CN116554128A - 一种自固化、高模高强的本征阻燃磺胺环氧树脂及其制备方法 - Google Patents
一种自固化、高模高强的本征阻燃磺胺环氧树脂及其制备方法 Download PDFInfo
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
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Abstract
本发明提供了式I所示的磺胺环氧树脂及其制备方法。本发明通过工艺控制巧妙地设计合成了同时含有环氧基和氨基的树脂,无需混合固化剂或其它组分即可实现自固化,并且本发明环氧树脂在具有较高和可控的反应活性,同时还兼具优异的物理机械性能和本征阻燃特性,具有广阔的应用前景。
Description
技术领域
本发明属于材料领域,具体涉及一种自固化、高模高强的本征阻燃磺胺环氧树脂及其制备方法。
背景技术
环氧树脂因其优良的加工性能、粘接性能、机械性能、电绝缘性能、化学稳定性和其他性能,被广泛用于电子包装以及涂料、粘合剂和复合材料基体。当环氧树脂作为复合材料基体应用时,一方面,随着电子电器、涂料、飞机与航天器等领域的不断发展,对环氧树脂基复合材料的阻燃性能也提出了更高的要求,而这就需要树脂基体具有良好的阻燃性;另一方面,对于以环氧树脂为基体的碳纤维复合材料而言,其抗压强度受到树脂基体模量的显著影响,新一代高性能纤维的引入需要具有更高模量的树脂基体与之匹配;除此之外,制备预浸料的过程中需要将环氧树脂与固化剂加热混合使用,工艺较为繁琐,且面临着固化剂冷却析出的问题。
为了提高环氧树脂的阻燃性能,大多采用添加阻燃剂的方法,例如将氢氧化铝、红磷、有机硅、有机卤类阻燃剂添加到环氧树脂基体中实现阻燃,但这些阻燃剂与环氧树脂基体间的相容性问题,也会对环氧树脂的机械性能带来显著的影响。虽然除了添加型阻燃环氧树脂外,目前也开发出了本征阻燃环氧树脂(反应型阻燃环氧树脂),即通过化学反应在树脂上引入阻燃基团来提升树脂的阻燃性,可以避免阻燃剂添加导致的不相容问题,但现有的本征阻燃环氧树脂往往合成路线繁琐,原料昂贵,成本较高,且力学性能也难以匹配新一代高模量碳纤维([1]Qi Y,Wang J,Kou Y,et al.Synthesis of an aromatic N-heterocycle derived from biomass and its use as a polymer feedstock[J].NatureCommunications,2019;[2]Qi Y,Weng Z,Kou Y,etal.Facile synthesis of bio-basedtetra-functional epoxy resin and its potential application as high-performance composite resin matrix[J].Composites Part BEngineering,2021,214:108749.[3]Yu Q A,Zw A,Yan K B,et al.Synthesize and introduce bio-basedaromatic s-triazine in epoxy resin:Enabling extremely high thermal stability,mechanical properties,and flame retardancy to achieve high-performancesustainable polymers-ScienceDirect[J].Chemical Engineering Journal,2020,406.)。
因此,为了进一步拓宽环氧树脂的应用,开发兼具良好机械性能和本征阻燃性的环氧树脂是非常重要的。目前还未见具有自固化、高模高强的本征阻燃环氧树脂报道。
发明内容
本发明的目的在于提供一种自固化磺胺环氧树脂的制备方法,包括如下步骤:
(1)对氨基苯磺酰胺与环氧氯丙烷混合在110~130℃反应22~26小时;
(2)降温至35~45℃,加碱反应3~5小时;
反应式如下:
进一步地,上述碱是氢氧化钠或氢氧化钾;优选为氢氧化钠。
进一步地,上述环氧氯丙烷和对氨基苯磺酰胺的摩尔比为(25~35):1,优选为30:1;
所述氨基苯磺酰胺和碱的摩尔比为1:(2~3),优选为1:2.25。
进一步地,上述步骤(1)所述反应是在120℃反应24小时。
进一步地,上述步骤(2)所述反应是40℃反应4小时。
本发明还提供了一种磺胺环氧树脂,包括式I所示结构:
进一步地,上述磺胺环氧树脂由上述的方法制备而成。
本发明还提供了一种固化环氧树脂,它是上述的磺胺环氧树脂固化而成。
进一步地,上述固化环氧树脂是上述磺胺环氧树脂于130~150℃反应1~3h,再于190~210℃反应2~4h自固化而成;优选地,为140℃反应2h,再于200℃反应3h自固化而成。
本发明还提供了上述的固化环氧树脂在阻燃材料中的应用。
本发明的有益效果:
本发明采用阻燃剂磺胺作为原料,利用官能团活性的差异,巧妙设计了一种同时含有胺基与环氧基的自固化环氧树脂,只需加热即可固化成型,大大优化了碳纤维复合材料的成型工艺。自固化这种特殊结构大大提高了体系中-SO2-基团的数量,使得该树脂兼具良好的机械性能与良好的本征阻燃性。除此之外,该树脂合成方法十分简便,原料便宜,具有良好的应用前景。
显然,根据本发明的上述内容,按照本领域的普通技术知识和惯用手段,在不脱离本发明上述基本技术思想前提下,还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式,对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为本发明磺胺环氧树脂的反应式与红外谱图、核磁共振氢谱图。
图2为对比例磺胺环氧树脂的核磁共振氢谱图。
图3为本发明固化磺胺环氧树脂和E51/DDM固化环氧树脂的垂直燃烧实验结果。
图4为本发明固化磺胺环氧树脂和E51/DDM固化环氧树脂的微型燃烧实验结果。
图5为本发明固化磺胺环氧树脂和E51/DDM固化环氧树脂的热失重分析结果。
图6为热失重分析实验结果图。
图7为不同升温速率下的DSC分析结果图。
具体实施方式
本发明所用原料与设备均为已知产品,通过购买市售产品所得。
实施例1、本发明磺胺环氧树脂的制备
将1摩尔份对氨基苯磺酰胺加入到30摩尔份环氧氯丙烷中,在120℃条件下反应24小时(无需催化剂),反应结束后降温到40℃,加2.25摩尔份氢氧化钠反应4小时,然后过滤,水洗,除去溶剂即得到产物。
对得到的磺胺环氧树脂(SAASC)与原料对氨基苯磺酰胺(SAA)进行红外光谱分析,并进行核磁共振氢谱检测,结果如图1所示,证明本发明式I结构的磺胺环氧树脂SAASC成功合成。
实施例2、固化磺胺环氧树脂的制备
实施例1得到的磺胺环氧树脂溶液,在140℃反应2h,然后在200℃反应3h,自固化得到固化的磺胺环氧树脂SAASC。
实施例3、本发明磺胺环氧树脂的制备
将1摩尔份对氨基苯磺酰胺加入到25摩尔份环氧氯丙烷中,在120℃条件下反应24小时(无需催化剂),反应结束后降温到40℃,加2.25摩尔份氢氧化钠反应4小时,然后过滤,水洗,除去溶剂即得到产物。
对得到的磺胺环氧树脂(SAASC)与原料对氨基苯磺酰胺(SAA)进行红外光谱分析,并进行核磁共振氢谱检测,结果如图1所示,证明本发明式I结构的磺胺环氧树脂SAASC成功合成。
实施例4、本发明磺胺环氧树脂的制备
将1摩尔份对氨基苯磺酰胺加入到35摩尔份环氧氯丙烷中,在120℃条件下反应24小时(无需催化剂),反应结束后降温到40℃,加2.25摩尔份氢氧化钠反应4小时,然后过滤,水洗,除去溶剂即得到产物。
对得到的磺胺环氧树脂(SAASC)与原料对氨基苯磺酰胺(SAA)进行红外光谱分析,并进行核磁共振氢谱检测,结果如图1所示,证明本发明式I结构的磺胺环氧树脂SAASC成功合成。
对比例1、
参照实施例1的方法,将对氨基苯磺酰胺和环氧氯丙烷的反应条件调整为:加入4-丁基溴化铵作催化剂,100℃反应12小时,反应结束后降温到40℃,加2.25摩尔份氢氧化钠反应2小时,其余条件不变,得到产物。
对得到的产物进行红外光谱分析,并进行核磁共振氢谱检测,结果如图2中序号1的图谱所示,可见,加入催化剂反应后,无法实现准确的选择性取代。
对比例2、
参照对比例1的方法,将催化剂替换为苄基三甲基氯化铵,其余条件不变,得到产物。
对得到的产物进行红外光谱分析,并进行核磁共振氢谱检测,结果如图2中序号2的图谱所示,可见,加入催化剂反应后,无法实现准确的选择性取代。
对比例3、
参照实施例1的方法,将对氨基苯磺酰胺和环氧氯丙烷的反应条件调整为:120℃反应12小时,反应结束后降温到40℃,加2.25摩尔份氢氧化钠反应2小时,其余条件不变,得到产物。
对得到的产物进行红外光谱分析,并进行核磁共振氢谱检测,结果如图2中序号3的图谱所示,可见,反应时间缩短后得到的产物取代不完全。
对比例4、E51环氧树脂/芳香胺固化剂体系
4,4'-亚甲基苯胺(DDM)被用来固化E51环氧树脂,环氧树脂的固化遵循活性官能团与氨基氢摩尔比1:1的比例。将90℃以上的纯环氧树脂与DDM的液体混合物倒入一个PTFE模具中。该树脂在120℃下固化2小时,150℃下固化3小时,然后在180℃下固化3小时。程序结束后,样品被退火至室温。制得E51/DDM固化环氧树脂。
以下通过实验例证明本发明的有益效果。
实验例1、本发明磺胺环氧树脂的性能表征
1、实验方法
核磁共振(NMR)光谱以四甲基硅烷(TMS)为内标,DMSO-d6为溶剂,在Bruker AV II(瑞士)上以600MHz记录1H NMR光谱。傅里叶红外光谱(FTIR)是用Nicolet 570(ThermoScientific,美国)测量的,扫描范围在室温下从600cm-1到4000cm-1。以上测试均为固化前的树脂(实施例1)。对固化后的树脂(实施例1)和对比例4进行力学性能测试,测试的样品尺寸为80×10×4毫米,三点弯曲测试在室温下进行,加载速度为2毫米/分钟,跨度为64毫米,使用万能试验机Instron 5567(Instron,美国)按照ASTM D7264标准进行。UL-94垂直燃烧试验在垂直燃烧试验机上进行,样品尺寸为80×10×3毫米。微尺度燃烧量热仪(MCC)根据ASTM D7309-13在FTT0001微尺度燃烧量热仪(英国)上进行,约5毫克的样品在80厘米3/分钟的氮气流量下,以1℃/秒的加热速率从70-700℃加热。在氮气环境下,用TG290-F1(NETZSCH,德国)研究了固化产品的分解温度和残留物,这些产品从40℃加热到800℃。
2、实验结果
从图1红外光谱中907cm-1处的出峰表明环氧基团的成功引入。而核磁谱图中对氨基苯磺酰胺(SAA)在5.9ppm处峰的消失以及6.9ppm处峰的残留表明实现了氨基的选择性取代,证实本发明成功合成了磺胺结构的环氧树脂SAASC。
固化的SAASC与E51/DDM的力学性能测试结果如表1。表明固化SAASC力学性能十分优异,且明显强于E51/DDM。
表1
图3是垂直燃烧实验结果,可以看出,SAASC在第一次点燃和第二次点燃后都快速熄灭,表现出良好的本征阻燃性。
图4是微型燃烧实验结果,可以看出SAASC的峰值放热量和总放热量都明显低于E51/DDM体系,表现出良好的阻燃性。
图5是锥形燃烧实验结果,可以看出SAASC的峰值放热量和总放热量都明显低于E51/DDM体系,且烟雾释放速率和总烟雾量均明显低于E51/DDM体系,表现出良好的阻燃性。
图6是热失重分析实验结果,可以看出,SAASC体系热残重更高,说明热稳定性更好。
图7是不同升温速率下的DSC分析结果,可以看出SAASC活性适中,在室温下不会反应。
综上,本发明通过工艺控制巧妙地设计合成了同时含有环氧基和氨基的环氧树脂,无需混合环氧树脂和固化剂即可实现自固化,大大提高了加工效率;并且本发明环氧树脂在具有高反应活性的同时还兼具优异的机械性能(弯曲模量达到5154.9MPa,弯曲强度达到125.7MPa)和本征阻燃性,以及优异的热稳定性,具有广阔的应用前景。
Claims (10)
1.一种自固化磺胺环氧树脂的制备方法,其特征在于,包括如下步骤:
(1)对氨基苯磺酰胺与环氧氯丙烷混合在110~130℃反应22~26小时;
(2)降温至35~45℃,加碱反应3~5小时;
反应式如下:
2.如权利要求1所述的制备方法,其特征在于,所述碱是氢氧化钠或氢氧化钾;优选为氢氧化钠。
3.如权利要求1所述的制备方法,其特征在于,所述环氧氯丙烷和对氨基苯磺酰胺的摩尔比为(25~35):1,优选为30:1;
所述氨基苯磺酰胺和碱的摩尔比为1:(2~3),优选为1:2.25。
4.如权利要求1所述的制备方法,其特征在于,步骤(1)所述反应是在120℃反应24小时。
5.如权利要求1所述的制备方法,其特征在于,步骤(2)所述反应是40℃反应4小时。
6.一种磺胺环氧树脂,其特征在于,包括式I所示结构:
7.如权利要求6所述的磺胺环氧树脂,其特征在于,它由权利要求1~5任一项所述的方法制备而成。
8.一种固化环氧树脂,其特征在于,它是权利要求6或7所述的磺胺环氧树脂固化而成。
9.如权利要求8所述的固化环氧树脂,其特征在于,它是权利要求6或7所述的环氧树脂于130~150℃反应1~3h,再于190~210℃反应2~4h自固化而成;优选地,为140℃反应2h,再于200℃反应3h自固化而成。
10.权利要求8或9所述的固化环氧树脂在阻燃材料中的应用。
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