CN102639544B - 由磷酰氯和二醇或者聚二醇的单烷基醚制造磷酸酯的方法 - Google Patents
由磷酰氯和二醇或者聚二醇的单烷基醚制造磷酸酯的方法 Download PDFInfo
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- CN102639544B CN102639544B CN201080044722.7A CN201080044722A CN102639544B CN 102639544 B CN102639544 B CN 102639544B CN 201080044722 A CN201080044722 A CN 201080044722A CN 102639544 B CN102639544 B CN 102639544B
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- Prior art keywords
- monoether
- phosphoryl chloride
- glycol
- reaction
- mixture
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- 238000000034 method Methods 0.000 title claims description 16
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000001346 alkyl aryl ethers Chemical class 0.000 title description 9
- 229920000151 polyglycol Polymers 0.000 title description 3
- 239000010695 polyglycol Substances 0.000 title description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 title description 2
- 150000002334 glycols Chemical class 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- -1 Phosphate ester compounds Chemical class 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 37
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 claims description 32
- 125000004076 pyridyl group Chemical group 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 3
- 235000013861 fat-free Nutrition 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 55
- 239000000203 mixture Substances 0.000 abstract description 46
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- 229920001515 polyalkylene glycol Polymers 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 55
- 239000000047 product Substances 0.000 description 28
- 235000021317 phosphate Nutrition 0.000 description 25
- 239000008151 electrolyte solution Substances 0.000 description 24
- 229910052744 lithium Inorganic materials 0.000 description 17
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Abstract
在存在每摩尔磷酰氯至少三摩尔无脂肪族氮原子的吡啶基化合物的情况下,通过使磷酰氯与至少一种单(烷撑二醇)单醚或聚(烷撑二醇)单醚或者至少一种单(烷撑二醇)单醚或聚(烷撑二醇)单醚和至少一种烷撑二醇或聚烷撑二醇的混合物反应制备的磷酸酯化合物。
Description
本申请要求2009年10月5日提交的美国临时申请号61/248,831的优先权。
本发明涉及一种由磷酰氯(POCl3,氯化磷的氧化物)和二醇或者聚二醇的单烷基醚生产磷酸酯的方法。
建议将具有如下通式结构的磷酸酯化合物作为添加剂用于电池电解质溶液:
其中n为1或者2。参见,例如美国专利号6,642,294、EP 906 641和solid State Electronics 133,2000,171-177。这些磷酸酯化合物可以赋予电解质溶液和含有该电解质溶液的电池某些所需的机械、热和电气性能。它们可以提供阻燃性,这是很重要的,特别是对于锂电池而言,因为这些电池含有非水电解质,而且它们还具有高能量和功率密度。电解质的有机性质与其高能量和功率密度的结合使得锂电池对热耗散事件非常敏感,比如耗散放热反应,甚至火灾。阻燃剂通常被加入锂电池电解质就是这个原因。
具有前述结构的磷酸酯化合物在磷酰氯和乙二醇单甲醚(也就是,HOCH2CH2OCH3)或者二甘醇单甲醚(也就是,HO(CH2CH2O)2CH3)之间的反应中制备。美国专利6,642,294描述了在氯化锌催化剂的存在下进行这个纯反应(也就是,没有溶剂)。获得了产物混合物,然后进行多次蒸馏步骤以便分离所需的磷酸酯产物。在EP 906641中,该反应在4-二甲氨基吡啶存在下进行。收率较差(56%),产物为材料混合物,从其中通过色析法回收得到所需产物。
Solid State Ionics,133,2000,171-177,描述了在三乙胺存在下进行该反应。三乙胺清除了在反应中形成的HCl副产物。该方法不是非常有选择性的,因为产生了大量的含磷反应产物,包括某些磷-氮化合物。这会导致原材料的大量浪费,且此外从反应混合物的其他组分中分离所需的产物需要费很大的劲。
由于这些原因,这些合成方法不是非常适合大规模采用。因此,需要一种方法,通过该方法制备的磷酸酯化合物具有较低的杂质含量。
本发明是这样一种方法。本发明是形成磷酸酯化合物的方法,包括,在存在每摩尔磷酰氯至少3摩尔无脂肪族氮原子的吡啶基化合物的情况下,使磷酰氯与至少一种单(烷撑二醇)单醚或聚(烷撑二醇)单醚反应,或者与至少一种单(烷撑二醇)单醚或聚(烷撑二醇)单醚和至少一种烷撑二醇或聚烷撑二醇的混合物反应。该方法以良好的收率形成相应的三磷酸酯化合物。该方法对于所需的三磷酸酯化合物选择性非常高。采用该方法,消耗磷的不需要的副反应趋于最小化。这就减少了起始材料转化成不需要的副产物的损失,而且也简化了从反应混合物中回收产物。
合适的单(烷撑二醇)单醚包括1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇(四甲撑二醇)、己二醇等的单烷基醚。烷基优选含有1-4个碳原子,最优选甲基。单烷基醚将含有一个羟基,其与磷酰氯反应形成酯。单(烷撑二醇)单醚中特别优选乙二醇单甲醚。
合适的聚(烷撑二醇)单醚包括聚乙二醇、聚-1,2-丙二醇、聚-1,3-丙二醇、聚-1,2-丁二醇、聚-1,4-丁二醇(聚丁二醇)、或者聚(己二醇)的单烷基醚,或者1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇(四甲撑二醇)和己二醇中任意两种或更多种的共聚物的单烷基醚。聚合度为2或者更大,但是优选不大于5。烷基优选含有1-4个碳原子,且最优选甲基。这些单醚含有一个羟基,其可以与磷酰氯反应形成酯。优选1,2-环氧乙烷聚合物和共聚物的单烷基醚。特别优选二甘醇和/或三甘醇的单烷基醚。
两种或多种单(烷撑二醇)单醚的混合物也可以使用,如两种或多种聚(烷撑二醇)单醚的混合物一样。一种或多种单(烷撑二醇)单醚与一种或多种聚(烷撑二醇)单醚的混合物也可以使用。
前述单醚可以与至少一种烷撑二醇或者聚烷撑二醇混合使用。如前对单醚所述的,同样适用于烷撑二醇和聚烷撑二醇,当然除了两个末端羟基都没有用甲基封端之外。因此,每分子烷撑二醇和聚烷撑二醇含有两个羟基,且能双官能地与两个磷酰氯分子反应以形成酯键。因此,烷撑二醇或者聚烷撑二醇,当存在时,作为偶联剂起作用,如果大规模使用,其可以导致高分子量酯的形成。由于该原因,烷撑二醇或者聚烷撑二醇,如果存在,则以相对小的比例存在。优选每4摩尔单醚使用不大于1摩尔的烷撑二醇和/或聚烷撑二醇。烷撑二醇或者聚烷撑二醇可以一起省去。
每摩尔磷酰氯可与三个当量的羟基反应。因此,对于每摩尔磷酰氯,反应混合物中至少存在三个当量的单醚或者单醚/二醇混合物。一般优选提供过量的单醚或单醚/二醇混合物。因此例如,每摩尔磷酰氯提供3-10个,优选4-6个当量的单醚或单醚/二醇混合物。
单醚或者单醚/二醇混合物与磷酰氯的反应在不含脂肪族氮原子的吡啶基化合物存在下进行。吡啶基化合物被认为起到HCl清除剂的作用,其在酯化反应中产生。应该存在足够的吡啶基化合物以便消耗产生的所有HCl。因此,每摩尔磷酰氯优选提供至少3摩尔的吡啶基化合物。优选过量的吡啶基化合物。因此,每摩尔磷酰氯可以提供3-10摩尔,优选3.1-6摩尔的吡啶基化合物。
吡啶基化合物中至少一部分具有下列结构:
其中R基独立地为氢、烷基、芳基、芳基取代的烷基等等。两个或更多个R基可以与它们所连接的碳原子(以及芳环中任何介于其间的碳原子,如果有)一起形成稠环结构。稠环结构可以是芳香族或脂肪族。任何取代基都应该不含脂肪族氮原子,虽然形成部分芳环结构的其他氮原子可能会存在。优选所有的R基是氢,在这种情况下吡啶基化合物是吡啶。
反应可以单纯进行(也就是,没有溶剂)或者在溶剂存在下进行。一般优选采用溶剂,因为在反应进行时形成的吡啶基化合物的HCl盐大多数情况下会从反应中沉淀;没有溶剂的情况下,该固相的存在会引起反应混合物太粘滞而不容易处理。合适的溶剂为用于单醚或者单醚/二醇混合物的溶剂,视情况而定,和用于产物磷酸酯和吡啶基化合物的溶剂,但是应该是吡啶基化合物的HCL盐在其中基本不溶的材料。该溶剂当然不应与任何的起始材料、反应条件下的产物或者反应副产物反应。大量的有机溶剂是有用的,包括非极性类比如脂肪族或者芳香烃,和极性类比如四氢呋喃和1,2-二氯乙烷。一般优选极性类,因为在极性溶剂中反应会进行得更快且在较温和条件下进行。所用溶剂的量并不认为很重要。
反应可以在温和条件下进行。在单醚或者单醚/二醇混合物中添加磷酰氯常常是有利的。吡啶基化合物优选在磷酰氯与单醚或单醚/二醇混合物中刚开始混合时存在,但是也可以随后加入,但是要在反应结束前。如果采用溶剂,单醚或单醚/二醇混合物优选在反应开始前溶解至溶液中。磷酰氯可以逐渐地加入单醚或单醚/二醇混合物中以防止由于放热反应导致的温度快速升高。混合磷酰氯和单醚或单醚/二醇混合物时的温度可以低于或者等于或者高于室温。例如,在它们相互反应之前,反应物的温度可以为-20℃至24℃或者-10℃至+10℃。在其他实施方式中,可以在20-40℃,或者更高的40-120℃的温度下使反应物反应。优选较冷的温度。
在磷酰氯/单醚或者单醚/二醇混合物/吡啶基化合物混合物形成后,使混合物达到例如0-120℃温度下以使反应继续。20-50℃的温度常常是合适的。一些反应通常在反应混合物形成后立即发生,正如吡啶基化合物的沉淀HCL盐的形成所表明的一样。反应可能需几个小时完成,时间量取决于反应的温度,且某种程度上取决于溶剂的选择。反应速度在极性溶剂中(比如四氢呋喃或者1,2-二氯乙烷)比非极性溶剂中(比如甲苯)更快。
磷酰氯和单醚或者单醚/二醇混合物反应形成磷酸酯化合物。该磷酸酯化合物合适地是三酯,相当于磷酰氯和3摩尔醇的反应。这个产物可以用以下结构表示:
其中,每个x独立地为1或更大,每个R为氢或者烷基,每个R1为烷基或者
当烷撑二醇或聚烷撑二醇在反应混合物中存在时,某些R1基会具有结构Ⅱ。否则,R1基将是烷基,且将对应于单醚化合物上的末端烷基。至少某些R1基是烷基。
每个x优选从1-5,更优选每个x从1-3。每个R优选是氢或者C1-2烷基。在每种情况下,R更优选是氢。优选不多于一个R1基具有结构Ⅱ。剩余的为C1-4烷基,特别是甲基。更优选每个R1基为C1-4烷基,更优选每个R1基为甲基。
除了上述的磷酸酯产物,粗反应混合物将含有:吡啶基化合物的HCl盐,其大部分情况下在其形成时会从反应混合物中沉淀;溶剂,如果采用;未反应的起始材料,特别是如果单醚、单醚/二醇混合物和/或吡啶基化合物过量使用时。某些其他磷酸酯化合物,包括以下实施例1描述类型的磷-氮化合物,可能在反应中形成。这些化合物,当胺比如三乙胺作为HCL净化剂时,其会大量形成,如果完全在本发明的方法中会以很小的量形成。粗反应混合物的液相倾向于无色或者几乎无色,因为不含或者几乎不含这些含磷杂质。
因为不需要的磷酸酯产物没有大量产生,产物回收就被简化了。吡啶基化合物的HCl盐可以用任何常规的固体-液体分离技术,比如过滤或者离心分离,容易地分离。溶剂,过量的吡啶基化合物以及未反应的单酯和二醇可以在大气压或者负压下从产物中馏出。其他的净化可以通过将磷酸酯产物溶液通过层析柱以层析法进行,其中的材料比如氧化铝作为固定相。在这种情况下,在除去溶剂和未反应起始材料后回收的磷酸酯产物可以在合适的溶剂中再溶解,比如乙腈或者前述的那些任何物质,以便形成用于层析分离的溶液。
磷酸酯产物可用作为电池电解质溶液的组分,特别是对于锂电池。该磷酸酯可以赋予电解质溶液热稳定性和/或阻燃性;其也可以在碳电极参与SEI(固体电解质界面)的形成。磷酸酯化合物中的烷撑二醇单元也被认为在充电和放电循环中促进锂离子传导通过电解质。含有如本发明产生的那些磷酸酯的电池电解质溶液在EP 906 641和US 6,642,294中有描述。
除了磷酸酯外,电池电解质溶液将含有至少一种锂盐。锂盐可以是任何适用于电池的物质,包括无机锂盐,比如LiAsF6、LiPF6、LiBF4、LiB(C2O4)2、LiBF2C2O4、LiClO4、LiBrO4和LiIO4,以及有机锂盐,比如LiB(C6H5)4、LiCH3SO3、LiN(SO2C2F5)2和LiCF3SO3。LiPF6、LiClO4、LiBF4、LiAsF6、LiCF3SO3和LiN(SO2CF3)2是优选的类型,LiPF6是特别优选的锂盐。锂盐在电解质溶液中存在的浓度适当的为至少0.5摩尔/升,优选至少0.75摩尔/升,最高达3摩尔/升,更优选最高达1.5摩尔/升。
大部分情况下,电池电解质溶液还将包括至少一种用于锂盐的非水溶剂。非水溶剂可以包括,例如一种或多种直链碳酸烷基酯、环状碳酸酯、环状酯、直链酯、环醚、烷基醚、腈、砜、环丁砜、硅氧烷和磺内酯。也可以使用前述类型的任意两种或多种混合物。环酯、直链碳酸烷基酯和环状碳酸酯是优选的非水溶剂类型。
合适的直链碳酸烷基酯包括碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯等等。合适的环状碳酸酯包括碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯等等。合适的环酯包括,例如γ-丁内酯和γ-戊内酯。环醚包括四氢呋喃、2-甲基四氢呋喃、四氢吡喃等等。烷基醚包括二甲氧基乙烷、二乙氧基乙烷等等。腈包括单腈,比如乙腈和丙腈,二腈比如戊二腈和它们的衍生物。砜包括对称的砜比如二甲基砜、二乙基砜等等,不对称的砜比如乙基甲基砜、丙基甲基砜等等,以及它们的衍生物。环丁砜包括四亚甲基环丁砜等等。
某些优选的溶剂混合物包括环状碳酸酯和直链碳酸烷基酯的混合物,重量比从15∶85至40∶60;环状碳酸酯/环酯混合物,重量比从20∶80至50∶50;环状碳酸酯/环酯/直链碳酸烷基酯的混合物,重量比从20-48∶50-78∶2-20;环酯/直链碳酸烷基酯混合物,重量比从70∶30至98∶2。
特别感兴趣的溶剂混合物为碳酸亚乙酯和碳酸亚丙酯的混合物,重量比从15∶85至40∶60;碳酸亚乙酯和二甲基碳酸酯的混合物,重量比从15∶85至40∶60;碳酸亚乙酯、碳酸亚丙酯和二甲基碳酸酯的混合物,重量比从20-48∶50-78∶2-20,以及碳酸亚丙酯和二甲基碳酸酯的混合物,重量比从15∶85至40∶60。
除了已经提到的组分,电池电解质溶液中可以存在各种其他添加剂。这些可包括,例如能够在石墨电极表面促进固体电解质界面形成的添加剂;各种阴极保护剂、锂盐稳定剂、锂沉积改进剂、离子溶剂化增强剂、防腐剂、润湿剂和降粘剂。这些种类的许多添加剂被Zhang描述于“A review on electrolyte additives for lithium-ion batteries”J.Power Sources 162(2006)1379-1394。
促进固体电解质界面(SEI)形成的试剂包括各种可聚合的烯属不饱和化合物、各种硫化合物以及其他材料。合适的阴极保护剂包括如下材料,如N,N-二乙胺基三甲硅烷和LiB(C2O4)2。锂盐稳定剂包括LiF、三(2,2,2-三氟乙基)亚磷酸酯、1-甲基-2-吡咯烷酮、氟化氨基甲酸酯和六甲基磷酰胺。锂沉积改进剂的实例包括二氧化硫、多硫化物、二氧化碳、表面活性剂比如四烷基铵氯化物、全氟辛烷磺酸盐的锂和四乙铵盐、各种全氟代聚醚等等。冠醚可以是合适的离子溶剂化增强剂、如各种硼酸盐、硼和硼杂环戊二烯(borole)化合物。LiB(C2O4)2和LiF2C2O4是铝防腐剂的实例。环己胺、三烷基磷酸酯和某些羧酸酯可以用作润湿剂和降粘剂。
各种其他添加剂合计可以构成电池电解质溶液总重量的最高达20%,优选最高达10%。
电池电解质溶液的水含量应该尽可能低。百万分之50(ppm)重量或更少的水含量是希望的,更优选水含量为30ppm或者更少。
含有电池电解质溶液的电池可以是任何有用的构造。典型的电池构造包括阳极和阴极,带有隔板,且电解质溶液插入阳极和阴极之间,以便离子能够迁移通过阳极和阴极之间的电解质溶液。组件一般被封装在壳中。电池的形状没有限制。电池可以是含有螺旋缠绕板电极和隔板的圆柱形。电池可以是具有包括片状电极组合和隔板并具有由内外翻(inside-out)结构的圆柱形类型。电池可以是含有被叠加的电极和隔板的板式。
合适的阳极材料包括,例如,碳质材料比如天然或人造石墨、炭化沥青、碳纤维、石墨化中间相微球、炉黑、乙炔黑和各种其他的石墨化材料。碳质材料可以采用粘结剂比如聚(偏二氟乙烯)、聚四氟乙烯、苯乙烯-丁二烯共聚物、异戊二烯橡胶、聚(醋酸乙烯酯)、聚(甲基丙烯酸乙酯)、聚乙烯或者硝酸纤维素粘合在一起。合适的碳质阳极和构造其的方法描述在例如,美国专利7,169,511。
其他合适的阳极材料包括锂金属、锂合金和其他锂化合物比如钛酸锂阳极。
合适的阴极材料包括无机化合物,比如过渡金属氧化物、过渡金属/锂复合氧化物、锂/过渡金属复合磷酸盐、过渡金属硫化物、金属氧化物和过渡金属硅酸盐。过渡金属氧化物的实例包括MnO,V2O5,V6O13和TiO2。过渡金属/锂复合氧化物包括锂/钴复合氧化物,其碱性组成大致为LiCoO2,锂/镍复合氧化物,其碱性组成大致为LiNiO2,和锂/锰复合氧化物,其碱性组成大致为LiMn2O4或者LiMnO2。在各自这些情况下,部分钴、镍或锰可以被一种或两种金属比如Al、Ti、V、Cr、Fe、Co、Ni、Cu、Zn、Mg、Ga或Zr代替。锂/过渡金属复合磷酸盐包括锂铁磷酸盐、锂锰磷酸盐、锂钴磷酸盐、锂铁锰磷酸盐等等。有用的金属氧化物实例包括SnO2和SiO2。有用的金属硅酸盐实例包括锂铁正硅酸盐。
电极各自一般与集电器电接触或者形成于集电器上。用于阳极的合适的集电器为金属或者金属合金,比如铜、铜合金、镍、镍合金、不锈钢等等。用于阴极的合适的集电器包括铝、钛、钽、这些物质两种或更多种的合金等等。
在阳极和阴极之间插入隔板以防止阳极和阴极相互接触和短路。有利的隔板为非导电材料。其在操作条件下,不应与电解质溶液反应或溶于电解质溶液或不应与电解质溶液中的任何组分反应或溶于电解质溶液中的任何组分。聚合物隔板一般是合适的。用于形成隔板的合适的聚合物实例包括聚乙烯、聚丙烯、聚丁烯-1、聚-3-甲基戊烯、乙烯丙烯共聚物、聚四氟乙烯、聚苯乙烯、聚甲基丙烯酸甲酯、聚二甲基硅氧烷、聚醚砜等等。
电解质溶液必须能够渗透通过隔板。为此,隔板一般是有孔的,是多孔板、无纺布或者纺织织物等形式。隔板的孔隙率一般为20%或者更高,最高达90%。优选的孔隙率是30-75%。孔一般不大于0.5微米,优选在它们的最长横截面尺寸上最高达0.05微米。隔板通常至少1微米厚,可以最高达50微米厚。优选的厚度为5-30微米。
电池优选二次(可再充电的)锂电池。在这类电池中,放电反应包括将锂离子从阳极溶解到电解质溶液中或者脱锂至电解质溶液中,且同时将锂离子引入阴极中。充电反应,可逆地,包括将锂离子从电解质溶液引入阳极中。充电后,在阳极侧的锂离子减少,同时,阴极材料中的锂离子溶解到电解质溶液中。
电池可以用于工业应用,比如电动车、混合动力车、插件式混合动力车、航天、电动-自行车等等。电池也可以用于操作大量的电气和电子设备,尤其是比如计算机、照相机、摄像机、手机、PDA、MP3和其他音乐播放器、电视、玩具、电子游戏机、家用电器、医疗器械比如起搏器和除颤器。
下面的实施例被提供用于举例说明本发明,但并非企图限定其范围。除非另有说明,所有的部分和百分数都以重量计。
实施例1
将四氢呋喃加入装配有搅拌棒和另外的漏斗的氩气冲洗的圆底烧瓶中。将二甘醇单甲醚和吡啶加入烧瓶中,然后在冰浴中冷却至0℃。然后将磷酰氯逐滴加入并搅拌。组分的比例应该使所得磷酰氯的起始浓度(也就是磷酰氯添加完成后)为约0.5M,每摩尔磷酰氯提供6当量的单醚,每摩尔的磷酰氯提供5摩尔的吡啶。一旦磷酰氯的添加开始,吡啶:HCl就开始沉淀。磷酰氯的添加完成后,反应混合物允许加热到室温(25℃),且搅拌约24小时。
吡啶:HCL从混合物中滤出,留下是清澈的、无色液相。溶剂在旋转蒸发器中去除,过量的单醚和吡啶在真空下蒸馏出来。分离的产物在乙腈中溶解,通过氧化铝柱,在真空下、65℃去溶剂化和干燥。
通过液相色谱法/质谱仪分析产物。此分析结果示于图1。仅出现一个单峰,在约8.45分钟的洗脱时间,材料分子量为404。该峰值对应的化合物具有结构:
其是希望的磷酰氯的三(二甘醇单甲醚)酯。
当实施例1重复纯反应或在1,2-二氯乙烷中重复时得到了类似的结果。当反应在甲苯中进行时,混合物需要被加热回流几天以完成反应;液相色谱法/质谱仪表明这种情况下的产物比其他情况下的杂质稍多。这证明了在极性溶剂中进行反应的另外的好处。
比较例A
重复实施例1,此次用三乙胺代替吡啶。反应进行得比实施例1更慢,在室温下需要约48小时达到完成。在反应中形成的三乙胺:HCL盐通过过滤从粗反应混合物中分离;剩余的液相颜色很深。溶剂去除后,过量的单醚和胺如实施例1所述,产物再次溶解在乙腈中,然后通过氧化铝柱,与实施例1相同。然后如实施例1将产物去溶剂化和干燥。
进行液相色谱/质谱仪分析,结果图示于图2。从图2可以看出,所得的产物是化合物的混合物。主要的峰是分子量404的材料,其代表所需的产物。另外,至少5种其他化合物以较大的量存在。这些包括分子量为630的化合物,图2中以点B表示;和分子量为414、357、385和385的化合物,其在图2中以点C至点F表示。点D、E和F表示的化合物为磷-氮化合物;点D和E化合物被认为具有下列结构:
点F表示的化合物被认为是点E化合物的异构体。
实施例2
重复实施例1,此次用单乙二醇单甲基醚代替实施例1采用的二甘醇单甲基醚。液相色谱/质谱仪分析与产物磷酰氯的三(单乙二醇单甲醚)酯一致。基本上没有检测到其他磷化合物。当此实施方式重复纯反应或在1,2-二氯乙烷中重复时得到了类似的结果。
实施例3
再次重复实施例1,此次用三甘醇单甲醚代替实施例1中使用的二甘醇单甲基醚。液相色谱/质谱仪分析与产物磷酰氯的三(三乙二醇单甲醚)酯一致。基本未检测到其他磷化合物。产物在25℃具有25cps的粘度。当此实施例重复纯反应或在1,2-二氯乙烷中重复时得到了类似的结果。
实施例1-3中所得的磷酸酯化合物的热稳定性通过热重力分析(TGA)评估。试样以5℃/分钟的速率从75℃被加热,重量损失作为温度的函数评估。确定试样损失其初始(在75℃)重量50%时的温度。实施例2中产物的50%重量损失的温度是约190℃.而实施例1和3的产物则分别为约265℃和288℃。
Claims (2)
1.一种形成磷酸酯化合物的方法,包括:在存在每摩尔磷酰氯至少三摩尔无脂肪族氮原子的吡啶基化合物的情况下,使磷酰氯与二甘醇单甲醚或三甘醇单甲醚反应,所述反应在作为溶剂的四氢呋喃或1,2-二氯乙烷中进行。
2.权利要求1的方法,其中所述吡啶基化合物是吡啶。
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KR101910131B1 (ko) | 2018-02-23 | 2018-10-19 | 에스케이씨 주식회사 | 인계 이형제, 이를 포함하는 광학용 중합성 조성물 및 이의 제조방법 |
US20190341614A1 (en) * | 2018-05-02 | 2019-11-07 | Ford Global Technologies, Llc | Perfluoropolyether additives for lithium ion battery anodes |
CN110931862B (zh) * | 2019-10-31 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | 一种双功能电解液添加剂及含有该添加剂的锂离子电池电解液 |
CN114388888B (zh) * | 2020-10-22 | 2023-07-11 | 比亚迪股份有限公司 | 电解液、正极、锂离子电池和车辆 |
KR102597591B1 (ko) * | 2021-04-14 | 2023-11-03 | 한국에너지기술연구원 | 고전압 안정성이 우수한 고분자 고체전해질 및 이의 제조방법 |
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US5302758A (en) * | 1993-05-10 | 1994-04-12 | General Electric Company | Deuterated dibutyl and monobutyl phosphates |
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AU9629298A (en) | 1997-10-02 | 1999-04-27 | Basf Aktiengesellschaft | Mixtures with special softening agents suited as a solid electrolyte or separator for electrochemical cells |
JP2000256377A (ja) * | 1999-03-10 | 2000-09-19 | Mitsui Chemicals Inc | 新規な燐酸エステル及び該化合物からなる離型剤 |
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AU2003280566A1 (en) | 2002-10-22 | 2004-05-13 | Mitsubishi Chemical Corporation | Nonaqueous electrolytic solution and nonaqueous electrolyte secondary battery containing the same |
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US7960420B2 (en) * | 2007-12-21 | 2011-06-14 | Joyant Pharmaceuticals, Inc | Diazonamide analogs with improved solubility |
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EP2519531A2 (en) | 2012-11-07 |
WO2011043934A3 (en) | 2011-06-16 |
KR20120093262A (ko) | 2012-08-22 |
US20120172613A1 (en) | 2012-07-05 |
WO2011043934A9 (en) | 2012-04-12 |
CN102639544A (zh) | 2012-08-15 |
WO2011043934A2 (en) | 2011-04-14 |
JP2013506711A (ja) | 2013-02-28 |
JP5702393B2 (ja) | 2015-04-15 |
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