CN1221406A - 二聚体含量低的空间位阻4-氨基哌啶及其制备方法和应用 - Google Patents
二聚体含量低的空间位阻4-氨基哌啶及其制备方法和应用 Download PDFInfo
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- CN1221406A CN1221406A CN97195198A CN97195198A CN1221406A CN 1221406 A CN1221406 A CN 1221406A CN 97195198 A CN97195198 A CN 97195198A CN 97195198 A CN97195198 A CN 97195198A CN 1221406 A CN1221406 A CN 1221406A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D211/58—Nitrogen atoms attached in position 4
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Abstract
本发明涉及一种抑制式Ⅰ的哌啶二聚的方法,式中,R1-R4为C1-C6烷基,R1和R2和/或R3和R4一起构成有2—5个碳原子的CH2链,该方法包括将0.001—0.2%(重量)的式MXH4-mYm抑制剂加到哌啶中,其中M为碱金属、NR4(其中R为相同的或不同的C1-C4烷基)或等当量的碱土金属或等当量的锌,X为硼或铝,Y为H或CN,m为0或1。本发明还涉及一种式Ⅰ的哌啶、0.001—0.2%(重量)抑制剂和1—1000ppm式Ⅰ哌啶的二聚体的混合物,以及涉及由它们制备位阻胺光稳定剂。
Description
式Ⅰ的空间位阻4-氨基哌啶在工业规模上通常由丙酮或丙酮衍生物来制备。Ⅰ可在氨和氢的存在下,由下式的化合物在催化闭环反应中一步制得(DE 2412750),或者由式Ⅲ的三丙酮胺通过催化还原胺化一步或两步制得 Ⅲ,(例如参见,DE 2040975、DE 2349962、DE 2621870、EP 33529、EP 42119、EP 303279、EP 410970、EP 611137、EP 623585和DE4210311)。在工业上制备的空间位阻4-氨基哌啶通常用蒸馏法纯化。
式Ⅰ的空间位阻4-氨基哌啶有各种应用。具体地说,它们用作制备用于合成聚合物的UV稳定剂的中间体。此外,本发明还涉及一种含有式Ⅰ的哌啶、1-1000ppm式Ⅱ的二聚体和0.001-0.2%(重量)抑制剂的混合物,以及涉及它们在制备HALS(位阻胺光稳定剂)化合物中的应用。HALS通常是这样的式Ⅰ哌啶,其中4-氨基中的氮原子已被烷基化或酰化(参见R.Gachter,H.Muller(编辑),《塑料添加剂技术手册(Taschenbuch der Kunststoff-additive)》,Carl Hanser Verlag,Munich,1979;F.Gugumus,《聚合物降解稳定剂(Polym.Degrad.Slabil)》44(1994),299-322)。
对于许多应用来说,式Ⅰ的哌啶具有高的化学纯度是重要的。如果式Ⅰ的哌啶用于制备HALS化合物,具有高纯度是特别重要的,因为产品质量、因此被稳定的聚合物的质量在很大程度上取决于所述纯度。具体地说,式Ⅰ的哌啶的二聚体(它为无色的)是一种产生干扰的副产物,甚至在保护气体下、在黑暗中、在室温下贮存时,也可由式Ⅰ的哌啶生成不可接受量的二聚体。
防止哌啶二聚的方法现在还不知道。
US 4316837公开了将在支链脂肪醇中的4-氨基哌啶基还原成相应的含4-氨基哌啶基的支链醇。未公开哌啶Ⅰ的二聚体Ⅱ。
DD 266799公开了用这样一种方法来纯化式Ⅰ的哌啶,其中使它们在丙酮/水溶液中与CO2反应,分离出沉淀,用丙酮洗涤,然后水解,产物用蒸馏法纯化。SU 1811527公开了用于式Ⅰ的空间位阻4-氨基哌啶的另一纯化方法,其中将未纯化的粗产物溶于非质子传递溶剂,并与乙二醇反应,然后蒸馏反应产物,并经多步纯化。这两种方法都极复杂和费用高。它们不能防止随后生成二聚体。
EP 477593公开,可通过加入金属硼氢化物并在水存在下、在一定条件下蒸馏混合物来改善N-烷基-二烷醇胺的颜色。但是,N-烷基二烷醇胺是与本发明的空间位阻4-氨基哌啶完全不同的一类物质。此外,《光谱化学(Spec.Chem.)》,4(2)(1984),38-41和US 3159276、US 3207790和US 3222 310公开,可通过将硼氢化钠加到乙醇胺、亚乙基胺或芳胺中来改善产物的颜色。这些公开物同样也未提及式Ⅰ的哌啶或无颜色的式Ⅱ二聚体。
本发明的一个目的是防止或抑制式Ⅰ的哌啶的二聚。
我们已发现,这一目的可用上述方法来达到,该方法包括,将基于式-的哌啶计0.001-0.2%(重量)的式MXH4-mYm抑制剂加到式Ⅰ的哌啶中,其中M为碱金属、NR4或等当量的碱土金属或等当量的锌,其中R为相同的或不同的C1-C4烷基,X为硼或铝,Y为H或CN,m为0或1。本发明还涉及以下物质的混合物:式Ⅰ的哌啶 Ⅰ,1-1000ppm式Ⅱ的化合物 Ⅱ,以及0.001-0.2%(重量)抑制剂,上述含量均基于式Ⅰ的哌啶计。此外,本发明还涉及这一混合物在制备HALS化合物中的应用。
本发明进一步的实施方案在从属权利要求中给出。
在式Ⅰ的空间位阻4-氨基哌啶中,基团R1、R2、R3和R4各自独立,优选为C1-C3烷基,特别是乙基或甲基,例如甲基。
所用的抑制剂为式MXH4-mYm的化合物,其中:M为碱金属、NR4(其中R为相同的或不同的C1-C4烷基)或等当量的碱土金属或等当量的锌,优选碱金属,特别是钠或钾,例如钠,X为铝或特别是硼,Y为CN或优选H,m为1或特别是0。一个例子是硼氢化钠。在某些情况下,(RaO)2TiBH4或(RaO)3TiBH4也证明是适用的,其中Ra为C1-C4烷基。
基于式Ⅰ的哌啶计,加到式Ⅰ哌啶中的抑制剂的量优选为10-1000ppm,在某些情况下至多500ppm,特别是至多200ppm。在某些情况下,基于式Ⅰ的哌啶计,抑制剂的量也可大于50ppm,特别是大于100ppm的量加入。
加入的方法不重要。抑制剂可一次或分几次加到装有式Ⅰ哌啶的容器中,例如用搅拌的方法混合。这一加入可间歇进行或连续进行,在后一情况下,例如也可将抑制剂计量加入到含有式Ⅰ哌啶的或由式Ⅰ哌啶组成的产物流中。原则上互换最初装入和加入的物质也是可能的。温度和压力不重要,抑制剂可在制备式Ⅰ哌啶的常规步骤中加入,例如在制备过程中在式Ⅰ的哌啶最后纯化的蒸馏步骤中或特别是蒸馏步骤后加入。抑制剂可以粉末形式或作为溶液加入,例如在式Ⅰ的纯哌啶中的溶液。
可用简单的方式制备含有式Ⅰ的哌啶、式Ⅱ的二聚体和抑制剂的权利要求5的混合物:首先用蒸馏法按所需的方式从式Ⅱ的二聚体中分离式Ⅰ的粗哌啶。这例如可用蒸馏法进行,因为式Ⅱ的二聚体的沸点比式Ⅰ哌啶的高得多。熟悉本专业的技术人员很容易确定二聚体含量,例如用气相色谱分析。抑制剂然后按上述的加入。
HALS化合物通常按传统的方式,通过在式Ⅰ哌啶的4-氨基的氮原子上的烷基化或酰化由本发明混合物制得。
本发明方法提供了一种制备基本上不含二聚体的纯的式Ⅰ的空间位阻4-氨基哌啶的简单且低成本的方法。这一稳定化操作可在室温下以简单的方式进行,常常得到至少数周内保持没有二聚体的易处理的溶液。
由它可制得副产物含量低的HALS化合物。
实施例
将4208克组成如下的粗4-氨基-2,2,6,6-四甲基哌啶(三丙酮二胺,TAD)在一实验室设备中粗馏:
85.6%三丙酮二胺(TAD)
9.0%H2O
约0.7%低沸物
4.7%中沸物和高沸物蒸馏柱装有2.4米Sulzer CY填料(约22块理论塔板,公称直径43毫米),回流比为5∶1,压力为从100到40毫巴。在第一操作中,从43到44℃和100毫巴下除去水后,在40毫巴和塔顶温度97-103℃下,在主操作中得到TAD含量大于99.6%的纯TAD馏分(气相色谱法,30米毛细管柱RTX-5胺);蒸馏产率:3022克(84%)。
纯TAD馏分(气相色谱法TAD含量:99.7%)经贮存,并在相同的条件下测量,首次测量不加硼氢化钠,第二次测量加入1000ppm硼氢化钠。结果列入下表:
贮存时间(周) | 气相色谱法组成(%面积) | |
不加NaBH4 | 加NaBH4 | |
TAD 二聚体Ⅱ* | TAD 二聚体Ⅱ* | |
023 | 99.69 0.0298.26 0.87 | 99.65 0.0199.64 0.0001-0.001 |
*R1、R2、R3和R4为甲基
Claims (7)
1.一种抑制式Ⅰ的哌啶二聚的方法 Ⅰ,式中,R1-R4为C1-C6烷基,R1和R2和/或R3和R4一起构成有2-5个碳原子的CH2链,该方法包括将基于哌啶计0.001-0.2%(重量)式MXH4-mYm的抑制剂加到哌啶中,其中M为碱金属、NR4或等当量的碱土金属或等当量的锌,其中R为相同的或不同的C1-C4烷基,X为硼或铝,Y为H或CN,并且m为0或1。
2.根据权利要求1的方法,其中R1、R2、R3和R4为C1-C3烷基。
3.根据权利要求2的方法,其中式MXH4-mYm的化合物为硼氢化钠。
5.根据权利要求4的混合物,其中R1、R2、R3和R4为C1-C3烷基。
6.根据权利要求4或5的混合物,其中式MXH4-mYm的化合物为硼氢化钠。
7.一种使用权利要求4-6中任一项的混合物制备HALS化合物的方法。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19622268.0 | 1996-06-03 | ||
DE19622268A DE19622268C1 (de) | 1996-06-03 | 1996-06-03 | Sterisch gehindertes 4-Amino-piperidin mit geringem Dimergehalt, seine Herstellung und Verwendung |
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CN1221406A true CN1221406A (zh) | 1999-06-30 |
CN1088697C CN1088697C (zh) | 2002-08-07 |
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CN97195198A Expired - Fee Related CN1088697C (zh) | 1996-06-03 | 1997-05-28 | 二聚体含量低的空间位阻4-氨基哌啶及其制备方法和应用 |
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US (1) | US6013803A (zh) |
EP (1) | EP0906280B1 (zh) |
JP (1) | JP2000515123A (zh) |
CN (1) | CN1088697C (zh) |
AT (1) | ATE192434T1 (zh) |
AU (1) | AU711518B2 (zh) |
BR (1) | BR9709519A (zh) |
CA (1) | CA2257094C (zh) |
CO (1) | CO5050411A1 (zh) |
CZ (1) | CZ291453B6 (zh) |
DE (2) | DE19622268C1 (zh) |
EA (1) | EA001211B1 (zh) |
ES (1) | ES2146471T3 (zh) |
GR (1) | GR3033454T3 (zh) |
HU (1) | HUP0001825A2 (zh) |
ID (1) | ID17018A (zh) |
MY (1) | MY121628A (zh) |
NZ (1) | NZ332521A (zh) |
PL (1) | PL189193B1 (zh) |
PT (1) | PT906280E (zh) |
TW (1) | TW372970B (zh) |
UA (1) | UA54430C2 (zh) |
WO (1) | WO1997046528A1 (zh) |
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DE19953908A1 (de) | 1999-11-10 | 2001-05-17 | Sms Demag Ag | Hochgeschwindigkeitsschere zum Querteilen von Walzband |
MX2008012897A (es) * | 2006-04-06 | 2008-12-17 | Dow Global Technologies Inc | Composiciones de poliolefina expandible con adhesión modificada y piezas de vehiculo aisladas que contienen composiciones de poliolefina expandidas con adhesion modificada. |
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US3207790A (en) * | 1961-07-06 | 1965-09-21 | Dow Chemical Co | Process for reducing the color of discolored alkanolamines |
NL266799A (zh) * | 1961-07-07 | |||
US3159276A (en) * | 1963-05-03 | 1964-12-01 | Allied Chem | Ethanolamines |
DE3003843A1 (de) * | 1980-02-02 | 1981-08-13 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur herstellung von 4-amino-2,2,6,6-tetramethylpiperidin |
US4316837A (en) * | 1980-09-10 | 1982-02-23 | Carstab Corporation | Polyalkylated 4-aminopiperidine derivatives as stabilizers for synthetic polymers |
EP0477593B1 (en) * | 1990-09-24 | 1995-01-18 | Elf Atochem North America, Inc. | Purification and decolorization of off-color alkyl alkanolamines |
DE4239437A1 (de) * | 1992-11-24 | 1994-05-26 | Basf Ag | Maleinsäureimid-alpha-Olefin-Copolymerisate und ihre Verwendung als Lichtschutzmittel und Stabilisatoren für organisches Material |
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1996
- 1996-06-03 DE DE19622268A patent/DE19622268C1/de not_active Expired - Lifetime
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1997
- 1997-05-28 EA EA199801029A patent/EA001211B1/ru not_active IP Right Cessation
- 1997-05-28 PL PL97330276A patent/PL189193B1/pl not_active IP Right Cessation
- 1997-05-28 US US09/180,580 patent/US6013803A/en not_active Expired - Fee Related
- 1997-05-28 JP JP10500198A patent/JP2000515123A/ja not_active Withdrawn
- 1997-05-28 BR BR9709519A patent/BR9709519A/pt not_active IP Right Cessation
- 1997-05-28 AU AU31687/97A patent/AU711518B2/en not_active Ceased
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- 1997-05-28 WO PCT/EP1997/002763 patent/WO1997046528A1/de active IP Right Grant
- 1997-05-28 HU HU0001825A patent/HUP0001825A2/hu unknown
- 1997-05-28 CN CN97195198A patent/CN1088697C/zh not_active Expired - Fee Related
- 1997-05-28 NZ NZ332521A patent/NZ332521A/xx unknown
- 1997-05-28 UA UA98126947A patent/UA54430C2/uk unknown
- 1997-05-28 DE DE59701590T patent/DE59701590D1/de not_active Expired - Fee Related
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- 1997-05-28 EP EP97927060A patent/EP0906280B1/de not_active Expired - Lifetime
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- 1997-06-03 TW TW086107600A patent/TW372970B/zh active
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Also Published As
Publication number | Publication date |
---|---|
CZ391698A3 (cs) | 1999-11-17 |
ATE192434T1 (de) | 2000-05-15 |
US6013803A (en) | 2000-01-11 |
CZ291453B6 (cs) | 2003-03-12 |
CO5050411A1 (es) | 2001-06-27 |
NZ332521A (en) | 1999-06-29 |
CA2257094C (en) | 2005-11-22 |
TW372970B (en) | 1999-11-01 |
UA54430C2 (uk) | 2003-03-17 |
HUP0001825A2 (hu) | 2000-09-28 |
WO1997046528A1 (de) | 1997-12-11 |
CN1088697C (zh) | 2002-08-07 |
BR9709519A (pt) | 1999-08-10 |
MY121628A (en) | 2006-02-28 |
DE59701590D1 (de) | 2000-06-08 |
EP0906280A1 (de) | 1999-04-07 |
AU3168797A (en) | 1998-01-05 |
EP0906280B1 (de) | 2000-05-03 |
AU711518B2 (en) | 1999-10-14 |
ID17018A (id) | 1997-12-04 |
GR3033454T3 (en) | 2000-09-29 |
EA001211B1 (ru) | 2000-12-25 |
JP2000515123A (ja) | 2000-11-14 |
DE19622268C1 (de) | 1997-10-23 |
CA2257094A1 (en) | 1997-12-11 |
PL189193B1 (pl) | 2005-07-29 |
PL330276A1 (en) | 1999-05-10 |
PT906280E (pt) | 2000-10-31 |
ES2146471T3 (es) | 2000-08-01 |
EA199801029A1 (ru) | 1999-06-24 |
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