CN110498922A - 一种n-(4-苯胺基苯基）甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂及其应用 - Google Patents

一种n-(4-苯胺基苯基）甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂及其应用 Download PDF

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CN110498922A
CN110498922A CN201910820007.0A CN201910820007A CN110498922A CN 110498922 A CN110498922 A CN 110498922A CN 201910820007 A CN201910820007 A CN 201910820007A CN 110498922 A CN110498922 A CN 110498922A
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aniiinophenyl
antioxidant
methyl methacrylate
ethylenediamine
macromolecular antioxidant
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何敏
刘玉飞
于杰
秦舒浩
徐国敏
张凯
张道海
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Guizhou University
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
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    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract

本发明公开了一种大分子抗氧剂，其特征在于：所述的抗氧剂含有官能团N‑(4‑苯胺基苯基)甲基丙烯酸甲酯。本发明制备了N‑(4‑苯胺基苯基)甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂；该类聚合物具有良好的抗热氧老化性能，不仅可以作为PVC、ABS等普通塑料的耐热氧老化改性剂，也可以作为聚丙烯，PA6、PPO等工程塑料的抗热氧老化剂且效果良好。

Description

一种N-(4-苯胺基苯基)甲基丙烯酸甲酯与乙二胺共聚大分子 抗氧剂及其应用
技术领域
本发明涉及一种大分子抗氧剂的制备及其改性尼龙6，具体属于树脂原料、医药农药中间体的合成领域。
背景技术
目前文献报道一般都是由链终止型和预防型两种抗氧剂复配，比如：醇酯抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)与亚磷酸酯抗氧剂168(三[2,4-二叔丁基苯基]亚磷酸酯)的复配[23]、受阻酚类1098(N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺)与抗氧剂168复配[24]、受阻酚类抗氧剂245与亚磷酸酯类辅助型抗氧剂626、铜盐类热稳定剂AN复配[19]等。但是，以上抗氧剂分子量皆较低，而小分子抗氧剂沸点低，在加工的过程中易挥发、易析出。
发明内容
本发明要解决的技术问题是：提供N-(4-苯胺基苯基)甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂，以解决现有技术中抗氧剂分子量皆较低，沸点低，在加工的过程中易挥发、易析出的局限性。
本发明的技术方案是：一种大分子抗氧剂，所述的抗氧剂含有官能团N-(4-苯胺基苯基)甲基丙烯酸甲酯。
所述的抗氧剂为含N-(4-苯胺基苯基)甲基丙烯酸甲酯的二元、三元及以上的共聚物。
所述的一种大分子抗氧剂的制备方法，其反应式如下所示：
n＝10-100。
所述的一种大分子抗氧剂的制备方法，其反应步骤如下：加热油浴锅至50-100℃，将溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯、乙二胺的环己酮溶液加入反应器，并在此温度下搅拌20-60min；加入二甲苯，通入N2气，搅拌、加热至95-130℃反应，反应3-5h，得到初产物，趁热将初产物溶于丙酮，用甲醇重沉淀，将得到的产物于40-130℃真空干燥4-24h，得到粉状二元共聚物树脂样品，即大分子抗氧剂。
所述的溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯与乙二胺摩尔比为1:18～22。
本发明的有益效果：本发明制备了N-(4-苯胺基苯基)甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂；该类聚合物具有良好的抗热氧老化性能，不仅可以作为PVC、ABS等普通塑料的耐热氧老化改性剂，也可以作为聚丙烯，PA6、PPO等工程塑料的抗热氧老化剂且效果良好。
具体实施方式
下面通过具体实例进一步说明本发明，但实例并不限制本发明的保护范围。
实施例1
N-(4-苯胺基苯基)甲基丙烯酸甲酯溴化：将4.24gN-(4-苯胺基苯基)甲基丙烯酸甲酯溶于50mL的CCl4和CH3COOH中；在0℃及以下，逐滴将2.93g Br2的CCl4溶液加到N-(4-苯胺基苯基)甲基丙烯酸甲酯的溶液中，反应1小时后将反应体系倒入到蒸馏水中，放置3-5分钟，趁冷抽滤。将滤饼放在70℃烘箱内烘干。
将溴化的N-(4-苯胺基苯基)甲基丙烯酸甲酯、乙二胺缩聚，得到二元共聚产物，制备方法如下：
加热油浴锅至76℃，将0.9g溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯和2.34g乙二胺的环己酮溶液加入烧杯，并在此温度下搅拌40min；把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的250ml四颈瓶中，加入70ml二甲苯，通入N2气，搅拌、加热至125℃反应，反应4h，得到初产物。趁热将初产物溶于丙酮，用甲醇作沉淀剂重沉淀去除残留的单体和小分子，将得到的产物与60℃真空干燥24h，以去除小分子。得到粉状二元共聚物树脂样品。
实施例2
N-(4-苯胺基苯基)甲基丙烯酸甲酯溴化：将42.4gN-(4-苯胺基苯基)甲基丙烯酸甲酯溶于50mL的CCl4和CH3COOH中；在0℃及以下，逐滴将29.3g Br2的CCl4溶液加到N-(4-苯胺基苯基)甲基丙烯酸甲酯的溶液中，反应1小时后将反应体系倒入到蒸馏水中，放置3-5分钟，趁冷抽滤。将滤饼放在70℃烘箱内烘干。
将溴化的N-(4-苯胺基苯基)甲基丙烯酸甲酯、乙二胺缩聚，得到二元共聚产物，制备方法如下：
加热油浴锅至76℃，将9g溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯和23.4g乙二胺的环己酮溶液加入烧杯，并在此温度下搅拌40min；把溶液转移到安装有搅拌器、冷凝器、温度计、导气管的1000ml四颈瓶中，加入700ml二甲苯，通入N2气，搅拌、加热至125℃反应，反应4h，得到初产物。趁热将初产物溶于丙酮，用甲醇作沉淀剂重沉淀去除残留的单体和小分子，将得到的产物与60℃真空干燥24h，以去除小分子。得到粉状二元共聚物树脂样品。
将实例2中得到的产物加入到聚丙烯(PP)，并对复合材料进行热氧老化性能研究，130℃下热氧老化50天，拉伸强度结果如下表所示：
试样编号 1 1 3 4
热氧老化前 23MPa 25MPa 26MPa 27MPa
热氧老化后 11MPa 15PMa 18MPa 22MPa
注：表中1号为未添加二元共聚，2号添加了1份三元共聚，3号添加了2份，4号添加了3份。
专业人员能够通过常识联想到的只要含有N-(4-苯胺基苯基)甲基丙烯酸甲酯的二元、三元及以上的共聚物也在保护的范围之内。

Claims (5)

1.一种大分子抗氧剂，其特征在于：所述的抗氧剂含有官能团N-(4-苯胺基苯基)甲基丙烯酸甲酯。
2.根据权利要求1所述的一种大分子抗氧剂，其特征在于：所述的抗氧剂为含N-(4-苯胺基苯基)甲基丙烯酸甲酯的二元、三元及以上的共聚物。
3.如权利要求1所述的一种大分子抗氧剂的制备方法，其特征在于：其反应式如下所示：
n＝10-100。
4.根据权利要求2所述的一种大分子抗氧剂的制备方法，其特征在于：其反应步骤如下：加热油浴锅至50-100℃，将溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯、乙二胺的环己酮溶液加入反应器，并在此温度下搅拌20-60min；加入二甲苯，通入N2气，搅拌、加热至95-130℃反应，反应3-5h，得到初产物，趁热将初产物溶于丙酮，用甲醇重沉淀，将得到的产物于40-130℃真空干燥4-24h，得到粉状二元共聚物树脂样品，即大分子抗氧剂。
5.根据权利要求4所述的一种大分子抗氧剂的制备方法，其特征在于：所述的溴化后的N-(4-苯胺基苯基)甲基丙烯酸甲酯与乙二胺摩尔比为1:18～22。
CN201910820007.0A 2019-08-31 2019-08-31 一种n-(4-苯胺基苯基）甲基丙烯酸甲酯与乙二胺共聚大分子抗氧剂及其应用 Pending CN110498922A (zh)

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CN116178708A (zh) * 2022-12-20 2023-05-30 山东秋水化学科技有限公司 一种复合型抗氧剂的制备方法

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CN116178708A (zh) * 2022-12-20 2023-05-30 山东秋水化学科技有限公司 一种复合型抗氧剂的制备方法

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Application publication date: 20191126