CN1154103A - 用于防止表面物理及化学降解的、丁基化羟基甲苯的脂肪胺衍生物 - Google Patents
用于防止表面物理及化学降解的、丁基化羟基甲苯的脂肪胺衍生物 Download PDFInfo
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Abstract
本发明涉及用于降低表面的物理或化学降解或脱色,尤其是各种表面在阳光曝晒后的褪色的新型抗氧剂化合物,其中的抗氧剂化合物是丁基化羟基甲苯或山梨酸的衍生物,选自(I)、(Ⅱ)、(Ⅲ)、(Ⅳ),其中每个R1及R3选自羟基、甲氧基、乙氧基、丙氧基、丁氧基、甲基、乙基、丙基、直链或支链丁基、直链或支链戊基及其混合物;R2是羟基;每个R4及R7选自饱和或不饱和C1-C22烷基、芳基、环烷基(可以是中间夹杂酯、酰胺或醚的)、氢及其混合物;每个R5、R6、R8及R9选自饱和或不饱和C1-C22烷基、芳基、环烷基(可以是中间夹杂酯、酰胺或醚基的)及其混合物;n为1-50;Y是氢或甲基;Z是氢或甲基;其中式(I)至(Ⅳ)化合物的氨基可被质子化或被R10X季铵化,其中R10是氢、C1-C6烷基、C1-C6羟基烷基、苄基及其混合物;且X-为任何相容的阴离子。
Description
技术领域
本发明涉及用于降低多种表面,即织物,因阳光照射而褪色、变色及降解的新型、不弄脏表面、光稳定抗氧剂化合物。这些抗氧剂化合物是丁基化羟基甲苯及山梨酸的衍生物,优选含有至少一个C8-C22烃脂肪胺有机部分,或为熔点低于约80℃的固体,或者在约40℃以下为液体。这些抗氧剂化合物优选地被加入到织物柔软(剂)组合物中。
发明背景
衣物、室内和汽车内装饰织物在阳光曝晒后其颜色受损是全球消费者的有的经历。例如,对于居住在热带和亚热带气候条件下的消费者而言,衣物在干燥和穿戴期间颜色损坏尤为严重。尽管产业界已进行了大量的工作,力图开发,例如室内和车内装饰物的光稳定表面;开发具有改进光照牢度的染料;采取提高织物染料光照牢度的后处理;以及开发抗褪色的塑料,日晒表面褪色的问题依然存在。
在先有技术中用于各种目的的抗氧剂化合物在技术上是已知。例如Ravichandran等人,Ciba-Geigy公司在公开日期为6/29/88的EPA273,011中公开了N,N-双(羟乙基)羟胺酯,它用于使有机材料(即有机聚烯烃、弹性体及润滑油)对氧化、热及酸的/降解稳定化。
美国专利第5,081,280号,Takee等,1992年1月14日授权,Yoshitomi Pharmaceutical Industries公司,公开了一种制备用于有机材料抗氧剂的酯化、空间位阻化合物,该化合物反应次数相对减少,褪色性较好。与本发明化合物不同的是,这些化合物不含胺官能团。
美国专利第3,330,859号,Dexter等,授权于7/11/67,Geigy化学公司,公开了用于稳定有机材料的空间位阻酚羧酸酯,所述有机材料是,例如有机聚合物及共聚物、脂族酯类润滑油、烃类材料例如汽油等。与本发明化合物不同的是、这些化合物不含胺官能团。
美国专利第3,920,729号,Sagawa等,授权于1975年11月18日,Sumitomo化学公司,公开了用于稳定有机物的空间位阻酚酯化异丙醇胺类,所述有机物尤指聚烯烃、卤化的乙烯基聚合物、卤化乙烯与聚合化合物的共聚物、丙烯腈、丁二烯及乙烯共聚物,聚胺酯,聚酯、聚缩醛、聚碳酸酯、聚苯乙烯及天然和合成橡胶。这些化合物在相对于氮原子的β碳原子上连有甲基,提高了热稳定值,当与聚烯烃混合时,喷霜减少了。
美国专利第4,305,868号,Whceler等,授权于1981年12月15日,Uniroyla,Inc.,公开了作为抗氧剂、用于防有机材料例如合成及天然橡胶、塑料和石油产品氧化降解的空间位阻酚取代的酯双酰胺(esterbisamide)。
另外,美国专利第4,900,969,Clorox公开了洗涤剂中用于漂白稳定(bleach stability)的抗氧剂。抗氧剂已用于柔软剂中,以防止织物泛黄及控制臭味(见JP72/116,783,Kao)。
因抗氧剂化合物价格昂贵,故需选择使用最有效的化合物,以使在这些化合物配剂时费用尽量低。
然而现已认识到,适用于某些应用场合的抗氧剂并不总在其它应用场合令人满意,如用于食品(防腐剂)、化妆品(防腐剂)、洗涤时添加的织物柔软剂组合物、加入干燥机的织物柔软剂组合物、洗涤剂、织物预处理或喷于织物上使用的产品(spray on products)、硬表面清洗剂(hard surface cleaner),用于地面覆盖材料(即地毯,乙烯)的组合物,车内装饰、室内装饰,头发护理产品,乙烯基处理及塑料等方面。
对于织物来说,现已发现可见光对导致衣物染料褪色起相当大的作用。例如,可见光比UV(紫外)-A对褪色的影响更甚,而后者又比UV-B对褪色的影响更甚。与防晒剂相比,抗氧剂可对织物提供更宽的阳光褪色保护,因为抗氧剂效率不依赖于光吸收。
故此,本发明的目的之一在于提供用量少、效率高的抗氧剂化合物,它们能降低各种各样表面的降解和/或脱色(即日晒褪色)的速率。
所有上述专利及专利申请并入此处,引为参考。
发明简述
本发明涉及用于降低表面的物理及化学降解或脱色,尤其是多种表面因日晒褪色的新型抗氧剂化合物,其中的抗氧剂化合物为不弄脏表面的光稳定化合物,优选含有至少一种C8-C22烃脂族有机部分,优选含有至少一种C12-C18烃脂族有机部分;其中该抗氧剂化合物为熔点低于约80℃,优选低于约50℃的固体材料;或者在低于约40℃,优选地在约0~25℃为液体。
这些抗氧剂化合物是丁基化的羟基甲苯或山梨酸的衍生物,它们选自:其中每个R1及R3选自:羟基、甲氧基、乙氧基、丙氧基、丁氧基、甲基、乙基、丙基、直链或支链丁基、直链或支链戊基、及其混合物,优选直链或支链丁基、直链或支链戊基,及其混合物,更优选叔丁基类;R2是羟基;每个R4及R7选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚基)、氢及其混合物,优选的是甲基。每个R5、R6、R8及R9选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚),优选C8-C22烷基,更优选C12-C18烷基,进一步更优选C12-C14烷基,及其混合物;n为1-50,优选1-10,更优选是1;Y为氢或甲基;且
Z是氢或甲基。
式I-IV化合物的氨基可为质子化的或者是与R10X季铵化,其中R10是氢、C1-C6烷基、C1-C6羟基烷基,优选C1-C3烷基或羟基烷基,如甲基(最优选)、乙基、丙基、羟乙基等、苄基、及其混合物;且X-为强酸的阴离子,如氯离子、溴离子、硫酸甲酯离子、甲酸根、硫酸根、硝酸根等。
本文所有百分数及比率均以占组合物总重量计。
发明详述
本发明涉及用于降低表面的物理及化学降解或脱色,尤其是多种表面因日晒褪色的新型抗氧剂化合物,其中的抗氧剂化合物为不弄脏表面的光稳定化合物,优选含有至少一种C8-C22烃脂族有机部分,优选含有至少一种C12-C18烃脂族有机部分;其中该抗氧剂化合物为熔点低于约80℃,优选低于约50℃的固体材料;或者在低于约40℃,优选地在约0~25℃为液体。
这些抗氧剂化合物是丁基化的羟基甲苯或山梨酸的衍生物,它们选自: 其中每个R1及R3选自:羟基、甲氧基、乙氧基、丙氧基、丁氧基、甲基、乙基、丙基、直链或支链丁基、直链或支链戊基、及其混合物,优选直链或支链丁基、直链或支链戊基,及其混合物,更优选叔丁基类;R2是羟基;每个R4及R7选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚基)氢及其混合物,优选的是甲基。每个R5、R6、R8及R9选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚),优选C8-C22烷基,更优选C12-C18烷基,进一步更优选C12-C14烷基,及其混合物;n为1-50,优选1-10,更优选是1;Y为氢或甲基;且
Z是氢或甲基。
式I-IV化合物的氨基可为质子化的或者是与R10X季铵化,其中R10是氢、C1-C6烷基、C1-C6羟基烷基,优选C1-C3烷基或羟基烷基,如甲基(最优选)、乙基、丙基、羟乙基等、苄基、及其混合物;且X-为强酸的阴离子,如氯离子、溴离子、硫酸甲酯离子、甲酸根、硫酸根、硝酸根等。优选地每个R1及R3为直链或支链丁基及其混合物;R4是甲基;R5选自饱和或不饱和C12-C18烷基;且n为1。
每个R1及R3更优选为叔丁基;R5选自饱和或不饱和C12-C14烷基;且n为1。
本发明特别优选的化合物是2-(N-甲基-N-椰子氨基)乙基3′,5′-二叔丁基-4-羟基苯甲酸酯。
本发明的抗氧剂化合物表现出光稳定性。“光稳定”意指在约25~45℃的温度下暴露于日光或者模拟目光下约2-60小时后本发明的抗氧剂不变色。
抗氧剂化合物及自由基清除剂通过首先防止单重态氧及过氧自由基的生成,进而终止降解通道可普遍地使表面稳定和/或防止染料降解或变色。虽不拟囿于理论,但对抗氧剂及自由基清除剂作用方式的一般讨论可参见Kirk Othmet,The Encyclopedia of Chemical Technology,第3卷,第128-148页,第三版(1978),全部收入本文作为参考。
生产方法
下述实施例进一步说明了本发明范围的实施方案。这些实施例仅为说明目的,不应视为对本发明的限制,因为在不背离本发明精神及范围内可以有多种多样的变化。
实施例1
15.64g(63.3mmol)N-甲基-N-(2-羟乙基)椰子胺溶于200mL二氯甲烷,所得溶液加热至40℃。加完6.41g(63.3mmol)三乙胺后,向溶液中加入17.00g(63.3mmol)的3,5-二叔丁基-4-羟基苯甲酰氯以维持反应温度为35-40℃。反应混合物在40℃之下再搅拌2小时,然后冷却至室温。搅拌16小时之后,过滤含反应产物的溶液,浓缩滤液。所得残余物重新溶于300mL氯仿,用50%K2CO3水溶液洗涤两次,,每次50mL。将有机层分离出来,MgSO4干燥,过滤,浓缩。产物用色谱柱提纯。产物纯度用薄层色谱测定,结构用13C NMR核磁共振鉴定。
实施例2
22.09克(78.1mmol)N,N-双(2-羟乙基)-椰子胺及15.79g(156.3mmol)三乙胺溶于100mL二氯甲烷。所得溶液用42.00g(156.3mmol)3,5-二叔丁基-4-羟基苯甲酰氯在100mL二氯甲烷中的溶液处理。加料期间反应温度保持在35-40℃。反应混合物在回流下再搅拌60分钟,然后冷却至室温。混合物过滤,滤液浓缩。将所得残余物重新溶于200mL二氯甲烷中,以50%K2CO3水溶液洗涤两次,每次100mL,用100mL饱和碳酸氢钠水溶液洗涤一次,用100mL盐水洗涤一次。分离出该有机层,用MgSO4将其干燥,过滤,浓缩得到粘稠油。产物纯度由薄层色谱测定,用13C NMR鉴定其结构。
实施例3
36.28g(144.0mmol)N-甲基-N-(2-羟乙基)椰子胺和14.62g(144.0mmol)三乙胺溶于250mL二氯甲烷中。所得溶液用18.80g(144.0mmol)2,4-反,反-己二烯酰氯处理。加料期间,反应温度维持于35-40℃。于回流下再搅拌反应混合物2小时,然后冷却至室温。将混合物过滤,滤液浓缩。所得残余物重新溶于300mL二氯甲烷中,以200mL50%K2CO3水溶液洗涤两次,200mL饱和NaHCO3水溶液洗涤两次。将有机层分离出来,用MgSO4将其干燥,以活性炭处理,过滤,浓缩得一油。产物纯度由薄层色谱测定,结构由13C NMR鉴定。
组合物
本发明同时涉及降低表面物理或化学降解的组合物,它包含:
(A)有效量的抗氧剂化合物;及
(B)有效量的载体材料;其中的抗氧剂化合物选自:其中每个R1及R3选自:羟基、甲氧基、乙氧基、丙氧基、丁氧基、甲基、乙基、丙基、直链或支链丁基、直链或支链戊基、及其混合物,优选直链或支链丁基、直链或支链戊基,及其混合物,更优选叔丁基类;R2是羟基;每个R4及R7选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚基)氢、及其混合物,优选的是甲基。每个R5、R6、R8及R9选自:饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚),优选C8-C22烷基,更优选C12-C18烷基,进一步更优选C12-C14烷基,及其混合物;n为1-50,优选1-10,更优选是1;Y为氢或甲基;且
Z是氢或甲基。
氨基可为质子化的或者是与R10X季铵化,其中R10是氢、C1-C6烷基、C1-C6羟基烷基,优选C1-C3烷基或羟基烷基,如甲基(最优选)、乙基、丙基、羟乙基等、苄基、及其混合物;且X为强酸的阴离子,如氯离子、溴离子、硫酸甲酯离子、甲酸根、硫酸根、硝酸根等。
本发明组合物所用载体和/或稀释剂是非毒性、非刺激性物质,当其与抗氧剂化合物混合时,促使抗氧剂分布在该表面上。本发明组合物优选含约25-95%,更优选50-90%的液态载体。由于水的成本较低及其安全性、环境相容性,故载体和/或稀释剂优选主要为水。按占载体重量计,液态载体中水的用量为至少约50%,优选至少约60%。水与低分子量,如<100g/mol,的有机溶剂,如低级醇如乙醇、丙醇、异丙醇或异丁醇,的混合物可用作载体。低分子量醇包括单羟基、二羟基(二元醇等)、三羟基(甘油等)及更多个羟基(多元醇)的醇。
Claims (9)
1.一种降低因日晒引起的表面降解或脱色的抗氧剂化合物,它选自:其中每个R1及R3选自羟基、甲氧基、乙氧基、丙氧基、丁氧基、甲基、乙基、丙基、直链或支链丁基、直链或支链戊基及其混合物;R2是羟基;每个R4及R7选自饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚基)、氢及其混合物;每个R5、R6、R8、及R9选自饱和或不饱和C1-C22烷基、芳基、环烷基(其中间可夹杂有酯、酰胺或醚基)、及其混合物;
n为1-50;
Y是氢原子或甲基;
Z是氢原子或甲基;其中式I至IV化合物的氨基可以是被质子化或被R10X季铵化了的,其中R10是氢、C1-C6烷基、C1-C6羟基烷基、苄基及其混合物;且X-为任何相容的阴离子。
2.权利要求1的抗氧剂化合物,其中的抗氧剂化合物是熔点低于80℃的固体材料,或者是在低于40℃时为液体。
3.权利要求1的抗氧剂化合物,其中的抗氧剂化合物是熔点低于50℃的固体材料,或者是在0-25℃时为液体。
4.权利要求3的抗氧剂化合物,其中该化合物是2-(N-甲基-N-椰子氨基)乙基3′,5′-二叔丁基-4-羟基苯甲酸酯。
5.权利要求1的抗氧剂化合物,其中每个R1及R3为线型或支链丁基、线型或支链戊基或其混合物;R4为甲基;R7为甲基;每个R5、R6、R8及R9选自饱和或不饱和C12-C18烷基及其混合物;且n是1。
6.权利要求5的抗氧剂化合物,其中每个R1及R3是叔丁基;每个R5、R6、R8及R9选自饱和或不饱和C12-C14烷基及其混合物。
7.权利要求6的抗氧剂化合物,其中该抗氧剂化合物选自式I的化合物、式II的化合物及其混合物。
8.权利要求7的抗氧剂化合物,其中该抗氧剂化合物是2-(N-甲基-N-椰子氨基)乙基3′,5′-二叔丁基-4-羟基苯甲酸酯。
9.一种降低表面物理或化学降解的组合物,它包含:
(A)有效量权利要求1、7或8的抗氧剂化合物;和
(B)有效量的载体物质。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/280,685 US5543083A (en) | 1994-07-26 | 1994-07-26 | Fatty amine derivatives of butylated hydroxy toluene for the protection of surfaces from physical and chemical degradation |
US08/280,685 | 1994-07-26 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN99121550.8A Division CN1273265A (zh) | 1994-07-26 | 1999-10-12 | 降低表面降解或脱色的抗氧剂化合物及含它的组合物 |
Publications (2)
Publication Number | Publication Date |
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CN1154103A true CN1154103A (zh) | 1997-07-09 |
CN1071310C CN1071310C (zh) | 2001-09-19 |
Family
ID=23074157
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95194353A Expired - Fee Related CN1071310C (zh) | 1994-07-26 | 1995-07-13 | 用于防止表面物理及化学降解的、丁基化羟基甲苯的脂肪胺衍生物 |
CN99121550.8A Pending CN1273265A (zh) | 1994-07-26 | 1999-10-12 | 降低表面降解或脱色的抗氧剂化合物及含它的组合物 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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CN99121550.8A Pending CN1273265A (zh) | 1994-07-26 | 1999-10-12 | 降低表面降解或脱色的抗氧剂化合物及含它的组合物 |
Country Status (13)
Country | Link |
---|---|
US (1) | US5543083A (zh) |
EP (2) | EP0773922B1 (zh) |
JP (1) | JPH10503491A (zh) |
CN (2) | CN1071310C (zh) |
AT (1) | ATE194137T1 (zh) |
AU (1) | AU2969495A (zh) |
CA (1) | CA2192803A1 (zh) |
DE (2) | DE69522972T2 (zh) |
DK (1) | DK0773922T3 (zh) |
ES (2) | ES2149367T3 (zh) |
GR (1) | GR3034371T3 (zh) |
PT (1) | PT773922E (zh) |
WO (1) | WO1996003369A1 (zh) |
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-
1994
- 1994-07-26 US US08/280,685 patent/US5543083A/en not_active Expired - Fee Related
-
1995
- 1995-07-13 JP JP8505771A patent/JPH10503491A/ja not_active Withdrawn
- 1995-07-13 DK DK95925625T patent/DK0773922T3/da active
- 1995-07-13 PT PT95925625T patent/PT773922E/pt unknown
- 1995-07-13 EP EP95925625A patent/EP0773922B1/en not_active Expired - Lifetime
- 1995-07-13 ES ES95925625T patent/ES2149367T3/es not_active Expired - Lifetime
- 1995-07-13 WO PCT/US1995/008711 patent/WO1996003369A1/en active IP Right Grant
- 1995-07-13 EP EP99870028A patent/EP0926132B1/en not_active Expired - Lifetime
- 1995-07-13 CA CA002192803A patent/CA2192803A1/en not_active Abandoned
- 1995-07-13 AU AU29694/95A patent/AU2969495A/en not_active Abandoned
- 1995-07-13 AT AT95925625T patent/ATE194137T1/de not_active IP Right Cessation
- 1995-07-13 DE DE69522972T patent/DE69522972T2/de not_active Expired - Fee Related
- 1995-07-13 ES ES99870028T patent/ES2161090T3/es not_active Expired - Lifetime
- 1995-07-13 DE DE69517690T patent/DE69517690T2/de not_active Expired - Fee Related
- 1995-07-13 CN CN95194353A patent/CN1071310C/zh not_active Expired - Fee Related
-
1999
- 1999-10-12 CN CN99121550.8A patent/CN1273265A/zh active Pending
-
2000
- 2000-09-08 GR GR20000402057T patent/GR3034371T3/el not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
DE69522972D1 (de) | 2001-10-31 |
CN1273265A (zh) | 2000-11-15 |
AU2969495A (en) | 1996-02-22 |
CA2192803A1 (en) | 1996-02-08 |
EP0926132A3 (en) | 1999-07-07 |
EP0926132B1 (en) | 2001-09-26 |
ATE194137T1 (de) | 2000-07-15 |
ES2149367T3 (es) | 2000-11-01 |
EP0926132A2 (en) | 1999-06-30 |
DK0773922T3 (da) | 2000-08-28 |
EP0773922B1 (en) | 2000-06-28 |
EP0773922A1 (en) | 1997-05-21 |
US5543083A (en) | 1996-08-06 |
DE69517690T2 (de) | 2001-02-22 |
JPH10503491A (ja) | 1998-03-31 |
CN1071310C (zh) | 2001-09-19 |
DE69522972T2 (de) | 2002-06-06 |
PT773922E (pt) | 2000-11-30 |
ES2161090T3 (es) | 2001-11-16 |
DE69517690D1 (de) | 2000-08-03 |
WO1996003369A1 (en) | 1996-02-08 |
GR3034371T3 (en) | 2000-12-29 |
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