CN111363122B - 一种三重交联高性能聚合物及其制备方法 - Google Patents
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Abstract
本发明公开了一种三重交联高性能聚合物及其制备方法,所述聚合物由双环氧单体、交联单体和功能单体固化交联形成,且含有由共价键和两种不同强度多层次氢键形成的交联网络结构,所述共价键与两种所述氢键的作用强度呈梯度递减,通过在聚合物内形成共价键和不同强度的多层次氢键的三重交联网络,克服高性能聚合物的强度‑延展性权衡的困境,动态的、层次化的氢键的及时、连续的断裂和充足过程使聚合物网络在保护结构完整性的同时,能够快速响应外界环境的传递和耗散,从而使得到的刚性聚合物不仅具有高拉伸强度和还具有很好的延伸性。
Description
技术领域
本发明涉及一种高性能聚合物,具体涉及一种三重交联高性能聚合物及其制备方法。
背景技术
高性能聚合物优异的耐高温性、耐腐蚀性;显著的机械强度;特别是其轻质性、结构可设计性、形状可调性等一系列突出的特点,使得这类材料已经逐渐替代大多数传统的金属、无机材料,在微电子、精密机械,特别是航空航天方面得到了广泛的应用,具有广阔的应用前景和巨大的商业价值。近年来,我国无论是在航天航空,还是医疗器械、军工制造及基础设施建设方面都取得了很大的发展,这些方面的发展都对相关材料的性能提出更高的要求,特别是对于在很多器件中用作核心部件的高性能聚合物材料,既要求其具有更加优异的热稳定性、机械强度的同时还具有较好的拉伸延展性能,而传统的高性能聚合物材料已很难同时满足上述要求。因此,研发具有更加优异的综合性能的新型高性能聚合物材料成为了当下亟待解决的、同时也是极具研究价值的科学问题。
增加化学交联密度和或在聚合物中加入填料等传统策略可以提高机械强度,但不幸的是,以牺牲必要的延展性为代价,总之,提高强度往往会导致延展性降低,反之亦然。例如,采用超分子相互作用,如氢键、阳离子-π和金属-配体相互作用,在降低脆性方面显示出显著的效果,因为超分子相互作用的缔合和解离可以有效地耗散能量,然而,非共价超分子相互作用比共价键弱得多,导致机械强度较低,这种强度-延展性权衡一直是聚合物科学中的一个长期难题。开发一种新的策略来同时赋予聚合物高强度和高延伸性是非常有必要的。
发明内容
本发明的目的在于提供一种三重交联高性能聚合物及其制备方法,解决现有聚合物高强度与高延展性难以权衡的问题。
为了实现上述目的,本发明采用的技术方案为:
一种三重交联高性能聚合物,所述聚合物通过双环氧单体、交联单体和功能单体固化交联制得,且所述聚合物含有由共价键和两种不同强度的多层次氢键形成的交联网络,所述共价键与两种所述氢键的作用强度呈梯度递减。
优选的,所述功能单体之间、和所述功能单体与所述双环氧单体之间可形成不同强度的多层次氢键,所述环氧单体与所述交联单体之间、所述双环氧单体与所述功能单体之间可形成共价键。
优选的,所述双环氧单体为官能度≥2的芳香族环氧树脂,所述交联单体为官能度>2的多元胺,所述功能单体为含有两种功能基团的化合物,其中一种所述功能基团的官能度≥1且能与环氧开环形成共价键,另一种所述功能基团同时含有氢键供体和氢键受体。
优选的,所述环单体为双酚A环氧树脂、双酚F环氧树脂中任意一种,所述交联单体为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、1,6-己二胺、甲基环戊二胺、间苯二甲胺、异佛尔酮二胺、以及2-甲基戊二胺中任意一种,所述功能单体为5-氨基-1H-苯并***。
一种三重交联高性能聚合物的制备方法,该方法的工艺步骤和条件如下:
(1)将双环氧单体、交联单体和功能单体混合后溶于适量的溶剂中,搅拌均匀得到混合溶液;
(2)将步骤(1)所得的混合溶液过滤后浇铸在干净的平板玻璃上,并在60-180℃和0-450托的条件下固化3-12小时。
优选的,所述步骤(1)中的双环氧单体、交联单体和功能单体摩尔比为10:2.5-4.5:1-5。
优选的,所述步骤(1)中的双环氧单体、交联单体和功能单体摩尔比为10:3:4。
优选的,所述溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚峰、1,4-二氧六环、对二甲苯、间二甲苯或乙腈中的任意一种。
与现有技术相比,本发明的优点在于:
1、本发明通过在聚合物内形成共价键和不同强度的多层次氢键的三重交联网络,克服高性能聚合物的强度-延展性权衡的困境,动态的、层次化的氢键的及时、连续的断裂和充足过程使聚合物网络在保护结构完整性的同时,能够快速响应外界环境的传递和耗散,从而使得到的刚性聚合物不仅具有高拉伸强度和还具有很好的延伸性;
2、本发明中当聚合物受到小应变时,共价交联和两种类型不用强度的的氢键一起工作以防止材料损坏,当加载较大的应力时,通过作用力较弱的可逆氢键的断裂和重组可耗散的能量,而作用力较强氢键作用与双方共价交联作用,以保护聚合物免受破坏;当进一步拉伸时,两种不同强度的分层氢键共同作用以传递和消除内应力,这使得聚合物膜被拉伸了很多,但没有被破坏,因为化学交联仍然保护了结构的完整性;
3、本发明的聚合物不同强度多层级氢键的加入并不会影响聚合物的热稳定性,该聚合物在具有高强度和高延展性的同时还具有良好的热稳定性;
4、本发明的聚合物中因为有化学交联的存在,所以在常用溶剂中均表现出良好的耐溶剂型,有很好的应用前景。
附图说明
图1为实施例1-5制备的聚聚合物的FT-IR光谱;
图2为对比例1制备的聚合物的FT-IR光谱;
图3为对比例2-5制备的聚合物的FT-IR光谱;
图4为是实施例2、实施例4和对比例1制备的聚合物的13C CP/MAS NMR光谱;
图5为实施例2、实施例4和对比例1的热重曲线;
图6为实施例2制备的聚合物在应变速率dε/dt=0.24mms-1下的循环应力-应变曲线;
图7为实施例4制备的聚合物在应变速率dε/dt=0.24mms-1下的循环应力-应变曲线。
具体实施方式
本发明的实施例中所采用的原料如下:
双酚A环氧树脂(平均环氧值=0.51):TCI Development Co.,Ltd,原装使用;
1,6-己二胺:J&K Technology Co.,Ltd.原装使用;
5-氨基-1H-苯并***:J&K Technology Co.,Ltd.原装使用;
4-氨基吡啶:J&K Technology Co.,Ltd.原装使用;
本发明的实施例中有关数据的测试方法如下:
在Nicolt 6700傅里叶变换红外光谱仪上记录了样品的FTIR光谱;
在Agilent-NMR-vnmrs 600光谱仪上记录了13C固态交叉极化幻角自旋(CP/MAS)NMR光谱;
在氮气流动条件下,以20℃/min的速率通过差示扫描量热量(DSC)测得聚合物玻璃化转变温度;
在氮气下,以20℃/min的升温速率,对Mettler tga2进行热重分析(TGA);
在室温下,加载单元为500N,试样为58×7mm的薄膜状试样,以拉伸速率1mm min-1,在KD-5材料试验机上进行单轴拉伸试验;
在室温下,应变速率为dε/dt=0.24mm s-1,进行循环加载试验,循环加载试验采用零周零力循环加载。
实施例
下列实施例进一步描述和证明了本发明范围内的优选实施方案,所给的这些实施例仅仅是说明性的,不可理解为是对本发明的限制。
实施例1
将0.2g摩尔比为10:4.5:1双酚A环氧树脂、1,6-己二胺和5-氨基-1H-苯并***的混合物溶于2.5mL N,N-二甲基甲酰胺(DMF)中,搅拌均匀形成混合溶液,过滤后浇铸在干净的平板玻璃上,并在80℃和450托的条件下固化12小时,制得聚合物样品PAHB-1。
实施例2
将双酚A环氧树脂、1,6-己二胺和5-氨基-1H-苯并***的摩尔比改为:10:4:2,其他条件同实施例1,制得聚合物样品PAHB-2。
实施例3
将双酚A环氧树脂、1,6-己二胺和5-氨基-1H-苯并***的摩尔比改为:10:3.5:3,其他条件同实施例1,制得聚合物样品PAHB-3。
实施例4
将双酚A环氧树脂、1,6-己二胺和5-氨基-1H-苯并***的摩尔比改为:10:3:4,其他条件同实施例1,制得聚合物样品PAHB-4。
实施例5
将双酚A环氧树脂、1,6-己二胺和5-氨基-1H-苯并***的摩尔比改为:10:2.5:5,其他条件同实施例1,制得聚合物样品PAHB-5。
发明人为了验证不同强度的氢键是赋予聚合物高强度和高延展性的必要条件,设计了对比例1(不包含氢键)和对比例2-5(结构相似但只含有共价交联和弱单氢键交联作用):
对比例1
将0.2g双酚A环氧树脂和1,6-己二胺的混合物溶解在2.5mL N,N-二甲基甲酰胺(DMF)中形成均一溶液,将混合溶液过滤后浇铸在干净的平板玻璃上,在80℃和450托下固化12小时,制得聚合物样品PHB,所述双酚A环氧树脂与1,6-己二胺的摩尔比为2:1。
对比例2
将0.2g摩尔比为10:4:2双酚A环氧树脂、1,6-己二胺和4-氨基吡啶的混合物溶于2.5mL N,N-二甲基甲酰胺(DMF)中,形成均匀溶液,滤后浇铸在干净的平板玻璃上,并在80℃和450托下固化12小时,制得聚合物样品PYHB-2。
对比例3
将双酚A环氧树脂、1,6-己二胺和4-氨基吡啶的摩尔比改为:10:3.5:3,其他条件同对比例2,制得聚合物样品PYHB-3。
对比例4
将双酚A环氧树脂、1,6-己二胺和4-氨基吡啶的摩尔比改为:10:3:4,其他条件同对比例2,制得聚合物样品PYHB-4。
对比例5
将双酚A环氧树脂、1,6-己二胺和4-氨基吡啶的摩尔比改为:10:2.5:5,其他条件同对比例2,制得聚合物样品PYHB-5。
发明人对采用傅里叶变换红外光谱仪和Agilent-NMR-vnmrs 600光谱仪对由实施例1-5,和对比例1-5所得到的聚合物样品进行了表征,得到图1、图2、图3和图4,由图1和图2的FT-IR光谱中可见,在2964、2871cm-1处的强吸收峰对应于拉伸振动,在1501、1457cm-1处的强吸收峰对应于-CH2-和-CH3的弯曲振动,1252、1184cm-1吸收峰的出现对应于-C-O-C-的伸缩振动,920和860cm cm-1的环氧环模式特征吸收峰缺失,表明发生了预期的固化反应,PHB和PAHBs聚合物成功合成;
由图3的FT-IR光谱中可见,在2973、2868cm-1处的强吸收峰对应于拉伸振动,而1508、1463cm-1处的强吸收峰对应于-CH2-和-CH3的弯曲振动,1255、1179cm-1吸收峰的出现对应于-C-O-C-的伸缩振动,在920和860cm-1附近没有环氧环模的特征吸收峰,表明固化反应顺利进行,对比例2-5制得的聚合物成功合成。
此外由图1可见随着苯并***基团含量的增加,FT-IR光谱中约1664cm-1(苯并***基团的-NH-的弯曲振动)和828cm-1(苯基C-H的振动)的吸收峰强度增加,由图4的13C CP/MAS NMR光谱中可见,随着苯并***基团含量的增加,123.5-110.2(苯基C)和27.4ppm(亚甲基C)之间的积分面积比增加,表明实施例所制备的聚合物中有效的引入了苯并***基团。
发明人实施例1-5、对比例1-5以及传统的聚合物材料进行了单拉伸实验,并测得了最大断裂应力和最大断裂应变,见表1:
表1实施例、对比例以及传统聚合物材料的力学机械性能
由表1可见,随着苯并***基团含量的增加,拉伸强度和断裂伸长率也是同步增加的,特别是针对实施例4制得的聚合物样品PAHB-4,断裂应力和断裂应变均为最大,分别为117.7MPa、14.93%,所以实施例4的原料摩尔比应为最优摩尔比,PAHB-4聚合物的综合性能最高,本发明通过调节苯并***基团在聚合物体系内的含量,来探究聚合物体系内共价键和氢键之间的比例对聚合物性能的影响;
实施例4所制得的聚合物样品PAHB-4的拉伸强度和延展性明显高于传统的环氧树脂、芳香族聚酰亚胺(PI)、聚芳醚酮(PAEK)、聚醚酰亚胺(PEIS)和聚乳酸(PLA),证明本发明所制得的聚合物,相比于传统的聚合材料具有更高的拉伸强度和更好的延伸性;并且聚合物样品PAHB-4的拉伸强度和断裂伸长率远高于对比例1制取的聚合物样品PHB和对比例2-5制得的聚合物样品,表明了聚合物网络中不同强度的层次氢键,是赋予PAHBs聚合物优异的抗拉强度和延展性的必要条件。
发明人为了进一步的该聚合物的性能,将对比例1、实施例2和实施例4制得的聚合物进行热重分析(TGA)、差示扫描量热量(DSC)测量,以及对实施例1-5进行了耐溶性试验,结果见图5、图6、图7和表2:
由图5可见,当热分解温度(TDS)在350℃以上时,所有聚合物都具有良好的热稳定性,满足通常情况下的实验需求这表明化学交联部分被氢键取代并不影响热稳定性;
由图6和图7可见,多循环PAHB-2和PAHB-4薄膜在应变速率dε/dt=0.24mms-1下的循环应力-应变曲线均表明PAHBs聚合物具有良好的循环性能。
表2 PAHBs的耐溶剂性
--:聚合物不能被溶解。DMF:N,N-二甲基甲酰胺;DMAc:N,N-二甲基乙酰胺;NMP:N-甲基吡咯烷酮;DMSO:二甲基亚峰;THF:四氢呋喃;Chloroform:氯仿。
由表2可见,由实施例1-5所制备的聚合物中因为化学交联的存在,可以发现这类聚合物在常用溶剂中均表现出良好的耐溶剂型。
Claims (5)
1.一种三重交联高性能聚合物,其特征在于:所述聚合物通过双环氧单体、交联单体和功能单体固化交联制得,且所述聚合物含有由共价键和两种不同强度的多层次氢键形成的交联网络,所述共价键与两种所述氢键的作用强度呈梯度递减,所述功能单体之间、和所述功能单体与所述双环氧单体之间可形成不同强度的多层次氢键,所述环氧单体与所述交联单体之间、所述双环氧单体与所述功能单体之间可形成共价键,所述双环氧单体为双酚A环氧树脂、双酚F环氧树脂中任意一种,所述交联单体为乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、1,6- 己二胺、甲基环戊二胺、间苯二甲胺、异佛尔酮二胺、以及2-甲基戊二胺中任意一种,所述功能单体为5-氨基-1H-苯并***。
2.一种如权利要求1所述的三重交联高性能聚合物的制备方法,其特征在于:该方法的工艺步骤和条件如下:
(1)将双环氧单体、交联单体和功能单体混合后溶于适量的溶剂中,搅拌均匀得到混合溶液;
(2)将步骤(1)所得的混合溶液过滤后浇铸在干净的平板玻璃上,并在60-180°C和0-450托的条件下固化3-12小时。
3.根据权利要求2所述的一种三重交联高性能聚合物的制备方法,其特征在于:所述步骤(1)中的双环氧单体、交联单体和功能单体摩尔比为10:2.5-4.5:1-5。
4.根据权利要求3所述的一种三重交联高性能聚合物的制备方法,其特征在于:所述步骤(1)中的双环氧单体、交联单体和功能单体摩尔比为10:3:4。
5.根据权利要求2所述的一种三重交联高性能聚合物的制备方法,其特征在于:所述步骤(1)中所用溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜、1,4-二氧六环、对二甲苯、间二甲苯或乙腈中的任意一种。
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