CN113443991A - 一种低迁移受阻酚抗氧化合物、制备方法及组合物 - Google Patents

一种低迁移受阻酚抗氧化合物、制备方法及组合物 Download PDF

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CN113443991A
CN113443991A CN202010222099.5A CN202010222099A CN113443991A CN 113443991 A CN113443991 A CN 113443991A CN 202010222099 A CN202010222099 A CN 202010222099A CN 113443991 A CN113443991 A CN 113443991A
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tert
butyl
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hydroxyphenyl
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曾裕峰
魏海涛
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Youdi Co ltd
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Youdi Co ltd
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Priority to CN202010222099.5A priority Critical patent/CN113443991A/zh
Priority to CN202211316611.8A priority patent/CN115819238A/zh
Priority to TW110110333A priority patent/TW202208327A/zh
Priority to KR1020227037289A priority patent/KR20220158070A/ko
Priority to JP2022558562A priority patent/JP2023520386A/ja
Priority to PCT/CN2021/082762 priority patent/WO2021190569A1/zh
Priority to US17/914,559 priority patent/US20230312457A1/en
Publication of CN113443991A publication Critical patent/CN113443991A/zh
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Abstract

本发明公开了一种低迁移受阻酚抗氧化合物、制备方法及组合物，聚合物在生产加工或使用中，会受到光、氧、热等因素的影响而发生降解。往往通过添加一种或多种常用抗氧剂来增加其抗氧化能力，以此抑制和延缓其氧化降解速率。传统受阻酚类抗氧化合物结构，在聚合物中会有迁移现象。本发明受阻酚类抗氧化合物，具有更多单元受阻酚，可实现低萃取、低迁移的目标。

Description

一种低迁移受阻酚抗氧化合物、制备方法及组合物
技术领域
本发明涉及一种低迁移受阻酚抗氧化合物、制备方法及组合物。
背景技术
聚合物材料在生产加工及使用中往往会受到光、氧、热等因素的影响而发生降解，导致聚合物材料的物理、化学性能下降。因此聚合物材料往往通过添加一种或多种抗氧剂来增加其抗氧化能力。并以此抑制或延缓其氧化降解，延长其使用寿命。
其中受阻酚类化合物是最重要的抗氧化合物之一。受阻酚类抗氧剂在改善聚合物抗热氧老化性能方面已有广泛应用。
但传统受阻酚类抗氧化合物，在聚合物中会有迁移现象，严重影响效能。
传统受阻酚抗氧剂，例如2，4，6-三叔丁基苯酚(AO333)、二丁基羟基甲苯(BHT)、Irganox 1076。因为挥发性强，容易从聚合物内扩散迁移至表面，最终使聚合物中抗氧剂的含量消失，严重影响效能。且抗氧剂进入环境，破坏生态，对人体健康也有危害。
因此，设计具有耐迁移性的受阻酚抗氧剂具有重要意义。目前解决这些问题的方法之一是开发出多单元受阻酚抗氧剂，延缓迁移。例如Irganox 245是2单元受阻酚抗氧剂，例如Irganox 1330是3单元受阻酚抗氧剂，例如Irganox 1010是4单元受阻酚抗氧剂。然而单纯增加受阻酚抗氧剂分子量，并不一定能同时兼顾抗迁移和抗氧化性质。如何开发出更佳的具有抗迁移性质的多单元受阻酚抗氧剂，成为业者努力目标。
发明内容
目的：为解决现有技术的不足，本发明提供一种低迁移受阻酚抗氧化合物、制备方法及组合物，使得(受阻酚单元/分子量)的比值维持在最佳范围。该方法包括对(受阻酚单元数/分子量)做优化，使得优化后与优化前的(受阻酚单元数/分子量)比值大于1。也就是说，新增加的紧致的抗氧剂单元不至于让分子量增加太多。例如，本发明化合物10(实例10)和Eunox 1035(实例60)的(受阻酚单元数/分子量)的比值为(4/966)∶(2/642)＝1.33(＞1)。
令人惊讶地，这样的设计，大幅提高抗氧剂在树脂中的留存，也就是解决了传统受阻酚抗氧剂易迁移的缺点。
技术方案：为解决上述技术问题，本发明采用的技术方案为：
第一方面，提供一种式(I)化合物或其盐，
Figure BDA0002426415630000021
其中，R1-R7，是取代基团，R1-R2各自独立地选自含C1-C12较佳地，C1-C12，的烷基、苯基、苄基、枯基(cumyl)、C1-C12硫烷、C1-C2亚甲基C1-C12硫烷；R3-R4选自氢、含C1-C6的烷基、苯基、苄基、枯基、C1-C12硫烷、C1-C2亚甲基C1-C12硫烷。R5-R6各自独立地选自氢、羟基、卤素、羧基、含C1-C6烷基、羰基、酰基、酯基、C1-C6烷基胺基、C1-C6烷氧基、苯基、或R5-R6合为一酮基。较佳地，R1-R2各自独立地选自含C1-C5的烷基、苯基、苄基、枯基；R3-R4各自独立地选自氢、羟基、含C1-C5的烷基、羰基、酰基、C1-C5烷基胺基、C1-C5烷氧基；R5-R6各自独立地选自氢、羟基、含C1-C5的烷基、苯基。特佳地，R1-R2各自独立地选自甲基、叔丁基、枯基；R3-R4各自独立地选自氢、羟基、甲基、叔丁基；R5-R6各自独立地选自氢、羟基、含C1-C4的烷基。
R7是q价基团。较佳地，R7包括一键、氢、未取代或经取代的杂原子、未取代或经取代的碳或碳链、未取代或經取代的经氧或硫或氮所中断的碳链、碳环、杂环。更佳地，碳是一级到四级碳，碳链是C1-C20碳链，经氧或硫或氮所中断的碳链，可以是非聚合的C1-C20杂碳链或是包含多个聚合单元的链，例如聚乙二醇。较佳地，碳环为五到七元环，杂环为含氧或硫或氮的五到七元环。
更佳地，R7包括H、一键、(C)a(CH)b(CH2)c(CH3)d，其中(C)a和(CH)b和(CH2)c和(CH3)d之间的顺序可交错或互换，a～d不同时为0，a～d＝0～18、(CH2CH2O)tH、(CH2CH2O)tOCH3、(CH)q-2(CH2)1～10(CH3)1～4，较佳地，(CH)q-2(CH2)1～10(CH3)1～3，其中(CH)q-2和(CH2)1～10和(CH3)1～3之间的顺序可交错或互换、S、SH、O、OH、N、NH、NHR8、P、Ca、Mg、Zn、Na、K、-(CHR8)1～18-、-(CH)q-2(CH2)1～18-，其中(CH)q-2和(CH2)1～18之间的顺序可交错或互换、-(C＝O)1-4-、-(CHR8)u-、-(C＝O)1-4(CHR8)u-，其中(C＝O)1-4和(CHR8)u之间的顺序可交错或互换、-(CHR8)uS1-4(CHR8)u-、-(CHR8)uO1-4(CHR8)u-、-(CH2CH2O)tCH2CH2-、
Figure BDA0002426415630000041
三嗪类、三聚氰胺类、未经取代或经取代苯基或苄基、C1-C8环烷基；q≥a+b+c+d；t＝1-20u＝1-20。其中(CH)q-2和(CH2)1～18之间的顺序可互换，较佳地，-(CH)q-2(CH2)1～18-是-(CH2)1(CH)(CH2)1-或-(CH2)2(CH)(CH2)2-。较佳地，(C)a(CH)b(CH2)c(CH3)d，是C、CH、CH2、CH3，a～d＝0-8，更佳地，a～d＝0-4。较佳地，t＝1-10。u＝1-10。更佳地，t＝1-5。u＝1-5。
X是碳或杂原子，较佳地，选自选自N、NH、NHR8、O、S、CH2、CHR8，R8选自H、OH、含C1-C6的烷基，更佳地，X选自NH、O、CH2，特佳地，X＝NH或O。
m＝0-5、n＝0-5、p＝0-18、q＝1-8、r＝0-3、s＝0-2。较佳地，m＝0-2、n＝0-2、p＝0-18、q＝1-6、r＝0-1、s＝0-1。更佳地，m＝1、n＝2、q＝1-4、r＝1、s＝0。
特佳地，式(I)为以下结构：
Figure BDA0002426415630000051
R1-R7、m、n、X、p、r如上所定义。
特佳地，式(I)为以下结构：
Figure BDA0002426415630000052
R1-R7、m、n、X、p、q、r如上所定义。当R7＝-(CH2CH2O)tCH2CH2-时，t＞1。
特佳地，式(I)为以下结构：
Figure BDA0002426415630000061
R1-R7、m、n、X、p、q、r如上所定义。
式(I)所示化合物的制备方法，其特征在于，包括一酯化或转酯化反应如下：
Figure BDA0002426415630000062
其中，R1-R6、n、r、s如上所定义；-X(CH2)pR7是OH或离去基。较佳地，离去基是OCH3或卤素。
其中化合物(IV)，由以下酯化或酯交换反应式所合成：
Figure BDA0002426415630000063
其中，R9是苯环上或非苯环上的可产生傅-克(Friedel-Crafts)烷基化或酰基化反应的基团，当R9是苯环上基团时，其包括卤素、C1-C8卤烷基、卤酰基、C1-C8卤酰基、C1-C8烯基。当R9是非苯环上基团时，其包括C1-C8烷基的醛或酮。
本发明反应，可以使用任何酯化或酯交换催化剂，较佳地，三异丙醇铝或锡化合物，特别是是二乙酸二丁基锡。可用于本发明实践的催化剂的例子包括辛酸亚锡，草酸亚锡，二月桂酸二丁基锡，二月桂酸二辛基酯，二丁基二辛基-2-乙基己酸酯，钛酸四异丙酯，钛酸四丁酯，钛酸四-2-乙基己酯，二丁基二呋喃基硫醇酯，二丁基二吲哚基辛基巯基乙酸盐，二月桂酸二丁基锡，二丁基氧化锡，丁基锡酸等。
本发明式(I)化合物，可用于组合物，提供抗氧化功能。组合物可应用于各种有机材料，例如但不限于多元醇或聚氨酯。多元醇在后续生产聚氨酯泡沫时过程中会释放大量热量，造成黄变，若添加一般抗氧化剂，因为抗氧化剂本身析出，也会造成黄变。本发明受阻酚抗氧剂适合各种材料，以尼龙-6树脂为例，100重量份计为0.1～5重量份。本发明的受阻酚类抗氧剂可与亚磷酸酯抗氧剂并用，受阻酚类抗氧剂与亚磷酸酯抗氧剂的混合重量比例，较佳为1∶4～1∶1。本发明的受阻酚类抗氧剂可也与其他安定剂并用，例如紫外线吸收剂、受阻胺等。
具体实施方式
下面结合实施例对本发明作进一步描述。以下实施例只是用于更加清楚地说明本发明的性能，而不能仅局限于下面的实施例。
本发明的受阻酚类抗氧剂，以实施例具体表示，但不限于实施例化合物。其中R7为一联结结构，例示如表1。
表1
Figure BDA0002426415630000081
Figure BDA0002426415630000082
Figure BDA0002426415630000091
表2
Figure BDA0002426415630000092
Figure BDA0002426415630000093
表3
Figure BDA0002426415630000101
Figure BDA0002426415630000102
实施例1
3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000103
取25.4g的2，4-二叔丁基-6-氯甲基酚(化合物1.1)和23.6g的3-(3-(叔丁基)-4-羟基苯基)丙酸甲酯(CAS No 36837-50-0，mp＝60℃)，溶于200mL干燥的CH2Cl2，氮气下室温下搅拌，加入14g的AlCl3继续搅拌。TLC监控反应，其间补充AlCl3。反应完成后，混合物倒入200mL冰水中，搅拌，用CH2Cl2萃取3次。合并萃取相，依次用1％稀盐酸和盐水洗涤，无水硫酸钠干燥。蒸干溶剂，得到的残余物使用柱层析纯化，得到化合物(1)。MS(m/z)＝454.3。H1-NMR(CDCl3)，化学位移4.0，(aromatic carbon-CH2 -aromatic carbon)新生，说明化合物(1)被合成。
Figure BDA0002426415630000111
2，4-二叔丁基-6-氯甲基酚(化合物1.1)制法：在50ml反应瓶加入3g的2，4-二叔丁基苯酚(96-76-4)、0.6g的多聚甲醛、20克的乙酸、35％盐酸3克，升温到60℃，保温反应10个小时，取样监控反应。降温、水洗、烘干得化合物1.1。熔点：62℃。
Figure BDA0002426415630000112
实施例2
3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苯甲酰基)-4-羟基苯基)丙酸甲酯(2)
Figure BDA0002426415630000113
根据实施例1方法，但以3，5-二叔丁基-2-羟基苯甲酰氯，代替2，4-二叔丁基-6-氯甲基酚(化合物1.1)，得到化合物(2)，还原得到化合物(1)。化合物(2)：MS(m/z)＝468.3。C13-NMR(CDCl3)，化学位移199.1，(aromatic-C(O)-aromatic)新生，说明化合物(2)被合成。
Figure BDA0002426415630000121
实施例3
3-(3-叔丁基-5-((3，5-二叔丁基-2-羟基苯基)(羟基)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000122
100ml乙醇和10g化合物(2)混合物用冰水冷却，加入7.4g NaBH4，混合物保反应搅拌1hr完成。反应体系用冰乙酸中和至，然后真空条件下浓缩。浓缩物在CH2Cl2和水中进行分层，然后把有机相分出，用饱和盐水洗涤，用无水Na2SO4干燥后浓缩。得到化合物(3)。MS(m/z)＝470.3。
H1-NMR(CDCl3)，化学位移6.2峰(aromatic carbon-HCOH-aromatic carbon)新生，说明化合物(3)被合成。
Figure BDA0002426415630000131
实施例4
3-(3-(叔丁基)-5-(1-(3-叔丁基-5-甲基-2-羟基苯基)乙基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000132
根据实施例1方法，但以乙醛代替聚甲醛，2-叔丁基-4-甲基酚代替2，4-二叔丁基酚，经层析法分离，得到化合物(4)。MS(m/z)＝426.3。
Figure BDA0002426415630000133
实施例5
3-(3-(叔丁基)-5-(3-甲基-5-(叔丁基)-2-羟基苄基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000134
根据实施例1方法，但以2-(氯甲基)-4-(叔丁基)-6-甲基苯酚，代替2，4-二叔丁基酚，得到化合物(5)。MS(m/z)＝412.3。
实施例6
3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸辛酯
Figure BDA0002426415630000141
将22.7g实施例1所制备的式(1)化合物，和10g辛醇(ExxonMobil Chemical)、0.2g三异丙醇铝(甲苯中)混合。将反应混合物搅拌并在氮气环境下85℃，升温，抽真空将生成的甲醇冷凝除去。监控反应，当反应完成，加入柠檬酸水溶液(50％)，连续搅拌20分钟。然后，在75℃将水加入并搅拌20分钟。将有机相分离，然后用盐水洗涤两次，然后用硫酸钠干燥。接着甲苯和过量的辛醇减压下蒸馏出，将残留物真空干燥。经层析法分离，得到化合物(6)。MS(m/z)＝552.4。
实施例7
3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸十八烷基酯
Figure BDA0002426415630000151
根据实施例6方法，但以硬脂醇代替辛醇，得到化合物(7)。MS(m/z)＝692.6。
实施例8
2，5，8，11，14，17，20-七氧杂多糖-22-基-3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯
Figure BDA0002426415630000152
同实施例7方法，以Methoxypolyethylene glycol 350代替辛醇，产物经GPC纯化，得到化合物(8)。
实施例9
2-(2-(2-羟基乙氧基)乙氧基)乙基-3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯
Figure BDA0002426415630000161
根据实施例6方法，但以三甘醇(triethylene glycol)，代替辛醇，控制三甘醇过量，得到化合物(9)和其二聚体。
实施例10
硫代双(乙烷-2，1-二基)双(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯)(10)
Figure BDA0002426415630000162
根据根据实施例6方法，控制化合物(1)和二元醇类莫尔比2∶1以上。使用100g化合物(1)和12.2g的2，2′-硫代二乙醇。得到化合物(10)。
MS(m/z)＝966.6。
实施例11
2-(2-(2-((3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酰基)氧基)乙氧基)乙氧基)3-(3-(3，5-二叔丁基-2-羟基苄基)-4-羟基-5-甲基苯基)丙酸酯
Figure BDA0002426415630000171
根据根据实施例10方法，但使用化合物(1)和三甘醇(triethylene glycol)。得到化合物(11)。MS(m/z)＝994.7。
实施例12
N，N′-(丙烷-1，3-二基)双(3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酰胺)
Figure BDA0002426415630000172
取化合物(1)水解产物3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸(化合物19-1)，66g(约1.5摩尔)、氯化亚砜27g(约2.25摩尔)，于90℃反应3小时后，减压蒸出过量的二氯亚砜。得到3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酰氯)(化合物12.2)。降温至60℃，加入甲苯100g，搅拌均匀。滴加由己二胺5.8g(0.5摩尔)、吡啶10g(1.25摩尔)和甲苯50克组成的混合液，控制温度小于60℃。滴完，升温至85℃，反应2小时。水洗后干燥，蒸去溶剂。经层析法分离，得到化合物(12)。MS(m/z)＝960.7。
Figure BDA0002426415630000181
化合物(1)水解：将45.4g化合物(1)，100ml甲醇，氮气下搅拌。60℃时开始滴加22ml的30％NaOH溶液。滴加完毕后，缓慢加热至65℃反应4h后，加入160mL的2N稀盐酸中和，搅拌2小时，水洗至中性、干燥后得到化合物(1)自由酸3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸)(化合物12-1)。
实施例13
1，6-二基双(3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸己酯)
Figure BDA0002426415630000182
根据根据实施例10方法，但使用化合物(1)和己二醇。得到化合物(13)。MS(m/z)＝947.6。
实施例14
双(乙烷-2，1-二基)双(3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基))-4-羟基苯基)丙酸(草酰二(氮杂-二基))酯
Figure BDA0002426415630000191
根据根据实施例10方法，但使用化合物(1)和N.N′-二羟乙基草酰胺(1871-89-2，mp＝168℃)。得到化合物(14)。MS(m/z)＝1020.6。
实施例15
(2，4，8，10-四氧杂螺[5.5]十一烷-3，9-二基)双(2-甲基丙烷-2，1-二基)双(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000192
根据根据实施例10方法，将化合物(1)和螺环乙二醇反应。得到化合物(15)。MS(m/z)＝1148.8。螺环乙二醇，是工业原料2，2′-(2，4，8，10-四氧杂螺[5.5]十一烷-3，9-二基)双(2-甲基丙-1-醇)(mp＝202℃)。
Figure BDA0002426415630000193
实施例16
3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)-N′-(3-(3-叔丁基-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酰基)丙烷酰肼
Figure BDA0002426415630000201
根据实施例12方法，但以水合肼代替己二胺。得到化合物(16)。MS(m/z)＝876.6。
实施例17
四(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)苯丙酸季戊四醇酯
Figure BDA0002426415630000202
根据根据实施例10方法，但使用化合物(1)和季戊四醇。得到化合物(17)。MS(m/z)＝1945.2。
Figure BDA0002426415630000211
实施例18
N，N”，N″-(1，3，5-三嗪-2，4，6-三基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基苄)-4-羟基苯基)丙酰胺)
Figure BDA0002426415630000212
根据实施例12方法，但以三聚氰胺代替己二胺。使用150g的3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酰氯和12.6g的三聚氰胺。得到化合物(18)。MS(m/z)＝1392.9。
Figure BDA0002426415630000213
实施例19
(2，4，6-三氧代-1，3，5-三嗪-1，3，5-三基)三(乙烷-2，1-二基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000221
根据实施例10方法，但使用150g化合物(1)和26g的三羟乙基异氰尿酸酯。三羟乙基异氰尿酸酯是工业原料(839-90-7，mp＝136℃)。得到化合物(19)。MS(m/z)＝1527.9。
Figure BDA0002426415630000222
实施例20
(2，4，6-三甲基苯-1，3，5-三基)三(亚甲基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000223
根据实施例10方法，但使用150g化合物(1)和21g的2，4，6-三甲基苯-1，3，5-三基)三甲醇。得到化合物(20)。MS(m/z)＝1477.0。
Figure BDA0002426415630000231
实施例21
(一-六基苯)三(亚甲基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸酯)混合物
根据实施例10方法，但使用30g化合物(1)和2.6g的1，2，3，4，5，6六甲醇苯。得到混合物(21)。
Figure BDA0002426415630000232
实施例22
1，2，3-三(3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸苯酯)丙烷
Figure BDA0002426415630000241
根据实施例10方法，但使用150g化合物(1)和9.2g的丙三醇。得到化合物(22)。MS(m/z)＝1358.9。
Figure BDA0002426415630000242
实施例23
3-(3-(叔丁基)-5-(3，5-二叔丁基-2-羟基苄基)-4-羟基苯基)丙酸钙
45.4g化合物(1)，在醇类混合溶液200ml中，氮气下搅拌。滴加约100ml的5％NaOH溶液。滴加完毕后，缓慢加热至60℃，反应4小时。旋蒸去除去醇类溶剂，加入100ml乙酸乙酯萃取。取水层，滴加稀盐酸中和至pH＝7-8，同时逐步加入0.5M二氯化钙水溶液，搅拌2小时，静置，过滤。碳酸钾水溶液清洗除去游离酸，水洗至中性、干燥后得到化合物(23)
实施例24
3-(3-(5-(叔丁基)-2-羟基-3-(2-苯基丙烷-2-基)苄基)-4-羟基-5-(2-苯基丙烷-2-基)苯基甲基)丙酸甲酯
Figure BDA0002426415630000251
根据实施例1方法，但使用4-(叔丁基)-2-(2-苯基丙-2-基)苯酚(化合物24-1)和3-(4-羟基-3-(2-苯基丙烷-2-基)苯基)丙酸甲酯化合物(24-2)进行反应。得到化合物(24)。
化合物(24-1)或化合物(24-2)制法如下：根据实施例1方法，15g的4-叔丁基苯酚(或29.8g的3-(4-羟基-3-(2-苯基丙烷-2-基)苯基)丙酸甲酯)和15.4g的2-氯-2-苯基丙烷(CAS RN，515-40-2)、加入200mL的二氯甲烷，氮气搅拌下，加入加入无水14g的AlCl3搅拌过夜。TLC监控显示反应完成。反应混合物倾倒入200mL冰水中，搅拌，用CH2Cl2萃取3次。合并萃取相，依次用1％稀盐酸和盐水洗涤，无水硫酸钠干燥。蒸发仪上蒸干溶剂，得到的残余物使用柱层析纯化，得到化合物(24-1)，MS(m/z)＝268.2或化合物(24-2)。MS(m/z)＝298.2。
Figure BDA0002426415630000252
实施例25
3-(3-(5-(叔丁基)-2-羟基苄基)-5-((十二烷基硫代)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000261
根据实施例1方法，但以3-(3-(十二烷基硫代)-4-羟基苯基)丙酸甲酯，代替化合物(1)，得到化合物(25)。MS(m/z)＝570.4。
Figure BDA0002426415630000262
3-(3-(十二烷基硫代)-4-羟基苯基)丙酸甲酯制法：100g的4-羟基苯基-丙酸甲酯加入十二烷硫醇86g、多聚甲醛19g、二甲基甲酰胺150mL、哌啶3.6g，在氮气保护下加热回流过夜。过滤、水洗、抽滤后得到化合物(25.2)。
Figure BDA0002426415630000263
实施例26
3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000271
取25.4g的2，6-二叔丁基-4-氯甲基酚(CAS No 955-01-1，mp＝40℃)和29g的3-(3-(叔丁基)-4-羟基苯基)丙酸甲酯(CAS No 36837-50-0，mp＝60℃)，溶于200mL干燥的CH2Cl2，氮气下室温下搅拌，加入无水14g的AlCl3搅拌。TLC监控反应，其间补充AlCl3。反应完成后，反应混合物倾倒入200mL冰水中，搅拌，用CH2Cl2萃取3次。合并萃取相，依次用1％稀盐酸和盐水洗涤，无水硫酸钠干燥。蒸发仪上蒸干溶剂，得到的残余物使用柱层析纯化，得到化合物(26)。MS(m/z)＝454.3。
Figure BDA0002426415630000272
实施例27
3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苯甲酰基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000273
根据实施例26方法，但以3，5-二叔丁基-4-羟基苯甲酰氯，代替2，6-二叔丁基-4-氯甲基酚，得到化合物(27)。MS(m/z)＝468.3。
Figure BDA0002426415630000281
实施例28
3-(3-叔丁基-5-((3，5-二叔丁基-4-羟基苯基)(羟基)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000282
根据实施例3方法，但以化合物(27)代替化合物(2)，得到化合物(28)。MS(m/z)＝470.3。
实施例29
3-(3-(叔丁基)-5-(1-(3，5-二叔丁基-4-羟基苯基)乙基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000283
根据实施例1方法，但以乙醛代替聚甲醛，得到化合物(29)。MS(m/z)＝468.3。
实施例30
3-(3-(叔丁基)-5-(3-(叔丁基)-4-羟基-5-甲基苄基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000291
根据实施例26方法，但以2-(氯甲基)-4-(叔丁基)-6-甲基苯酚，代替2，4-二叔丁基-6-氯甲基酚，得到化合物(30)。MS(m/z)＝412.3。
实施例31
3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸辛酯
Figure BDA0002426415630000292
根据实施例6方法，但以，但以化合物(26)代替化合物(1)，得到化合物(31)。MS(m/z)＝552.4。
实施例32
3-(3，5-二叔丁基-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸十八烷基酯
Figure BDA0002426415630000301
根据实施例7方法，但以，但以化合物(26)代替化合物(1)，得到化合物(32)。MS(m/z)＝692.6。
实施例33
氧代双(乙烷-2，1-二基)双(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000302
将120g化合物(26)，和13g二甘醇、0.5g三异丙醇铝(甲苯中)混合。将反应混合物搅拌并在氮气环境下85℃，升温，抽真空将生成的甲醇冷凝除去。监控反应，当反应完成，加入柠檬酸水溶液(50％)，连续搅拌20分钟。然后，在75℃将水加入并搅拌20分钟。将有机相分离，然后用盐水洗涤两次，然后用硫酸钠干燥。接着甲苯和过量的辛醇从有机相在减压下蒸馏出，将残留物真空干燥。经层析分离，得到化合物(33)。MS(m/z)＝950.6。
实施例34
(乙烷-1，2-二基双(氧基))双(乙烷-2，1-二基)双(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-)羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000311
根据实施例33方法，但以三甘醇代替二甘醇，得到化合物(34)。MS(m/z)＝994.7。
实施例35
硫代双(乙烷-2，1-二基)双(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000312
根据实施例33方法，但以2，2′-硫代二乙醇代替二甘醇，得到化合物(35)。MS(m/z)＝966.6
实施例36
3，6，9，12，15，18，21，24-八氧代二十六烷-1，26-二基双(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-)羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000321
根据实施例33方法，但以九甘醇代替二甘醇，经层析得到化合物(36)。
实施例37
N，N′-(丙烷-1，3-二基)双(3-(3-叔丁基-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酰胺)
Figure BDA0002426415630000322
根据实施例12方法，但以，但以化合物(26)代替化合物(1)，得到化合物(37)。MS(m/z)＝960.7。
实施例38
1，6-二基双(3-(3-叔丁基-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸己酯)
Figure BDA0002426415630000323
根据实施例13方法，但以化合物(26)代替化合物(1)，得到化合物(38)。MS(m/z)＝962.7。
实施例39
双(乙烷-2，1-二基)双(3-(3-叔丁基-5-(3，5-二叔丁基-4-羟基苄基))-4-羟基苯基)丙酸(草酰二(氮杂-二基))酯
Figure BDA0002426415630000331
根据根据实施例14方法，但使用化合物(26)代替化合物(1)。得到化合物(39)。MS(m/z)＝1020.6。
实施例40
(2，4，8，10-四氧杂螺[5.5]十一烷-3，9-二基)双(2-甲基丙烷-2，1-二基)双(3-(3-叔丁基)-5-(3，5-二-叔丁基-4-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000332
根据实施例15方法，但以化合物(26)代替化合物(1)。得到化合物(40)。MS(m/z)＝1148.8。
实施例41
N-3-(3-叔丁基-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)-N′-(3-(3-叔丁基-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酰基)丙烷酰肼
Figure BDA0002426415630000341
根据实施例16方法，但以化合物(26)代替化合物(1)。得到化合物(41)。MS(m/z)＝876.6。
实施例42
四(3-(3-叔丁基)-5-(3，5-二-叔丁基-2-羟基苄基)-4-羟基苯基)苯丙酸季戊四醇酯
Figure BDA0002426415630000342
根据实施例17方法，但使用化合物(26)代替化合物(1)。得到化合物(42)。MS(m/z)＝1945.2。
Figure BDA0002426415630000351
实施例43
N，N”，N”′-(1，3，5-三嗪-2，4，6-三基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酰胺)
Figure BDA0002426415630000352
根据实施例18方法，但使用化合物(26)代替化合物(1)。得到化合物(43)。MS(m/z)＝1392.9。
Figure BDA0002426415630000353
实施例44
(2，4，6-三氧代-1，3，5-三嗪-1，3，5-三基)三(乙烷-2，1-二基)三(3-(3-(叔丁基)-5-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000361
根据实施例19方法，但使用化合物(26)代替化合物(1)。得到化合物(44)。MS(m/z)＝1527.9。
Figure BDA0002426415630000362
实施例45
1，3，5-三基三(乙烷-2，1-二基)三(3-(3-(叔丁基)-5-((3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸苯酯)
Figure BDA0002426415630000363
根据实施例20方法，但使用化合物(26)代替化合物(1)。1，3，5苯三甲醇(4464-18-0)代替2，4，6-三甲基苯-1，3，5-三基)三甲醇。得到化合物(45)。MS(m/z)1434.9。
Figure BDA0002426415630000371
实施例46
1，2，3-三(3-(3-(叔丁基)-5-(2，4-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸苯酯)丙烷
Figure BDA0002426415630000372
根据实施例22方法，但使用化合物(26)代替化合物(1)。得到化合物(45)。MS(m/z)＝1358.9。
实施例47
3-(3-(3-(叔丁基)-4-羟基-5-(2-苯基丙烷-2-基)苄基)-4-羟基-5-(2-苯基丙烷-2-基)苯基甲基)丙酸甲酯
Figure BDA0002426415630000373
根据实施例24方法，但使用2-(叔丁基)-4-(氯甲基)-6-(2-苯基丙-2-基)苯酚(化合物47.1)，代替化合物(24.1)。得到化合物(47)。MS(m/z)＝578.3。
Figure BDA0002426415630000381
实施例48
己烷-1，6-二基双(3-(3-(3-(叔丁基)-4-羟基-5-(2-苯基丙烷-2-基)苄基)-4-羟基-5-(2-苯基丙-2-基)苯基)丙酸甲酯)
Figure BDA0002426415630000382
根据实施例13法，但使用化合物(47)代替化合物(1)。得到化合物(48)。MS(m/z)＝1210.7。
实施例49
3-(3-(3，5-二叔丁基-4-羟基苄基)-5-((十二烷基硫代)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000391
根据实施例25法，但使用2，6-二-叔丁基-4-(氯甲基)苯酚，代替化合物(25.1)。得到化合物(49)。MS(m/z)＝612.4。
实施例50
丁烷-1，4-二基双(3-(3-(3，5-二叔丁基-4-羟基苄基)-5-((十二烷基硫代)甲基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000392
根据实施例13方法，但使用代替化合物(49)代替化合物(1)。丁二醇代替己二醇。得到化合物(50)。MS(m/z)＝1250.9。
实施例51
3-(3，5-二叔丁基-2-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000401
25.4g的3，5-二叔丁基-4-羟基苄基氯化物(CAS No 955-01-1，mp＝40℃)和29.2g的(3，5-二叔丁基-4-羟基苯基)丙酸甲酯(CAS No 6386-38-5，mp＝66℃)，溶于200mL干燥的CH2Cl2，氮气下室温下搅拌，加入无水14g的AlCl3搅拌。TLC监控反应，其间补充AlCl3。反应完成后，反应混合物倾倒入200mL冰水中，搅拌，用CH2Cl2萃取3次。合并萃取相，依次用1％稀盐酸和盐水洗涤，无水硫酸钠干燥。蒸干溶剂，得到的残余物使用柱层析纯化，得到化合物(51)。MS(m/z)＝510.4。
Figure BDA0002426415630000402
实施例52
3-(3，5-二叔丁基-2-(3，5-二叔丁基-4-羟基苯甲酰基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000403
根据实施例51方法，但以3，5-二叔丁基-4-羟基苯甲酰氯，代替3，5-二叔丁基-4-羟基苄基氯化物，得到化合物(2)。MS(m/z)＝524.4。
Figure BDA0002426415630000411
实施例53
3-(3，5-二叔丁基-2-((3，5-二叔丁基-4-羟基苯基)(羟基)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000412
根据实施例3的方法，但以化合物(52)代替化合物(2)，得到化合物(53)。MS(m/z)＝526.4。
实施例54
3-(3，5-二叔丁基-2-(氯(3，5-二叔丁基-4-羟基苯基)甲基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000413
将51克的化合物(53)溶于甲苯中，在冷凝分水器配置下，110℃加热回流。甲苯溶液中加入6克乙酸和1.5mL浓硫酸。监控反应，反应完成后。加入饱和的NaHCO3中和，再以二氯甲烷萃取。然后以饱和NaCl洗涤，无水MgSO4干燥。过滤后蒸干，通过柱层析，得到化合物(54)。MS(m/z)＝568.4。
Figure BDA0002426415630000421
实施例55
3-(5-(叔丁基)-2-(1-(3，5-二叔丁基-2-羟基苯基)-2-苯乙基)-4-羟基苯基)丙酸甲酯
Figure BDA0002426415630000422
根据实施例4方法，但以苯乙醛代替乙醛，化合物2，6-二-叔丁基酚代替化合物(4.1)，化合物(51.2)代替化合物(1.2)。经层析法分离，得到化合物(55)。MS(m/z)＝600.4。
实施例56
3-(3，5-二叔丁基-2-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)丙酸辛酯
Figure BDA0002426415630000431
根据实施例6的方法，但以化合物(51)代替化合物(1)，得到化合物(56)。MS(m/z)＝608.5。
实施例57
(乙烷-1，2-二基双(氧))双(乙烷-2，1-二基)双(3-(5-(叔丁基)-2-(3，5-二叔丁基-4-)羟基苄基)-4-羟基苯基)丙酸酯)
Figure BDA0002426415630000432
根据实施例10的方法，但以化合物(51)代替化合物(1)，得到化合物(57)。MS(m/z)＝1106.8。
实施例58
3-(5-(叔丁基)-2-(3，5-二叔丁基-4-羟基苄基)-4-羟基苯基)-N′-(3-(5-(叔丁基)-2--(3，5-二-叔丁基-4-羟基苄基)-4-羟基苯基)丙酰基)丙烷酰肼
Figure BDA0002426415630000441
根据实施例16的方法，但以化合物(51)代替化合物(1)，得到化合物(58)。MS(m/z)＝988.7。
实施例59
2-(乙酰氧基亚氨基)-1-(4-((4-(3-氧代-3-苯基丙-1-烯-1-基)苯基)硫基)苯基)己-1-酮
Figure BDA0002426415630000442
根据实施例17的方法，但以化合物(51)代替化合物(1)，得到化合物(59)。MS(m/z)＝2155.5。
实施例60：抗氧化剂在聚氨酯的析出测试
聚醚多元醇是聚氨酯原料。混合50重量分聚醚多元醇(triol，分子量3000)、2.0重量分水、0.1重量分三乙烯二胺、1.0重量分硅油后。加入包括0.2重量分辛酸亚锡、0.15重量分的实施例化合物或对照组化合物、50重量分甲苯二异氰酸酯、50重量分聚醚多元醇(triol，分子量3000)，的混合物。二者混合后，倒入盒中进行发泡反应。室温静置1小时，在烘箱中熟化。反应完成后，将掺有或未掺有抗氧化剂的聚氨酯切下1克样品，放到加盖的玻璃罐中进行抗萃取或抗老化分析。加入100ml溶剂进行萃取，并对萃取液进行分析。HPLC检测各种化合物的萃取量。以对照组所萃取出的量为100％。萃取出的量愈少，代表愈不容易析出。基本上，受测试化合物所具有抗老化或抗黄变能力，和受阻酚单元数正相关。抗萃取测试结果显示于表4。以对照组被萃取为100％，换算实例化合物被萃取的相对比例。实例化合物被萃取出百分比＝(100÷对照组被萃取出量a)×(实例化合物萃取出量b)×％。实例化合物的总体抗氧化效率，正比于萃取后在聚氨酯的残余量，且正比于(受阻酚单元数/分子量)。例如，化合物10和Eunox 1035的(受阻酚单元/分子量)的比值为(4/966)：(2/642)＝1.33，只要残余量比值大于1，即可推定具有进步性。表4实例化合物被萃取出的百分比都小于75％，即残余量比值都大于1。
表4.抗氧化剂的析出测试
Figure BDA0002426415630000451
Figure BDA0002426415630000461
表4.续
Figure BDA0002426415630000462
对照品全都来自市面商品或专利，Eunox是申请人商标名，41028-42-6(CAS no)来自专利(JP56052073)，结构式如下：
Figure BDA0002426415630000463
Figure BDA0002426415630000471
Figure BDA0002426415630000481
以上已以较佳实施例公开了本发明，然其并非用以限制本发明，凡采用等同替换或者等效变换方式所获得的技术方案，均落在本发明的保护范围之内。

Claims (12)

1.一种式(I)化合物或其盐，
Figure FDA0002426415620000011
其中，R1、R2各自独立地选自含C1-C10的烷基、苯基、苄基、枯基(cumyl)、C1-C12硫烷或C1-C2亚甲基C1-C12硫烷；R3、R4各自独立地选自氢、含C1～C6的烷基、苯基、苄基、枯基、C1-C12硫烷或C1-C2亚甲基C1～C12硫烷；R5、R6各自独立地选自氢、羟基、卤素、羰基、羧基、酰基、酯基、苯基、C1～C6烷基、C1～C6烷基胺基、C1～C6烷氧基、或R5～R6合为一酮基；
R7是q价基团；
X选自N、NH、NHR8、O、S、CH2、CHR8，R8选自H、OH、C1-C6烷基；
m＝0～3；n＝0～3；p＝0～18；q＝1～8；r＝0～3；s＝0～2。
2.根据权利要求1所述的化合物，其特征在于，R7选自一键、氢、未取代或经取代的碳或碳链、未取代或经取代的氧或硫或氮或金属原子、未取代或经取代的经氧或硫或氮所中断的碳链、未取代或经取代的5-7元碳环或含氧或硫或氮的5-7元杂环。
3.根据权利要求2所述的化合物，其特征在于，式(I)化合物为以下结构：
Figure FDA0002426415620000021
4.根据权利要求2所述的化合物，其特征在于，式(I)化合物为以下结构：
Figure FDA0002426415620000022
5.根据权利要求4所述的化合物，其特征在于，当R7是-(CH2CH2O)tCH2CH2-时，t＞1。
6.根据权利要求1-5任一项所述的化合物，其特征在于，R1、R2各自独立地选自含C1-C5的烷基、苯基、苄基、枯基；R3、R4各自独立地选自氢、羟基、C1-C5的烷基、酰基、C1-C5烷基胺基、C1-C5烷氧基；R5、R6各自独立地选自氢、羟基、苯基、C1-C5的烷基、酰基；R7选自H、一键、(C)a(CH)b(CH2)c(CH3)d，其中a、b、c、d＝0～18，a、b、c、d不同时为0、(CH2CH2O)tH、(CH2CH2O)tOCH3、(CH)q-2(CH2)0～12(CH3)1～3、
Figure FDA0002426415620000031
Figure FDA0002426415620000032
S、SH、O、OH、N、NH、NHR8、P、Ca、Mg、Zn、Na、K、-(CHR8)1～18-、-(CH)q-2(CH2)1～18-、-(C＝O)1-4-、-(CHR8)u(C＝O)1-4(CHR8)u-、-(CHR8)uS1-4(CHR8)u-、-(CHR8)uO1-4(CHR8)u-、-(CH2CH2O)tCH2CH2-、三嗪类、三聚氰胺类、未取代或经取代的苯基或苄基；q≥a+b+c+d；t＝1-20；u＝1-10。
7.根据权利要求6所述的化合物，其特征在于，其中，m＝0-2；n＝0-2；p＝0-18；q＝1-6；r＝0-1；s＝0-1；X＝NH或O；R7选自H、一键、C、CH、(CH2)1～18、CH3、(CH2CH2O)1～8H、(CH2CH2O)1～ 8OCH3、(CH)q-2(CH2)1～18(CH3)1～2、
Figure FDA0002426415620000033
Figure FDA0002426415620000034
(S)1～2、SH、O、OH、N、NH、NHR8、P、Ca、Mg、Zn、-(C＝O)1-2-、-(CH2)1～2(CH)1(CH2)1～2-、-(CHR8)uO1-4(CHR8)u-、三嗪、三聚氰胺、苯基、C1-4烷基取代苯基。
8.根据权利要求7所述的化合物，其特征在于，m＝1；n＝2；q＝1-4；r＝1；s＝0。
9.根据权利要求8所述的化合物，其特征在于，选自：
Figure FDA0002426415620000041
Figure FDA0002426415620000051
Figure FDA0002426415620000061
Figure FDA0002426415620000071
10.一种式(I)所示化合物的制备方法，其特征在于，包括一酯化或转酯化反应：
Figure FDA0002426415620000072
其中，R1-R7、n、X、p、r、s如权利要求1中所定义；-X(CH2)pR7是OH或离去基团。
11.一种组合物，其包括至少一种权利要求1-8任一项所述的式(I)化合物或其盐。
12.一种受阻酚抗氧化剂的制备方法，其包括对一受阻酚化合物的(受阻酚单元数/分子量)做优化，使得优化后与优化前的(受阻酚单元数/分子量)比值大于1。
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