CN1167488A - 双(烃基膦酸)烃基酯的制备方法 - Google Patents
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- 239000002904 solvent Substances 0.000 description 7
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- GRJISTUCPUHFOJ-UHFFFAOYSA-N 1,3-dibromo-2,2-dimethylpropane-1,3-diol Chemical class BrC(O)C(C)(C(O)Br)C GRJISTUCPUHFOJ-UHFFFAOYSA-N 0.000 description 1
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- 229940122361 Bisphosphonate Drugs 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
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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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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Abstract
本发明涉及双(二烃基膦酸)烃基酯如双(二芳基膦酸)烃基酯的合成方法，其中包括使不稳定的含烃基二醇如含芳基的二醇与二烃基磷酰卤如二苯基磷酰氯在路易斯酸催化剂如MgCl2存在下在有效量(例如多达约100％(重)二醇和磷酰卤)液态烃例如脂族烃如庚烷或芳烃如甲苯存在下反应以便促进脱除卤化氢副产物，从而提高双(二烃基膦酸)烃基酯的产率。
Description
通过烃基二醇与二烃基膦酰卤在路易斯酸催化剂存在下发生反应来合成双(二羟基膦酸)烃基酯的方法属于公知内容。例如J.J.Giammaria等在US3254 973中描述了一种通用反应并且采用氮气吹扫反应介质以及脱除副产物氯化氢。J.A.Albright在U.S.4133 846中描述了一种无氮气吹扫的类似反应。最近，T.Zama等在U.S.4343 732中介绍了特定二醇、磷酰氯与特定醇和酚在作为催化剂的氯化铝存在下进行的反应(第4栏，第21～22行)，其中使用甲苯与二甲苯之类的惰性溶剂，但是未表明使用溶剂的优点。
当用于上述反应的二醇具有亚烷基的特性如为新戊二醇时，含有所需二磷酸酯化合物的反应混合物通常包含不需要的会降低含二磷酸酯组合物的热稳定性的环状副产物如和磷酸三苯酯。若所用的二醇含有与如双酚A中的苯基部分相连接的亚烷基的话，则该杂质举例来说会是二苯基膦酸异丙基苯酯。就上述副产物的形成过程而言，这种二醇的不稳定性是由于诸如在支链新戊二醇试剂之类情况下发生的分子内反应与重排和/或诸如在含有2个与亚烷基即-C(CH3)2-连接在一起的苯基的双酚A之类情况下发生的二醇分子的断裂造成的。“含不稳定烃基”一词被用于表示这两类二醇的特征。
本发明涉及双(二烃基膦酸)烃基酯如双(二芳基膦酸)烃基酯的合成方法，其中包括使不稳定的含烃基二醇如含亚烷基或亚烷基桥接芳基的二醇与二烃基磷酰卤如二苯基磷酰氯在路易斯酸催化剂如MgCl2存在下在有效量(例如多达约100％(重)二醇和磷酰卤)液态烃例如脂族烃如庚烷存在下反应以便促进脱除卤化氢副产物，从而提高双(二烃基膦酸)烃基酯的产率，与此同时降低不需要的环状副产物的生成量。
本发明的目的在于合成下式所示双膦酸烃基酯
式中R为烃基(如被取代或未被取代芳基)，R′可以是亚烷基如由新戊二醇衍生的亚烷基或含亚烷基桥接的亚芳基如由双酚A衍生的基团。
用于该方法的二烃基磷酰卤反应物如下式所示其中R为烃基(例如被取代或未被取代的芳基)，X为卤素。优选化合物为二芳基膦酰氯(例如二苯基磷酰氯)。在下列二羟基反应中，反应物存在量(以摩尔为基准)优选约为2∶1。
该二羟基反应物(HOR′OH)用于在目的化合物中形成桥基R′。该反应在升温(约高于20℃)下但不得高至足以引发环状副产物和/或磷酸三羟基酯的温度下采用有效量(例如约0.01％～1％(重)二烃基磷酰卤)路易斯酸催化剂进行。该催化剂包括过渡金属卤化物如MgCl2、AlCl3、ZnCl2、TiCl4等。
本发明的实施有赖于附加量液态烃，例如脂族烃如庚烷或芳族溶剂如甲苯的存在，以便作为“追击者”有助于排除卤化氢副产物。一般地，溶剂用量高达约100％(重)二醇与磷酰卤，以多达约50％为佳，以多达约20％为更佳。采用这种液态烃能够在比不存在液态烃的情况更低的温度下制成高纯度产物。在此较低温度下不易形成不需要的副产物如在使用双酚A的情况下产生磷酸三苯酯与二苯基膦酸异丙烯酯以及在使用新戊二醇的情况下产生环状磷酸酯。
下列实施例描述本发明。
实施例1
将二苯基磷酰氯(0.5摩尔)、双酚A(0.25摩尔)、MgCl2(2.63×10-1摩尔)与庚烷(20％重)回流加热(约99℃)6小时。借助红外分析监测羟基官能团的消失。反应混合物的液相色谱分析(％面积)给出下列组成：1.5％磷酸三苯酯；0.49％二苯基膦酸异丙烯基苯酯；1.7％二苯基膦酸双酚A酯；92.3％在实施例2-5中的表中被称作“P2”的双(二苯基膦酸)双酚A酯和2.4％含3个磷原子的双(二苯基膦酸)双酚A酯低聚物。
实施例2-5
在这些实施例中，确定温度、氮气吹扫与庚烷浓度对实施例1中产物纯度的影响(下表中给出的所有产物数量均以面积百分比为基准，磷酸三苯酯TPP以重量百分比为基准)：
| 实施例编号 | 时间(小时) | 温度(℃) | 庚烷(wt％) | N2 | A* | TPP | 半酯 | P2 |
| 2 | 6.5 | 115℃ | 10 | 无 | 2.5 | 1.5 | 0.79 | 91.2 |
| 3 | 5 | 130 | 0 | 无 | 14.7 | 3.5 | 3.1 | 65.9 |
| 4 | 13 | 120 | 0 | 有 | 8.5 | 1.9 | 0.42 | 84.7 |
| 5 | 5.5 | 150 | 0 | 无 | 9.6 | 4.3 | 0.27 | 70.6 |
*＝“A”被用于识别二苯基膦酸异丙烯基苯酯。
实施例6-10
通过加热回流1.1mol(295.5g)二苯基磷酰氯、0.5mol(52.0g)新戊二醇、0.2g MgCl2和100ml非极性溶剂制备双(二苯基膦酸)新戊二醇酯。反应完毕，通过真空汽提回收溶剂并且用2％硫酸水溶液、2％NaOH水溶液和水洗涤反应混合物。脱除痕量水后得到下列结果：
*ISOPAR E：EXXON公司产品。试验9的溶剂用量为50ml，而试验10则为100ml。
| 试验编号 | 溶剂 | 试验温度(℃) | 时间(小时) | 产率(％) |
| 6 | 己烷 | 70 | 20 | 94 |
| 7 | 庚烷 | 95 | 17 | 92 |
| 8 | 异链烷烃* | 115 | 11 | 90 |
| 9 | 异链烷烃* | 130 | 11 | 93 |
| 10 | 二甲苯 | 140 | 8 | 95 |
| 11 | 无 | 100 | 17 | 85 |
高压液相色谱分析
| 试验编号 | 双膦酸酯(面积％) | 磷酸三苯酯(wt％) | 环状副产物(面积％) |
| 6 | 96.3 | 1.4 | 1.1 |
| 7 | 93.1 | 1.3 | 2.5 |
| 8 | 96.7 | 1.2 | 1.4 |
| 9 | 76.3 | 15.2 | 3.0 |
| 10 | 62.5 | 18.9 | 7.4 |
| 11 | 88.6 | 6.2 | 2.2 |
实施例12
通过回流加热(117℃)约1.1mol(295.5g)二苯基磷酰氯、约0.5mol(131.0g)二溴代新戊二醇、0.2g MgCl2和100ml ISORAR E异链烷烃溶剂来制备双(二苯基膦酸)二溴新戊二醇酯。在此温度下经过15小时后，通过分层去除溶剂。如实施例6-10所述洗涤反应混合物。得到348g油(96％产率)，通过高压液相色谱在81.5％面积评估目的产物。副产物为磷酸三苯酯(8.2％重)和环状phosphorinane(2.6％面积)。
上述实施例用于描述本发明的某些优选实施方案，因此不构成对本发明的限制。本发明的保护范围如权利要求书所述。
Claims (12)
1.双(二烃基膦酸)烃基酯的合成方法，其中包括使不稳定的含烃基二醇与二烃基磷酰卤在路易斯酸催化剂存在下反应其改进之处包括额外存在有效量液体烃以便促进脱除卤化氢副产物与降低反应温度，与此同时提高双(二烃基膦酸)烃基酯的产率与纯度。
2.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯。
3.按照权利要求1的方法，其中烃基二醇选自含亚烷基二醇与含亚烷基桥接芳基的二醇。
4.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯，烃基二醇为含亚烷基的二醇。
5.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯，烃基二醇为含亚烷基桥接芳基的二醇。
6.按照权利要求1的方法，其中路易斯酸催化剂为MgCl2。
7.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯，烃基二醇选自含亚烷基二醇和含亚烷基桥接芳基的二醇，路易斯酸催化剂为MgCl2。
8.按照权利要求1的方法，其中液态烃为脂族烃。
9.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯，烃基二醇选自含亚烷基二醇和含亚烷基桥接芳基的二醇，路易斯酸催化剂为MgCl2，液态烃为脂族烃。
10.按照权利要求1的方法，其中液态烃存在量多达约50％(重)二醇与磷酰卤。
11.按照权利要求9的方法，其中液态烃存在量多达约50％(重)二醇与磷酰卤。
12.按照权利要求1的方法，其中双(二烃基膦酸)烃基酯为双(二芳基膦酸)烃基酯，烃基二醇选自含亚烷基二醇和含亚烷基桥接芳基的二醇，路易斯酸催化剂为MgCl2，液态烃为脂族烃，该方法在高于约20℃下进行。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/332,671 | 1994-11-01 | ||
| US08/332,671 US6136997A (en) | 1994-11-01 | 1994-11-01 | Process for the formation of hydrocarbyl BIS(hydrocarbyl phosphate) |
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| Publication Number | Publication Date |
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| CN1167488A true CN1167488A (zh) | 1997-12-10 |
| CN1076354C CN1076354C (zh) | 2001-12-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95196541A Expired - Fee Related CN1076354C (zh) | 1994-11-01 | 1995-10-20 | 双(烃基磷酸)烃基酯的制备方法 |
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| Country | Link |
|---|---|
| US (1) | US6136997A (zh) |
| EP (1) | EP0789703B1 (zh) |
| JP (1) | JPH10508021A (zh) |
| CN (1) | CN1076354C (zh) |
| DE (1) | DE69530503T2 (zh) |
| WO (1) | WO1996013508A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616945B (zh) * | 2006-11-20 | 2012-10-03 | 苏普雷斯塔有限责任公司 | 含有阻燃剂混合物的聚氨酯泡沫 |
| CN110143980A (zh) * | 2019-06-05 | 2019-08-20 | 南京恒桥化学技术材料有限公司 | 一种粉末型双酚a双（二苯基磷酸酯）及其制备方法 |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750756A (en) * | 1994-11-01 | 1998-05-12 | Akzo Nobel Nv | Process for the formation of hydrocarbyl bis(hydrocarbyl phosphate) |
| JP2001508401A (ja) * | 1996-06-13 | 2001-06-26 | グレート・レークス・ケミカル・コーポレーション | アリールジホスフェートエステル類の製造法 |
| GB9715770D0 (en) | 1997-07-25 | 1997-10-01 | Nycomed Imaging As | Process |
| US6613820B2 (en) | 1997-08-29 | 2003-09-02 | General Electric Company | Polycarbonate resin composition |
| US6486241B2 (en) | 1997-08-29 | 2002-11-26 | General Electric Company | Polycarbonate resin composition |
| US6388120B1 (en) | 1998-02-13 | 2002-05-14 | Pabu Services, Inc. | Continuous process for the manufacture of phosphoric acid esters |
| US6031035A (en) * | 1998-02-13 | 2000-02-29 | Great Lakes Chemical Corporation | Process for making and using bisaryl diphosphates |
| DE10036057A1 (de) * | 2000-07-25 | 2002-02-07 | Bayer Ag | Flammwidrige Polycarbonat-Zusammensetzungen |
| US6399685B1 (en) * | 2000-12-11 | 2002-06-04 | Albemarle Corporation | Purification of arylene polyphosphate esters |
| GB2405148B (en) * | 2002-05-07 | 2006-08-23 | Akzo Nobel Nv | Neopentyl glycol bis(diaryl phosphate) esters |
| JP4011441B2 (ja) * | 2002-05-10 | 2007-11-21 | ダイハツ工業株式会社 | 車両のインストルメントパネル構造 |
| CN100362001C (zh) * | 2005-12-06 | 2008-01-16 | 河北工业大学 | 一种缩聚型磷酸酯及其制备方法和应用 |
| SE1100784A1 (sv) * | 2011-10-21 | 2013-01-08 | Perstorp Ab | Ny fosfatförening |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520090A (en) * | 1947-12-30 | 1950-08-22 | Monsanto Chemicals | Polyphosphates of divalent aryl hydrocarbons |
| US2952666A (en) * | 1957-09-11 | 1960-09-13 | Eastman Kodak Co | Phosphoro-polyesters and polyesterurethanes derived from phosphorodichloridates and aliphatic glycols |
| US3254973A (en) * | 1962-07-31 | 1966-06-07 | Socony Mobil Oil Co Inc | Gasolines and phosphorus-containing additives therefor |
| US3642959A (en) * | 1968-10-11 | 1972-02-15 | Stauffer Chemical Co | Process for preparing alkyl aryl phosphates |
| US3737487A (en) * | 1970-08-19 | 1973-06-05 | Stauffer Chemical Co | Process for preparing aryl alkyl phosphates |
| US4133846A (en) * | 1977-06-30 | 1979-01-09 | Velsicol Chemical Corporation | Hydroxyl containing phosphates and polyphosphates |
| JPS5661446A (en) * | 1979-10-24 | 1981-05-26 | Ajinomoto Co Inc | Stabilizer for halogen-containing resin |
| US5281741A (en) * | 1990-11-13 | 1994-01-25 | Fmc Corporation | Process for preparing aryldiphosphate esters |
| AU655284B2 (en) * | 1991-06-14 | 1994-12-15 | Ethyl Corporation | Organic phosphates and their preparation |
-
1994
- 1994-11-01 US US08/332,671 patent/US6136997A/en not_active Expired - Lifetime
-
1995
- 1995-10-20 JP JP8514639A patent/JPH10508021A/ja not_active Withdrawn
- 1995-10-20 DE DE69530503T patent/DE69530503T2/de not_active Expired - Fee Related
- 1995-10-20 CN CN95196541A patent/CN1076354C/zh not_active Expired - Fee Related
- 1995-10-20 WO PCT/US1995/013408 patent/WO1996013508A1/en active IP Right Grant
- 1995-10-20 EP EP95937516A patent/EP0789703B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101616945B (zh) * | 2006-11-20 | 2012-10-03 | 苏普雷斯塔有限责任公司 | 含有阻燃剂混合物的聚氨酯泡沫 |
| CN110143980A (zh) * | 2019-06-05 | 2019-08-20 | 南京恒桥化学技术材料有限公司 | 一种粉末型双酚a双（二苯基磷酸酯）及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0789703B1 (en) | 2003-04-23 |
| US6136997A (en) | 2000-10-24 |
| WO1996013508A1 (en) | 1996-05-09 |
| EP0789703A4 (en) | 1998-02-25 |
| EP0789703A1 (en) | 1997-08-20 |
| DE69530503D1 (de) | 2003-05-28 |
| JPH10508021A (ja) | 1998-08-04 |
| CN1076354C (zh) | 2001-12-19 |
| DE69530503T2 (de) | 2004-01-29 |
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