10至50℃，优选-5至0℃之间。在优选于室温下继续搅拌较长时间后，反应结束，吸滤出胺的盐酸盐并洗涤。蒸馏滤液以除去溶剂。蒸馏可在真空或常压下进行。由此得到约95％纯的NTTBP粗产物。如果在真空中直至120℃内温(于1毫巴)除去溶剂，则得到无定形固体变体。如果于常压下蒸馏除去溶剂，则在约160-180℃的温度下得到熔体变体的NTTBP。该方法宜在隔绝水分的条件下进行，以防止减少产率的水解。
取决于所需变体，这些粗产物可以借助于一定的溶剂被转化为纯α或β变体。
WO94/12508建议的溶剂适于获得β变体。出乎预料地发现，1-丁醇也适于将粗产物转化为β变体。
实施例1
将24.32克(0.163摩尔)三乙醇胺和49.48克(0.489摩尔)三乙胺溶于200毫升邻二甲苯和50毫升四氢呋喃中。在搅拌下，历时75分钟将232克(0.489摩尔)氯-亚磷酸酯于800毫升邻二甲苯中的热(60℃)溶液滴加入于-5至0℃的上述混合物中，滴加结束之后，加热混合物至室温并随后搅拌约60小时。接着吸滤出胺的盐酸盐并用邻二甲苯洗涤。常压下蒸馏滤液直至内温达160-176℃。接着将所得的熔融物迅速倾入500毫升丙酮中。获得透明溶液，冷却下结晶出NTTBP，吸滤并用丙酮冲洗，接着于真空50℃下干燥。得到224.4克熔点为154-158℃的α变体产物(按31-P-NMR测得的纯度为99.4％)。产率为理论值的94％。
实施例2
强烈搅拌下，例1制得的熔融物慢慢加至690毫升1-丁醇中。慢慢结晶出产物。随后搅拌约15小时后，吸滤出产物，洗涤并在真空柜于80-90℃干燥。得到206克熔点为192-198℃的β变体的产物(根据31-P-NMR的纯度为92.6％)。产率为理论值的86％。
Claims (6)
1.一种制备式I的2，2’，2”-次氮基[三乙基-三(3，3’，5，5’-四叔丁基-1，1’-联苯-2，2’-二基)亚磷酸酯](NTTBP)的方法
其中包括以氯-亚磷酸酯∶叔胺∶三乙醇胺为3.3-2.9∶3.3-2.9∶1的摩尔比将式II的氯-亚磷酸酯加入三乙醇胺和叔胺的溶液中，并且在反应结束之后分离叔胺的盐酸盐
2.根据权利要求1的方法，其中氯-亚磷酸酯∶叔胺∶三乙醇胺的摩尔比为3∶3∶1。
3.根据权利要求1或2的方法，其中叔胺为三乙胺。
4.根据权利要求1-3中任一项的方法，其中冷却引入的胺溶液至0℃或更低。
5.根据权利要求1-4中任一项的方法，其中随后于室温下搅拌混合物。
6.根据权利要求1-5中任一项的方法，其中在隔绝水分条件下进行该方法。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19624425A DE19624425A1 (de) | 1996-06-19 | 1996-06-19 | Verfahren zur Herstellung von 2,2',2"-Nitrilo(triethyl-tris(3,3',5,5'-tetra- tert.-butyl-1,1'-biphenyl-2,2'-diyl)phosphit" |
| DE19624425.0 | 1996-06-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1174199A true CN1174199A (zh) | 1998-02-25 |
Family
ID=7797353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112792A Pending CN1174199A (zh) | 1996-06-19 | 1997-06-17 | 2,2′,2″-次氮基[三乙基-三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]的制备方法 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0816370A1 (zh) |
| JP (1) | JPH1059988A (zh) |
| KR (1) | KR980002057A (zh) |
| CN (1) | CN1174199A (zh) |
| DE (1) | DE19624425A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585135A (zh) * | 2012-03-05 | 2012-07-18 | 中北大学 | 聚氨酯用反应型膨胀型阻燃剂及其合成方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004731A1 (ja) * | 2005-07-05 | 2007-01-11 | Sumitomo Chemical Company, Limited | 亜リン酸エステル類の結晶 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374219A (en) * | 1980-11-24 | 1983-02-15 | Ciba-Geigy Corporation | Alkanolamine ester of 1,1-biphenyl-2,2-diyl-and alkylidene-1,1-biphenyl-2,2-diyl-cyclic phosphites |
| US4318845A (en) * | 1980-11-24 | 1982-03-09 | Ciba-Geigy Corporation | Alkanolamine esters of 1,1'-biphenyl-2,2'-diyl-and alkylidene-1,1'-biphenyl-2,2'-diyl-cyclic phosphites |
| US5310890A (en) * | 1992-07-22 | 1994-05-10 | Ciba-Geigy Corporation | Carbohydrate substituted dibenzoi(d,g)(1,3,2)dioxaphosphocin stabilizers |
| US5334739A (en) * | 1992-11-30 | 1994-08-02 | Ciba-Geigy Corporation | Process an alpha monoclinic crystalline modification of 2,2',2"-nitrilo[triethyl-tris-(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite] |
-
1996
- 1996-06-19 DE DE19624425A patent/DE19624425A1/de not_active Withdrawn
-
1997
- 1997-06-10 EP EP97109378A patent/EP0816370A1/de not_active Withdrawn
- 1997-06-17 CN CN97112792A patent/CN1174199A/zh active Pending
- 1997-06-17 KR KR1019970024980A patent/KR980002057A/ko not_active Application Discontinuation
- 1997-06-17 JP JP9160035A patent/JPH1059988A/ja not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585135A (zh) * | 2012-03-05 | 2012-07-18 | 中北大学 | 聚氨酯用反应型膨胀型阻燃剂及其合成方法 |
| CN102585135B (zh) * | 2012-03-05 | 2013-08-07 | 中北大学 | 聚氨酯用反应型膨胀型阻燃剂及其合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR980002057A (ko) | 1998-03-30 |
| EP0816370A1 (de) | 1998-01-07 |
| DE19624425A1 (de) | 1998-01-08 |
| JPH1059988A (ja) | 1998-03-03 |
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