WO2016095735A1 - 一种多功能协同高分子抗氧化稳定剂及其制备方法和应用 - Google Patents

一种多功能协同高分子抗氧化稳定剂及其制备方法和应用 Download PDF

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WO2016095735A1
WO2016095735A1 PCT/CN2015/096773 CN2015096773W WO2016095735A1 WO 2016095735 A1 WO2016095735 A1 WO 2016095735A1 CN 2015096773 W CN2015096773 W CN 2015096773W WO 2016095735 A1 WO2016095735 A1 WO 2016095735A1
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reaction
product
dichloromethane
solvent
room temperature
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PCT/CN2015/096773
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French (fr)
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毛丽娟
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绍兴瑞康生物科技有限公司
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Priority to KR1020177016410A priority Critical patent/KR20170084283A/ko
Priority to JP2017533346A priority patent/JP6594982B2/ja
Priority to US15/535,413 priority patent/US10501395B2/en
Priority to EP15869243.4A priority patent/EP3235862A4/en
Publication of WO2016095735A1 publication Critical patent/WO2016095735A1/zh

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    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
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    • 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
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    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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Definitions

  • the invention relates to a multi-functional hybrid synergistic polymer anti-oxidation stabilizer, a preparation method and application thereof, and a new material anti-oxidation stability additive, which can be directly applied to a polymer material as an anti-wear, color retention, retention function, etc.
  • Oxidation stabilizing additive for use in plastics, rubber, fiber, coatings, paints and petroleum.
  • antioxidant stabilizing additives especially the heat stabilizer market
  • special antioxidant stabilizers have grown with the growth of polymer materials applications and technology development.
  • the automotive industry, organic electronics, agriculture, film, plastics, rubber, fiber, computer materials and other industries require special special antioxidant additives and stabilizers to expand the lifespan and application of these materials.
  • antioxidant stabilizing additives are also widely used in the plastics industry, particularly in the field of olefinic polymers, chlorinated high polymers (PVC).
  • PVC products are mainly used in the construction sector, especially for the manufacture of pipes and cables. More than 85% of antioxidant additives are used in this industry. Demand in the Asia Pacific region is expected to grow further. Light antioxidant additives will grow even faster. In particular, the increase in polypropylene and polyethylene products will be even more impressive.
  • the antioxidant stability additives currently used on the market have small molecular weight, volatile or degradation loss, and are unevenly distributed in the material, so that the materials are damaged during handling or use, especially under high temperature and strong light irradiation conditions. It causes problems such as short service life, damaged color, weakened strength or embrittlement cracking.
  • the invention is thus produced.
  • the object of the present invention is to provide a multifunctional synergistic polymer antioxidant stabilizer and a preparation method and application thereof, the novel polymer material multifunctional hybrid antioxidant stabilizer with stable ether Bond or thioether bond or amine bond or amide bond as a primary anti-light and anti-heat hybrid bonding method or as a primary and secondary anti-oxidant stabilizer bonding mode to form a multi-functional synergy by designing a suitable space control structure Working antioxidant stabilizer.
  • a multifunctional synergistic polymer antioxidant stabilizer having the following structure:
  • R1 is a linking chain, and the linking chain is a fatty chain, an aromatic structural chain or a mixed chain of a fat and an aromatic structure;
  • X is O, S, N or NH, or -CONR-, Z is O, S, N or NH, and X is not the same as Z;
  • R is a fatty chain, an aromatic group, a hindered amine or a hindered phenol, and R3 is a fatty chain, an aromatic group, a hindered amine or a hindered phenol, R is the same as R3, or R is different from R3;
  • n is a positive integer including 1, n1 is a positive integer including 1, n is the same as n1, or n is different from n1.
  • the multifunctional synergistic polymer antioxidant stabilizer is:
  • the R3 is H, an aliphatic hydrocarbon side chain, an aromatic hydrocarbon side chain, a fatty aromatic hydrocarbon mixed side chain or a hetero atom side chain; n is a positive integer.
  • the antioxidant stabilizer is:
  • a preparation method of multifunctional synergistic polymer antioxidant stabilizer comprises the following steps:
  • n is a natural number ⁇ 1
  • thiol is added dropwise to a mixture containing 1.1 to 5 equivalents of iodide, bromide or chloride under a nitrogen atmosphere with 10-20% NaI or KI, or activated alcohol (eg toluene sulfate of alcohol) , trifluoroacetate, etc.) dry THF, DCM, acetone, acetonitrile or ethanol, methanol, chloroform, toluene or DMF (1:5-15, w/v), then add Na 2 CO 3 or K 2 CO 3 In an inorganic base or an organic base solution such as NEt 3 or DMAP or DBU or an organic base (1.2-2.0 equivalents), the mixture is stirred at room temperature for 30 minutes, then heated to 40-90 ° C for 5-12 hours, and the reaction progresses until the reaction is monitored by TLC.
  • inorganic base or an organic base solution such as NEt 3 or DMAP or DBU or an organic base
  • the average molecular weight of the multifunctional antioxidant stabilizer polymer product can be controlled from 1000 to 5000 Dalton by adjusting the size of n using a polyfunctional material.
  • the polyfunctional starting material may be a polyfunctional starting material other than a polyamine such as a polyhydric alcohol, a polyhydric mercaptan, a polybasic organic acid, a polyvalent aldehyde, a polybasic acid chloride or the like.
  • a polyamine such as a polyhydric alcohol, a polyhydric mercaptan, a polybasic organic acid, a polyvalent aldehyde, a polybasic acid chloride or the like.
  • reaction equation of the preparation method of the multifunctional synergistic polymer antioxidant stabilizer is:
  • a multifunctional synergistic polymer antioxidant stabilizer is used as an antioxidant.
  • the multifunctional synergistic polymeric antioxidant stabilizer is used in plastics, rubber, petroleum products, coatings, fiber products or paints.
  • the invention connects the various anti-oxidation functional fragments with anti-light, heat resistance and anti-processing by using a designed space link chain (Link Spacer) with a thioether bond, a secondary or tertiary amine bond, and an ether bond as a bridge.
  • Link Spacer space link chain
  • a new class of antioxidant stabilizers with design functions is formed.
  • the polymer antioxidant stabilizer of the invention can adjust the compatibility of the antioxidant stabilizer with the specific structure of the polymer through the space connecting chain and the substituted side chain, so as to improve the migration of the current antioxidant stabilizer in the polymer, leakage and Bad defects such as extraction; on the other hand, introduction of resistance
  • the type of oxidizing functional group can produce a new type of antioxidant stabilizer with different hybrid multifunctional synergies.
  • the large-molecular-weight polymer can be produced by designing the space-ligating fragment and the side chain structure.
  • the introduced antioxidant functional fragments belong to different kinds of antioxidant mechanisms (for example: primary antioxidant functions, anti-heat-blocking phenols and anti-photo-hindered amines, primary antioxidant functional sterically hindered phenols or hindered amines and auxiliary antioxidant functions Fragment thioether or phosphite) forms a novel multifunctional hybrid synergistic antioxidant stabilizer.
  • the properties of the polymer hybrid synergistic antioxidant stabilizer of the present invention are not only the addition of different antioxidant properties, but also the superiority of higher strength to molecular protection and the matching of specific polymers with different structures.
  • the invention is designed and invented for the first time to invent a multi-functional hybrid flower, which has a sustained release and long-acting effect, and has a novel antioxidant stabilizer against hydrolysis, acid resistance, alkali resistance and the like.
  • the stable ether bond or amine bond or amide bond is used as the primary anti-light and anti-heat hybrid bond mode to form a multi-functional synergistic anti-oxidation stabilizer by designing a suitable space control structure.
  • the multifunctional synergistic polymer anti-oxidation stabilizer of the invention has the multi-functional hybrid synergistic property of stable bonding, has the advantages of heat resistance, hydrolysis resistance, acid and alkali resistance, and makes up for the weakness of similar products in the current market. To lay the foundation for the development of a new generation of effective antioxidant stabilizers.
  • reaction was monitored by TLC, cooled to room temperature, then aqueous solution of NaCI, dichloromethane or ethyl acetate or MTBE or petroleum ether was used to extract intermediate 1 (20 ml x 3), anhydrous Na the organic phase was dried 2 SO 4, filtered and the filtrate concentrated in vacuo, silica gel column chromatography to give a yield of 81-92% intermediate as a pale yellow powder.
  • An equimolar amount of Intermediate 2 is added to an equimolar reaction of Intermediate 1, while adding an equimolar amount of Na 2 CO 3 or K 2 CO 3 or NEt 3 or DBU or DMAP organic or inorganic base.
  • the reaction mixture was stirred at room temperature for 1 hour and then heated to 50-90 ° C for 5-18 hours.
  • the high molecular weight of the product can be adjusted by heating temperature and reaction time.
  • an aqueous solution of ice is added, and the water-soluble impurities are washed away to obtain an oily substance in an organic solvent, whereby a waxy solid can be obtained to obtain a white solid product as the objective product 1 in a yield of from 73 to 91%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

一种抗氧化稳定剂，其具有以下结构（A）其中，R1为连接链，所述的连接链为脂肪链、芳香结构链或脂肪与芳香结构混合链；R2为（B），X为O、S、N或NH，或-CONR-，Z为O、S、N或NH，且X与Z不相同；R为脂肪链、芳香基、位阻胺或位阻酚，R3为脂肪链、芳香基、位阻胺或位阻酚，R与R3相同，或R与R3不相同；n为包括1的正整数，n1为包括1的正整数，n与n1相同，或n与n1不相同。

Description

一种多功能协同高分子抗氧化稳定剂及其制备方法和应用 技术领域
本发明涉及一种多功能杂化协同高分子抗氧化稳定剂及其制备方法和应用，为新材料抗氧化稳定添加剂，可直接应用于高分子材料中作为保质、保色、保持功能等的抗氧化稳定添加剂，应用于塑料，橡胶，纤维，涂料，油漆和石油等系列产品中。
背景技术
全世界抗氧化稳定添加剂销售市场非常庞大，单一塑料抗氧剂在2011年全球就消耗42万吨左右。目前亚太地区用量最大，其次为欧洲和北美，预计2016年亚太地区材料抗氧化稳定剂产品销售额将达48亿美元。
材料抗氧化稳定添加剂的需求和生产陆续地从美国、西欧和日本转移到亚洲的新兴市场，特别是中国和印度。目前国内抗氧剂的消耗量增长较快。但是，少数大的国际供应商仍然控制着材料抗氧化稳定剂世界市场价格。
抗氧化稳定添加剂市场特别是热稳定剂市场在印度，亚太增长率很快。专用抗氧化稳定剂随着聚合物材料应用的增长和技术发展而增长。目前，汽车业、有机电子、农业、影片、塑料、橡胶、纤维、计算机材料等行业需要特殊专用抗氧化添加剂和稳定剂来扩大这些相应材料的使用期限和应用。
抗氧化稳定添加剂的需求还大量应用于塑料工业，特别烯类聚合物，氯化高聚物(PVC)领域的发展。PVC产品主要用于建筑领域，特别是用于管道和缆绳制造。超过85％的抗氧化添加剂用于这一行业。预期亚太地区的需求将进一步增长。轻型抗氧化添加剂增长将更为迅速。特别是用于聚丙烯和聚乙烯产品的增量将更为可观。
大多数聚合物材料需要在200℃以上的温度下进行加工或处理，而由于其在连续经受高温和强光环境中，通常材料会出现使用寿命缩短，颜色容易受到破坏，强度削弱或材料表面脆化龟裂等问题。然而，这些影响可以通过引入特定的抗氧化稳定添加剂防止和减少材料损伤，延长材料使用寿命，保持美观，耐用，降低成本，减少废料产量,保护环境。
目前市场上所使用的抗氧化稳定添加剂，分子量小，易挥发或降解损失，在材料中作用分布不均，从而使材料在处理或使用期间特别是在高温和强光照射条件下，受到损伤,造成使用寿命短，颜色受到破坏，强度削弱或脆化龟裂等问题。
今年开始有抗光和抗热分子内的多功能抗氧化稳定剂文章报道，有些国际大公司也开始设计生产此类产品，数据表明这类分子内多功能抗氧剂对材料的协同保护作用大大优于两种抗氧剂的复方使用协同作用。
本发明人设计研发的高分子抗氧化稳定剂及其制备方法和应用，很好地克服了上述问题，使相应的材料能够在高温和强光照射条件下保持稳定的性质。本发明由此产生。
发明内容
针对现有技术的上述技术问题，本发明的目的是提供一种多功能协同高分子抗氧化稳定剂及其制备方法和应用，该新型高分子材料多功能杂化抗氧化稳定剂以稳定的醚键或硫醚键或胺键或酰胺键作为一级抗光和抗热杂化键合方式或作为一级和二级抗氧化稳定剂的键合方式通过设计适宜的空间控制结构形成多功能协同工作的抗氧化稳定剂。
为达到上述目的，本发明是通过以下技术方案实现的：
一种多功能协同高分子抗氧化稳定剂，具有以下结构：
Figure PCTCN2015096773-appb-000001
其中，R1为连接链，所述的连接链为脂肪链、芳香结构链或脂肪与芳香结构混合链；
R2为
Figure PCTCN2015096773-appb-000002
X为O、S、N或NH，或-CONR-，Z为O、S、N或NH，且X与Z不相同；R为脂肪链、芳香基、位阻胺或位阻酚，R3为脂肪链、芳香基、位阻胺或位阻酚，R与R3相同，或R与R3不相同；
n为包括1的正整数，n1为包括1的正整数，n与n1相同，或n与n1不相同。
所述的多功能协同高分子抗氧化稳定剂为：
Figure PCTCN2015096773-appb-000003
Figure PCTCN2015096773-appb-000004
Figure PCTCN2015096773-appb-000005
所述的R3为H、脂肪烃侧链、芳香烃侧链、脂肪芳香烃混合侧链或有杂原子侧链；n为正整数。
作为这类抗氧化稳定剂实例结构的，所述的抗氧化稳定剂为：
Figure PCTCN2015096773-appb-000006
Figure PCTCN2015096773-appb-000007
一种多功能协同高分子抗氧化稳定剂的制备方法，包括以下步骤：
n为≥1的自然数
1当量的醇原料在氮气保护下加入到含有1.5-5当量的NaH的无水THF、DMF、丙酮、乙酸乙酯，甲苯或乙氰(1；5-15，w/v)溶剂中，室温或加热30-50摄氏度下搅拌30分钟至1小时，滴加1.2-5.0当量的碘化物、溴化物或氯化物配有10％的NaI或KI，或活化的醇(例如：醇的甲苯硫酸酯，三氟乙酸酯等)，混合物室温搅拌30分钟到1小时，，加热到40-90℃，TLC监测反应进程直到反应完成；饱和NH4Cl水溶液(反应有机溶剂体积的1-3倍)淬灭反应，加入乙酸乙酯或二氯甲烷充分混合，分离有机相，水相萃取三次，Na2OS4干燥合并的有机相，过滤，真空下除去有机溶剂；固体产物通过重结晶获取，油状或液体产物通过萃取或硅胶柱层析方式纯化；产率79-96％。
或
1当量的醇原料加入到含有1-3当量的NaOH和10-20％的四丁基溴化铵(w/w)的THF、丙酮、乙酸乙酯或乙氰、二氯甲烷，氯仿，甲苯或DMF(1；5-20，w/v)溶剂中，室温或加热到30-50摄氏度搅拌1-3小时，滴加1.5-3.0当量的碘化物、溴化物或氯化物配有10％的NaI或KI，或活化的醇(例如：醇的甲苯硫酸酯，三氟乙酸酯等)，混合物室温搅拌1小时，加热到40-100℃反应1-25小时，TLC监测反应进程直到反应完成，固体产物通过重结晶获取，油状或液体产物通过萃取方式纯化；产率83-92％。
或
在氮气保护下1当量硫醇滴加到含有1.1-5当量的当量的碘化物、溴化物或氯化物配有10-20％的NaI或KI，或活化的醇(例如：醇的甲苯硫酸酯，三氟乙酸酯等)干燥THF、DCM、丙酮、乙氰或乙醇、甲醇，氯仿，甲苯或DMF(1：5-15，w/v)，然后加入Na2CO3或K2CO3等无机 碱或NEt3或DMAP或DBU等有机碱(1.2-2.0当量)等有机碱溶液中，混合物室温搅拌30分钟，然后加热到40-90℃搅拌5-12小时，TLC监测反应进程直到反应完成；NaCl饱和水溶液和等量的乙酸乙酯或二氯甲烷加入到反应体系，充分混合，分离有机相，水相用同样有机溶剂洗三次，Na2SO4干燥合并的有机相，过滤，真空下除掉有机溶剂；重结晶得到固体产物，硅胶柱层析或萃取分离得到液体或油状产物；产率78-97％。
或
1当量的胺溶于二氯甲烷、乙酸乙酯、丙酮、乙氰、THF、乙醇、甲醇，氯仿，甲苯或DMF(1：5-20，w/v)溶剂中，在氮气保护搅拌下滴加到1-3当量的有机碘化物、溴化物(10-50％NaI，w/w)、氯化物(10-50％NaI，w/w)或活化的醇类化合物，(MsO-，TsO-，TfO-)同样有机溶剂1-3当量碱(NaOH，KOH，Na2CO3，K2CO3，NEt3，DBU，DMAP等无机或有机碱)的溶液中，用无机碱时配比加入10％的四丁基溴化胺，室温搅拌1-3小时，然后热到40-90℃搅拌额外1-25小时；冷却，NH4Cl水溶液洗掉碱性和水溶性杂质，重结晶得到在有机相里的固体产物，液体或油状物产品通过硅胶柱层析或萃取方式得到纯化；产率67-93％。
或
1当量的胺和1当量碱(无机碱或有机碱)溶于或悬浮于无水二氯甲烷、THF、MTBE、丙酮、乙氰，氯仿，甲苯或DMF溶剂(1：5-20，w/v)，在氮气保护下0-10℃滴加1-2当量羧酰氯同样干溶剂(1：5-10，w/v)的溶液，混合物0-10度搅拌30分钟，室温或加热到30-60℃反应3-24小时，TLC监测反应进程直到反应完全；加入(1：20)的二氯甲烷、乙酸乙酯或MTBE和0.1N的盐酸冰水溶液，混合后分出有机相，水相用同样有机溶剂洗两次，无水Na2SO4干燥合并的有机相，过滤，浓缩；固体产物通过重结晶得到，液体或粘稠油状产物通过硅胶柱色层分离或萃取得到；产率75-96％。
或
通过使用多官能团原料调节n的大小可控制多功能抗氧化稳定剂高分子产物的平均分子量从1000到5000道尔顿
1当量的二胺、多胺溶于干燥二氯甲烷、乙酸乙酯、THF、丙酮、乙氰、乙醇、甲醇，氯仿，甲苯或DMF中(1：5-15，w/v)中，再搅拌和氮气保护下滴加多碘、多溴或多氯有机物原料(溴和氯化物要加10-50％的NaI或KI，以及相应的Bu4NBr)，室温搅拌30分钟-1小时，然后加热到40-100℃反应6-72小时直到沉淀不再增多；过滤出固体粉末产品(白色或浅黄色)，用二氯甲烷溶剂洗3次；(1；2＝w/v)，产率约87-100％。
多官能团原料可以是除多胺以外的其它多官能团原料，例如：多元醇，多元硫醇，多元有机酸，多元醛，多元酰氯等。
所述多功能协同高分子抗氧化稳定剂的制备方法的反应方程式为：
Figure PCTCN2015096773-appb-000008
一种多功能协同高分子抗氧化稳定剂作为抗氧化剂的应用。
作为优选的，所述的多功能协同高分子抗氧化稳定剂在塑料、橡胶、石油品、涂料、纤维产品或油漆中的应用。
本发明通过有设计的空间连接链(Link Spacer)以硫醚键，仲胺键或叔胺键，以及醚键作为桥梁将具有抗光，抗热，和抗加工各类抗氧化功能片段连接起来形成新的一类具有设计功能的抗氧化稳定剂。本发明的高分子抗氧化稳定剂一方面可通过空间连接链和取代侧链调整抗氧化稳定剂与高分子特定结构的匹配性，以改善现抗氧化稳定剂在高分子中的迁移，漏出与被萃取等不良缺陷；另一方面通过引入抗 氧化功能团的种类可产生不同杂化多功能协同作用的新型抗氧化稳定剂。当引进的抗氧化功能团属于同一类型(例如：主抗热位阻酚功能片断，主抗光位阻胺功能片段，)通过设计空间连接片段和侧链结构可产生大分子量的与高分子匹配性能好的新型抗热抗光抗氧剂。当引进的抗氧化功能片段隶属不同种类抗氧化机理时(例如：主抗氧功能抗热位阻酚和抗光位阻胺，主抗氧化功能位阻酚或位阻胺片断与辅助抗氧化功能片段硫醚或亚磷酸酯)就形成了新型多功能杂化协同抗氧化稳定剂。本发明的高分子杂化协同抗氧化稳定剂的性质不仅仅是不同抗氧剂性质的加合，有更高强度对分子保护的优越性和与不同结构特定高分子匹配性的体现。
本发明首次设计发明了多功能杂花，缓释长效，具有抵抗水解，抵抗酸，抵抗碱等右翼品质的新型抗氧化稳定剂。以稳定的醚键或胺键或酰胺键作为一级抗光和抗热杂化键合方式通过设计适宜的空间控制结构形成多功能协同工作的抗氧化稳定剂。
本发明的多功能协同高分子抗氧化稳定剂都具有稳定键合的多功能杂化协同性质，抗热性能，抗水解，抗酸抗碱等特性具有优势，弥补了现市场同类产品的弱势，为发展新一代有效抗氧化稳定剂奠定基础。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
实施例1
1、结构式
Figure PCTCN2015096773-appb-000009
2、合成路线：
Figure PCTCN2015096773-appb-000010
3、4-溴甲基-2，6-二叔丁基苯酚(中间体1)合成步骤1：
5克2，6-二叔丁基对甲苯酚(22.69毫摩尔)溶于CCl4或CHCl3或二氯甲烷或THF或甲苯或DMF等溶剂(20-50毫升)中,在氮气保护和紫外灯(汞灯350瓦)照射下滴加液体溴(1.2-1.5毫摩尔)以上溶剂溶液(15-50毫升),滴加速度可随反应快慢而定，TLC监测反应进程。滴定结束后搅拌5-20分钟，真空下除掉有机溶剂，油状产物直接在下一步使用。
4、4-溴甲基-2，6-二叔丁基苯酚(中间体1)合成步骤2：
5.0克2，6-二叔丁基对甲苯酚(22.69毫摩尔)溶于CCl4或CHCl3或二氯甲烷或THF或氯苯等溶剂(25-50毫升)中，滴加到4.1克NBS(22.90毫摩尔)含3-10％的过氧化苯甲酰同样溶剂(20-60毫升)的溶液中。混合物回流2-5小时，冷却至室温，过滤掉固体悬浮物，真空下除掉有机溶剂，浅棕色液体直接在下一步使用。
5、目标产物1的制备：
2克季戊四醇(1.98毫摩尔)，氢氧化钾或氢氧化钠(11.89毫摩尔)和四丁基溴化铵(0.5毫摩尔)溶于20毫升THF或乙氰或丙酮或DMF，室温下搅拌1小时，加热至50-70度搅拌30分中至2小时；冷却至室温，氮气保护下加入3.49克2，6-二叔丁基-4-溴甲基苯分(15.45毫摩尔)，混合物回流18小时，TLC监测反应进程直到季戊四醇的原料消失，有一个主要产物点形成。加入0.1N冰水盐酸溶液和同样体积的二氯甲烷或乙酸乙酯，充分混合后分离有机相，水相用同样的有机溶剂萃取两次，无水Na2SO4干燥有机相，过滤，真空除去有机溶剂，硅胶柱层析纯化得到3.98克目标产物1，产率83.7％。
1H NMR(400MHz，CHCl3)，δ(ppm):7.26(s,CHCl3在CDCl3中)，7.15(s,2H,2CH),7.00(s,2H,2CH),6.92(s,2H,2CH),6.87(s,2H,2CH),6.66(s,4H,2CH2),5.62(s,4H),3.17(s,4H,2CH2),2.29(s,4H,2CH2),2.26(s,4H,2CH2),1.22-1.43(m,72H,24CH3)。
实施例2
1、结构式
Figure PCTCN2015096773-appb-000011
2、合成路线：
Figure PCTCN2015096773-appb-000012
3、中间体1的制备：
6.1克硫醇(42.30毫摩尔)滴加到3克2，2-二氯乙基胺(21.12毫摩尔)和10-50％ KI的THF或丙酮或乙氰或二氯甲烷或乙醇等(1：5-20，w/v)溶液中，混合物加热至40-90℃，反应3-9小时，TLC监测反应进程直到反应完全。真空除去有机溶剂，加入NaCl水溶液和二氯甲烷或乙酸乙酯，充分混合，将有机相分离，水相萃取两次。无水Na2SO4干燥有机相，过滤，浓缩后中间体1直接在下一步使用。
4、中间体2的制备：
5.93克3-(3，5-二叔丁基-4-羟基苯)丙酸(21.30毫摩尔)溶于干燥的THF或二氯甲烷或乙酸乙酯或MTBE或丙酮(1：5-20，w/v)，冷却至0-10℃，在氮气保护下滴加1.82毫升草酰氯(21.50毫摩尔)和0.5毫升滴DMF，搅拌30分钟，升温至室温搅拌2-7小时，TLC监测反应进程直到反应完全。真空下除去有机溶剂和过量的草酰氯，剩余中间体2直接用于下步反应。
3、目标产物1的制备：
中间体1(21.12毫摩尔)和中间体2(21.30毫摩尔)溶于干燥丙酮或THF或乙酸乙酯或乙氰或甲苯或二氯甲烷等有机溶剂，冷却至0-10℃，滴加三乙胺(21.30毫摩尔)，混合物在0-10℃搅拌1小时，然后室温搅拌3-7小时，TLC监测反应进程直到反应完全。向反应体系加入0.1N 的冰盐酸水溶液和同样体积的二氯甲烷或乙酸乙酯，充分混合，分离有机相，有机相用0.1N冰水盐酸洗两次，然后NaCl饱 和溶液洗两次，无水Na2SO4干燥，过滤，真空下除去有机溶剂，硅胶柱层析纯化得到9.87克目标产物1，产率75.1％。
1H NMR(400MHz,CDCl3),δ(ppm):7.25(s,CHCl3来源于CDCl3)，6.97(s,2H,2CH),2.76-2.99(m,8H,4CH2),1.52-1.59(m,4H,2CH2),1.43(s,18H,2But),1.26-1.43(m,24H,12CH2),0.88(t,6H,3JHH＝7.20,2CH3)。
实施例3
1、结构式
Figure PCTCN2015096773-appb-000013
2、合成路线：
Figure PCTCN2015096773-appb-000014
3、2，2，6，6-二叔丁基-4-溴甲基苯酚(中间体1)的合成步骤1：
5克2，2，6，6-二叔丁基对甲苯酚(27.11毫摩尔)溶于CCl4或CHCl3或CH2Cl2或THF或氯苯或甲苯或二溴乙烷溶剂(1：5-20，w/v)中,在氮气保护下，在350瓦汞灯照射下滴加溴(28.01-37.57毫摩尔)同样体积溶剂的溶液，TLC监测反应进程。滴加完毕后搅拌5-40分钟， 真空下除去有机溶剂得到浅红棕色油状物直接用于下一步反应中，产率95-100％。
4、2，2，6，6-二叔丁基-4-溴甲基苯酚(中间体1)的合成步骤2：
5克2，2，6，6-二叔丁基对甲苯酚(27.11毫摩尔)溶于CCl4或CHCl3或CH2Cl2或THF或氯苯或甲苯或二溴乙烷溶剂(1：5-20，w/v)中,加入3-10％的过氧化苯甲酰，加热至回流，滴加6.3克NBS(35.25毫摩尔)同样体积同样溶剂溶液，滴加完毕后再回流2-5小时。冷却至室温，过滤到悬浮固体，滤液在真空下浓缩得到淡红色油状物直接用于下一步，产率90-95％。
5、2，2，6，6-二叔丁基-4-氨甲基苯酚(中间体2)的合成步骤：
3克2，2，6，6-二叔丁基-4-溴甲基苯酚溶于THF或丙酮或乙醇或甲醇等溶剂，加入氨水或通入氨气，室温反应2-6小时，TLC监测反应进程至苄溴原料消失，加入二氯甲烷或石油醚或乙酸乙酯或甲苯或MTBE萃取苄胺产物到有机相里(10mlx3)。无水Na2SO4干燥合并的有机相，过滤，滤液在真空下除掉有机溶剂。得到淡黄色蜡状固体直接用于下一步反应，产率81-93％。
6、目标产物1的制备：
1克三聚氯氰(5.42毫摩尔)溶于无水二氯甲烷或THF或MTBE或乙酸乙酯或乙醇或丙酮或DMF等溶剂(1：5-20，w/v)，在氮气保护下加入5.75克Na2CO3(5.42毫摩尔)和上面制备好的粗苄胺(21.68毫摩尔)，混合物室温搅拌1小时，加热至40-80℃2-18小时，TLC监测反应进程之反应完全。加入NaCl水溶液，用二氯甲烷或乙酸乙酯萃取(10mlx3),无水Na2SO3干燥合并的有机相，过滤，真空下浓缩，硅胶柱层析得到白色固体3.18克，产率75.2％。1H NMR(400MHz，CDCl3)，δ(ppm):7.31(t,3H,3CH),7.30(s,CHCl3来源于CDCl3),7.18(t,3H,3CH),2.35(s,6H,3CH2),1.31(s,54H,18CH3)。
实施例4
1、结构式
Figure PCTCN2015096773-appb-000015
2、合成路线：
Figure PCTCN2015096773-appb-000016
3、目标产物2的制备方法：
1克2，2，6，6-二叔丁-4-溴甲基苯酚(3.342毫摩尔)溶于二氯甲烷或乙酸乙酯或石油醚或THF或MTBE或丙酮或乙醇等溶剂(1：5-20，w/v)中，在氮气保护下滴加到正十八胺和K2CO3或Na2CO3或NaOH或三乙胺或DBU或DMAP等碱同样体积相同溶剂的溶液中，混合物室温下搅拌1-5小时，TLC监测反应进程直到反应完成。加入NaCl水溶液，二氯甲烷或乙酸乙酯或MTBE或石油醚有机溶剂萃取产物(10mlx3),用无水Na2SO4干燥，过滤，真空下除去有机溶剂。硅胶柱层析得到显黄色油状物，产率83-92％。1H MNMR(400MHz,CDCl3),δ(ppm):7.34(s,CHCl3来源于CDCl3)，7.15(s,2H,2CH),3.45(m,2H,CH2N),2.76(m,2H,CH2N),1.13-1.49(m,52H)。
实施例5
1、结构式
Figure PCTCN2015096773-appb-000017
2、合成路线：
Figure PCTCN2015096773-appb-000018
3、中间体1的合成：
6克1,2-二氯乙氧基乙烷(32.08毫摩尔)溶于丙酮或乙氰或甲苯或乙醇或MTBE溶剂(1：5-20，w/v)，加入10-20％的NaI或KI，32.08毫摩尔Na2CO3或K2CO3或NEt3或DBU或NaOH等有机或无机碱和10.16克的4-氨基-2，2，6，6-四甲基哌啶(65.00毫摩尔)在同体积同样溶剂溶液中。混合物加热至40-70℃搅拌3-18小时，TLC监测反应进程，冷却到室温，加入NaCl水溶液，二氯甲烷或乙酸乙酯或MTBE或石油醚萃取中间体1三次(20mlx3),无水Na2SO4干燥有机相，过滤，滤液在真空中浓缩，硅胶柱层析得到淡黄色粉沫中间体1，产率81-92％。
4、中间体2的合成步骤：
5.93克3-(3，5-二叔丁基-4-羟基苯)丙酸(21.30毫摩尔)溶于干燥的THF或二氯甲烷或乙酸乙酯或MTBE或丙酮(1：5-20，w/v)，冷却至0-10℃，在氮气保护下滴加1.82毫升草酰氯(21.50毫摩尔)和0.5毫升滴DMF，搅拌30分钟，升温至室温搅拌2-7小时，TLC监测反应进程直到反应完全。真空下除去有机溶剂和过量的草酰氯，剩余中间体2直接用于下步反应。
5、目标产物1的制备：
3克中间体1(7.06毫摩尔)和7.36毫摩尔Na2CO3或K2CO3或NEt3或DMAP或DBU等碱溶于无水丙酮或THF或二氯甲烷或乙氰或乙酸乙酯溶剂中，冷却到0-10℃，滴加14.25毫摩尔中间体2同样体积相同溶剂的溶液，滴加完毕后混合物在0-10℃搅拌30分钟，室温1-3小时，加热至40-60℃搅拌另外2-5小时。过滤不溶物，滤液浓缩至除掉一般溶剂，加入同样体积的石油醚，搅拌下冷却至0℃。收集析出的白色固体4.79克，产率71.7％。
1H NMR(400MHz,DMSO-D6),δ(ppm):6.92(s,2H,2CH),6.89(s,2H,2CH),6.75(s,CH2Cl2溶剂)，4.01(m,4H,2OCH2),3.58(sb,H2O),3.41(m,4H,2OCH2),2.71(m,6H,2NCH2,2NCH),2.50(m,DMSO来源于DMSO-d6),2.42(m,4H,2CH2),2.26(m,4H,2CH2),1.59(m,4H),0.93-1.48(m,64H)。
实施例6
1、结构式
Figure PCTCN2015096773-appb-000019
2、合成路线：
Figure PCTCN2015096773-appb-000020
3、中间体1的合成：
1克三聚氯氰(5.42毫摩尔)和5.42毫摩尔Na2CO3或K2CO3或NEt3或DBU或DMAP溶于干燥的丙酮或二氯甲烷或乙氰或THF或甲苯溶剂，在氮气保护下加入1.03克辛硫醇(7.05毫摩尔)，混合物室温搅拌1小时，加热至35-65℃搅拌2-7小时，TLC监测反应进程到反应完全。此反应直接使用在下一步合成。
4、中间体2的合成：
3克1，6-二溴己烷(12.30毫摩尔)，10-30％的NaI或KI和25毫摩尔Na2CO3或K2CO3或NEt3或DBU或DMAP等碱溶于二氯甲烷或丙酮或THF或MTBE或乙氰或甲苯或乙醇等溶剂(1：7-20，w/v)中，室温下加入3.88克4-氨基-2，2-6，6-四甲基哌啶(24.80毫摩尔)。室温搅拌1小时，加热至40-70℃搅拌3-15小时，TLC监测反应进程直到反应完成。加入NaCl水溶液，用二氯甲烷或乙酸乙酯或MTBE萃取中间体2(15mlx3),无水MgSO4干燥合并的有机相，过滤，真空下出去溶剂，粗产品中间体2直接在下一步使用。
5、目标产物1(高聚物)的制备：
等摩尔的中间体2加入到等摩尔的中间体1的反应体系中，同时加入等摩尔的Na2CO3或K2CO3或NEt3或DBU或DMAP有机或无机碱。反应混合物室温搅拌1小时，然后加热至50-90℃搅拌5-18小时。通过加热温度和反应时间可调整产品高分子量大小。冷却至室温，加入冰 水溶液，洗去水溶性杂质，可以得到溶于有机溶剂的油状物，可以得到蜡状固体，可以得到白色固体产物作为目标产物1，产率73-91％。1H NMR(400MHz,CDCl3),δ(ppm):7.32(s,CHCl3来源于CDCl3)，4.86(m,2H,2CHN),3.41(m,2H,2CHN),3.05(m,8H,4CH2N),1.98(m,2H,CH2S),1.67(m,8H),1.11-1.49(m,63H)。
上述实施例仅用于解释说明本发明的发明构思，而非对本发明权利保护的限定，凡利用此构思对本发明进行非实质性的改动，均应落入本发明的保护范围。

Claims (7)

  1. 一种多功能协同高分子抗氧化稳定剂，其特征在于具有以下结构：
    Figure PCTCN2015096773-appb-100001
    其中，R1为连接链，所述的连接链为脂肪链、芳香结构链或脂肪与芳香结构混合链；
    R2为
    Figure PCTCN2015096773-appb-100002
    X为O、S、N或NH，或-CONR-，Z为O、S、N或NH，且X与Z不相同；
    R为脂肪链、芳香基、位阻胺或位阻酚，R3为脂肪链、芳香基、位阻胺或位阻酚，R与R3相同，或R与R3不相同；
    n为包括1的正整数，n1为包括1的正整数，n与n1相同，或n与n1不相同。
  2. 如权利要求1所述的多功能协同高分子抗氧化稳定剂，其特征在于：所述的抗氧化稳定剂为：
    Figure PCTCN2015096773-appb-100003
    Figure PCTCN2015096773-appb-100004
    Figure PCTCN2015096773-appb-100005
    所述的R3为H、脂肪烃侧链、芳香烃侧链、脂肪芳香烃混合侧链或有杂原子侧链；
    n为正整数。
  3. 如权利要求2所述的多功能协同高分子抗氧化稳定剂，其特征在于所述的抗氧化稳定剂为：
    Figure PCTCN2015096773-appb-100006
    Figure PCTCN2015096773-appb-100007
  4. 一种如权利要求2所述多功能协同高分子抗氧化稳定剂的制备方法，其特征在于包括以下步骤：
    n为≥1的自然数
    1当量的醇原料在氮气保护下加入到含有1.5-3当量的NaH或t-BuONa或t-BuOK的无水THF、DMF、丙酮、乙酸乙酯，氯仿，甲苯,MTBE,DME或乙氰溶剂中，室温下搅拌10-30分钟，滴加1.0-2.5当量的碘化物、溴化物或氯化物配有10％的NaI或KI，或活化的醇，混合物室温搅拌30分钟到1小时，TLC监测反应进程，加热到40-90℃，直到反应完成；饱和NH4Cl水溶液淬灭反应，加入乙酸乙酯或二氯甲烷或石油醚或甲苯或MTBE或DME充分混合，分离有机相，水相萃取三次，Na2OS4干燥合并的有机相，过滤，真空下除去有机溶剂；固体产物通过重结晶获取，油状或液体产物通过萃取方式纯化；
    或
    1当量的醇原料加入到含有1-3当量的NaOH或KOH或Bu4OH和10％的四丁基溴化铵的THF、丙酮、乙酸乙酯或乙氰、二氯甲烷，氯仿，甲苯，DME，MTBE，氯苯或DMF溶剂中，室温下搅拌5-30分钟， 滴加1.0-3.0当量的碘化物、溴化物或氯化物配有5-30％的NaI或KI，或活化的醇，混合物室温搅拌1-3小时，加热到40-100℃反应1-25小时，TLC监测反应进程直到反应完成，固体产物通过重结晶获取，油状或液体产物通过萃取方式纯化；
    或
    在氮气保护下1当量硫醇滴加到含有1.0-3.5当量的当量的碘化物、溴化物或氯化物配有5-30％的NaI或KI，或活化的醇干燥THF、DCM、丙酮、THF，DME，乙氰或乙醇、甲醇，氯仿，甲苯或DMF溶液中，然后加入Na2CO3或K2CO3，NaOH,KOH，Bu4OH或NEt3或DMAP或DBU或DIPEA或吡啶，混合物室温搅拌30分钟，然后加热到40-90℃，TLC监测反应进程直到反应完成；NaCl饱和水溶液和等量的乙酸乙酯或二氯甲烷加入到反应体系，充分混合，分离有机相，水相用同样有机溶剂洗三次，Na2SO4干燥合并的有机相，过滤，真空下除掉有机溶剂；重结晶得到固体产物，硅胶柱层析或萃取分离得到液体或油状产物；
    或
    1当量的胺溶于二氯甲烷、乙酸乙酯、丙酮、乙氰、THF、乙醇、甲醇，氯仿，MTBE，DME，甲苯或DMF溶剂中，在氮气保护搅拌下滴加到1-3当量的有机碘化物、溴化物、氯化物或活化的醇类化合物含有1-3当量NaOH或KOH或Bu4OH或K2CO3或Na2CO3或DIPEA或NEt3或吡啶同样有机溶剂的溶液中，用无机碱时5-30％的四丁基溴化胺应当配比加入，混合物室温反应1-3小时，加热到40-90℃搅拌额外1-25小时；冷却，NH4Cl水溶液洗掉碱性和水溶性杂质，在有机相里的固体产物重结晶得到产物，液体或油状物产品通过硅胶柱层析或萃取方式得到纯化；
    或
    1当量的胺和1当量碱溶于或悬浮于无水二氯甲烷、THF、MTBE、DME，丙酮、乙氰，氯仿，甲苯或DMF溶剂，在氮气保护下0-10℃滴加1当量羧酰氯同样干溶剂的溶液，混合物0-10度搅拌30分钟至2小时，室温或加热到30-60℃反应3-24小时，TLC监测反应进程直到反应完全；加入二氯甲烷、乙酸乙酯，甲苯，DME或MTBE和0.1N的 盐酸冰水溶液，混合后分出有机相，水相用同样有机溶剂洗两次，无水Na2SO4干燥合并的有机相，过滤，浓缩；固体产物通过重结晶得到，液体或粘稠油状产物通过硅胶柱色层分离或萃取得到；
    或
    通过调节n的大小可控制高分子产物平均分子量从1000到5000道尔顿
    1当量的二胺、多胺溶于干燥二氯甲烷、乙酸乙酯、THF、丙酮、乙氰、乙醇、甲醇，氯仿，甲苯或DMF中，再搅拌和氮气保护下滴加多碘、多溴或多氯有机物，室温搅拌30分钟，然后加热到40-100℃反应6-72小时，通过反应温度和时间来控制聚合物产物平均分子量的大小，过滤出固体粉末产品，用二氯甲烷溶剂洗3次得到固体产物，或用萃取的方式纯化得到粘稠油状产物。
  5. 如权利要求4所述多功能协同高分子抗氧化稳定剂的制备方法，其特征在于：所述的反应方程式为：
    Figure PCTCN2015096773-appb-100008
  6. 一种如权利要求1-3任一权利要求所述的多功能协同高分子抗氧化稳定剂作为抗氧化剂的应用。
  7. 如权利要求6所述的多功能协同高分子抗氧化稳定剂在塑料、橡胶、石油品、涂料、纤维产品或油漆中的应用。
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