CN105669972B - 侧链型电活性聚酰胺、制备方法及其在防腐方面的应用 - Google Patents
侧链型电活性聚酰胺、制备方法及其在防腐方面的应用 Download PDFInfo
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Abstract
一种新型的以苯胺齐聚物作为侧链的电活性聚酰胺聚合物、制备方法及其在盐水条件下对钢铁材料的防腐应用,属于功能高分子材料领域。首先是双胺单体M和二酐单体N聚合得到侧链型电活性聚酰胺聚合物。然后将该聚合物配成适当浓度,涂覆在钢铁材料表面,将钢铁材料的其余部分用环氧乙烯密封绝缘,在盐水中测试其电化学阻抗以及极化曲线。该聚合物是由二酐和含有苯胺四聚体的双胺单体反应制备而成。该聚合物具有数量可控的侧链基团,通过引入苯胺链段来提升聚合物的防腐性能。在酸性溶液中具备较好的电化学活性,同时在金属防腐实验中,表现出优异的防腐性能,在防腐领域具有巨大的应用潜力。
Description
技术领域
本发明属于功能高分子材料领域,具体涉及一种新型的以苯胺齐聚物作为侧链的电活性聚酰胺聚合物、制备方法及其在盐水条件下对钢铁材料的防腐应用。
背景技术
导电聚合物因其良好的导电性、优异的电学性能在钢铁材料防腐蚀领域受到广泛关注,其中聚苯胺原料易得,合成简单,具有多样化的结构和特殊的掺杂机制,这些优点使其在电池隔膜、抗静电涂料和防腐涂料等领域中具有巨大的潜在应用。值得注意的是聚苯胺防腐涂料因其独特的防腐机理,突出的防腐性能等优点,完全可以取代传统的防腐涂料,解决有毒有害,污染环境和资源紧缺等严峻问题。但由于聚苯胺不溶不熔,可加工性差,使其应用受到很大限制。苯胺齐聚物作为聚苯胺模型化合物,由于其分子结构规整,溶解性以及加工性好等优点引起众多研究者的兴趣,将苯胺齐聚物作为功能单元引入到高分子结构中制备电活性高分子材料已成为目前研究的热点。
本发明旨在合成一种含有苯胺链段的侧链型电活性聚酰胺聚合物,解决聚苯胺溶解性加工性差等问题,并对该聚合物在盐水条件下对钢铁材料的防腐性质进行研究。
发明内容
本发明提供了侧链型电活性聚酰胺的制备方法以及其在盐水条件下对钢铁材料的防腐应用。
本发明所述的侧链型电活性聚酰胺,其结构式如下所示:
其中,
为
n为正整数,表示聚合度;x、y、z为0到1之间的任意数字,且x+y+z=1。
首先是利用还原态母体苯胺四聚体和二氟苯甲酰氯反应得到含有苯胺链段的双氟单体F(该单体的合成、表征等内容详见中国专利:201010293748.7,侧链型电活性聚芳醚聚合物及其制备方法),然后将双氟单体F和4-氨基苯酚反应制备双胺单体M(该单体的合成、表征等内容详见中国专利:201410010359.7,侧链型电活性聚脲聚合物、制备方法及其在防腐方面的应用)。再利用双胺单体M和二酐单体N聚合得到侧链型电活性聚酰胺聚合物。将该聚合物配成适当浓度,涂覆在钢铁材料表面,将钢铁材料的其余部分用环氧乙烯密封绝缘,在盐水中测试其电化学阻抗以及极化曲线。
本发明所述的侧链型电活性聚酰胺聚合物的制备方法,其步骤如下:
(1)将无水的双胺单体M(结构式如(Ⅱ)所示)、二酐单体N(结构式如(Ⅲ)所示)等当量加入到有机溶剂(例如:N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基酰胺或二甲基亚砜)中,反应体系固含量为10~20%,氮气保护下搅拌反应8~10h小时;
(2)在0~5℃条件下向步骤(1)得到的溶液中缓缓滴加4-二甲氨基吡啶(DMAP)(结构式如(Ⅴ)所示)溶液得到混合溶液1,DMAP的加入量为步骤(1)得到的聚合物中羧基摩尔量的1.05~1.1倍;待混合溶液1恢复到室温后,将苯胺四聚体(结构式如(Ⅳ)所示)溶液和二环己基碳二亚胺(DCC)(结构式如(Ⅵ)所示)溶液组成的混合溶液2缓缓滴入混合溶液1中,苯胺四聚体的用量为步骤(1)中得到的聚合物中羧基摩尔量的0~1倍,DCC的摩尔用量为DMAP摩尔量的0.1~0.13倍,氮气保护下室温反应8~10h;用于溶解4-二甲氨基吡啶(DMAP)、苯胺四聚体和DCC的有机溶剂与步骤(1)使用的有机溶剂相同;(注:若所加入的苯胺四聚体的量为0,则此步骤可省略。)
将步骤(2)所得混合物倾倒入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3~4次,用无水乙醇洗涤2~3次,再用二氯甲烷洗涤1~2次(注:若所加入的苯胺四聚体的量为0,则可以不用二氯甲烷洗涤),将洗涤产物在40~50℃、真空条件下干燥24~30h,得到结构式如(Ⅰ)所示的侧链型电活性聚酰胺聚合物。
双胺单体M的结构式:
二酐单体N结构式:
N1:
N2:
N3:
苯胺四聚体结构式:
4-二甲氨基吡啶结构式:
二环己基碳二亚胺的结构式:
本发明所涉及的金属防腐测试方法如下:
本发明中测试所用钢铁材料以T301钢为例。
首先将本发明所制备的侧链型电活性聚酰胺聚合物于N,N’-二甲基乙酰胺中配制成质量分数为20%的溶液,将表面磨光的1cm×2cm T301钢片在甲苯、丙酮、蒸馏水、无水乙醇中分别超声清洗2次,置于烘箱中干燥;然后将配置好的聚酰胺溶液涂在铁片上,控制涂膜面积为1cm×1cm,膜厚分别为10μm、20μm、40μm、60μm、80μm左右,将钢片背面及四周边缘用环氧乙烯密封,使其除涂膜位置全部绝缘,这样就成功制备出了聚酰胺/T301钢电极。以质量分数为3.5%的氯化钠溶液作为测试溶液,以聚酰胺/T301钢电极为工作电极,铂丝为对电极,Ag/AgCl为参比电极的三电极体系作为测试条件进行防腐测试。
附图说明
图1:本发明合成的聚酰胺聚合物的红外谱图;
图2:本发明合成的聚酰胺聚合物的核磁谱图;
图3:本发明合成的聚酰胺聚合物的热失重曲线;
图4:本发明合成的聚酰胺聚合物的紫外氧化监控上升曲线谱图;
图5:本发明合成的聚酰胺聚合物的紫外氧化监控下降曲线谱图;
图6:本发明合成的聚酰胺聚合物在不同扫描速度下的循环伏安曲线;
图7:本发明合成的聚酰胺聚合物x=1,y=z=0的塔菲尔曲线测试谱图;
图8:本发明合成的聚酰胺聚合物x=1,y=z=0的电化学阻抗测试谱图;
图9:本发明合成的聚酰胺聚合物0<x<1,0<y<1,0<z<1的塔菲尔曲线测试谱图;
图10:本发明合成的聚酰胺聚合物0<x<1,0<y<1,0<z<1的电化学阻抗测试谱图;
图11:本发明合成的聚酰胺聚合物x=y=0,z=1的塔菲尔曲线测试谱图;
图12:本发明合成的聚酰胺聚合物x=y=0,z=1的电化学阻抗测试谱图;
图1~图6、图11、图12结果来自于实施例3,图7、图8结果来自于实施例1、图9、图10结果来自于实施例2。
图1、图2为双胺单体M与二酐单体N1制备的聚酰胺聚合物(x=y=1)的红外光谱图与氢谱核磁图,红外光谱图中,3444cm-1为N-H的伸缩振动峰;1643cm-1是羰基的振动吸收峰;1509cm-1和1565cm-1为苯环上碳碳键的振动吸收峰;1311cm-1为C-N的伸缩振动峰;1232cm-1为C-O的伸缩振动峰;819cm-1、750cm-1、676cm-1为苯环上指纹区的变形振动吸收峰。1H NMR(d6-DMSO)归属:δ=10.53-10.19(s,5H,-CO-NH-),δ=7.46-7.73(d,-NH-),δ=7.50-6.41(m,Ar-H)。
如图3所示,为双胺单体M与二酐单体N1制备的聚酰胺聚合物在空气中的热失重曲线,从热失重曲线可以看出,聚合物开始热分解的温度在210℃,失重10%的温度为485℃。
如图4、图5所示,为双胺单体M与二酐单体N1制备的聚酰胺聚合物的紫外氧化监控谱图,还原态(LEB)的聚合物在340nm处出现了一个吸收峰,这由苯环上的π-π跃迁引起的,随着氧化的进行,聚合物中出现了醌式结构,在580nm处出现一个新的吸收峰,这是由苯环和醌环之间的激子跃迁引起的,随着氧化的进行,苯环的吸收峰逐渐降低,而由醌式结构引起的吸收峰逐渐升高,当激子跃迁的峰强达到最大时,说明聚合物中的苯胺链段已处于中间氧化态(EB),聚合物继续氧化后,所有的吸收峰强度逐渐下降,并且发生一定程度的红移,最终吸收峰消失,表明聚合物中的苯胺链段已经变为最高氧化态(PNB)。
如图6所示,为双胺单体M与二酐单体N1制备的聚酰胺聚合物在不同扫速下的循环伏安图,扫速分别为10mV/s、20mV/s、30mV/s、40mV/s、50mV/s、60mV/s、70mV/s、80mV/s、90mV/s和100mV/s。图中显示聚合物有二对氧化还原峰,分别对应着聚合物的三种氧化还原状态,即还原态、中间氧化态和最高氧化态。插图中可以看出循环伏安曲线的峰电流与扫速成线性关系,说明此电化学过程是表面控制过程。
如图7所示,为双胺单体M与二酐单体N1制备的聚酰胺聚合物(x=1,y=z=0)的极化曲线谱图,从左向右依次为T301钢片,涂覆10μm厚聚酰胺薄膜的T301钢片,涂覆20μm厚聚酰胺薄膜的T301钢片,涂覆40μm厚聚酰胺薄膜的T301钢片,的极化曲线图,平衡电压依次为-0.610V,-0.396V,-0.142V,0.161V,腐蚀电流为6.085x10-6A,3.606x10-7A,2.429x10-7A,1.326x10-8A,可以看出,随着涂膜厚度的增加,T301钢片的平衡电压增大,腐蚀电流减小且变化明显。证明了聚合物的存在较好的防腐作用。
如图8所示,为双胺单体M与二酐单体N1制备的聚酰胺(x=1,y=z=0)聚合物的电化学阻抗谱图,T301钢片的阻抗为17742Ω,涂覆10μm厚聚酰胺薄膜的T301钢片的阻抗为18752Ω,涂覆20μm厚聚酰胺薄膜的T301钢片的阻抗为47329Ω,涂覆40μm厚聚酰胺薄膜的T301钢片的阻抗为150975Ω,随着涂膜厚度的增大,阻抗值明显增大,涂覆40μm膜厚的铁片阻抗值为T301钢片的8.5倍,证明了聚合物具有良好的防腐效果。
如图9所示,为双胺单体M与二酐单体N1制备的聚酰胺(0<x<1,0<y<1,0<z<1)聚合物的极化曲线谱图,从左向右依次为T301钢片,涂覆10μm厚聚酰胺薄膜的T301钢片,涂覆20μm厚聚酰胺薄膜的T301钢片,涂覆40μm厚聚酰胺薄膜的T301钢片的极化曲线图,平衡电压依次为-0.610V,-0.114V,-0.001V,0.188V,腐蚀电流为6.085x10-6A,1.689x10-7A,1.679x10-7A,1.196x10-7A,可以看出,随着涂膜厚度的增加,T301钢片的平衡电压增大,腐蚀电流减小且变化明显。证明了聚合物的存在较好的防腐作用。
如图10所示,为双胺单体M与二酐单体N1制备的聚酰胺(0<x<1,0<y<1,0<z<1)聚合物的电化学阻抗谱图,T301钢片的阻抗为17742Ω,涂覆10μm厚聚酰胺薄膜的T301钢片的阻抗为82721Ω,涂覆20μm厚聚酰胺薄膜的T301钢片的阻抗为107439Ω,涂覆40μm厚聚酰胺薄膜的T301钢片的阻抗为212662Ω,随着涂膜厚度的增大,阻抗值明显增大,涂覆40μm膜厚的铁片阻抗值为T301钢片的12倍,证明了聚合物具有良好的防腐效果。
如图11所示,为双胺单体M与二酐单体N1制备的聚酰胺(x=y=0,z=1)聚合物的极化曲线谱图,从左向右依次为T301钢片,涂覆10μm厚聚酰胺薄膜的T301钢片,涂覆20μm厚聚酰胺薄膜的T301钢片,涂覆40μm厚聚酰胺薄膜的T301钢片,平衡电压依次为-0.610V,0.036V,0.233V,0.407V,腐蚀电流为6.085x10-6A,1.686x10-7A,1.024x10-7A,5.033x10-8A,可以看出,随着涂膜厚度的增加,T301钢片的平衡电压增大,腐蚀电流减小且变化明显。证明了聚合物的存在较好的防腐作用。
如图12所示,为双胺单体M与二酐单体N1制备的聚酰胺(x=y=0,z=1)聚合物的电化学阻抗谱图,T301钢片的阻抗为17742Ω,涂覆10μm厚聚酰胺薄膜的T301钢片的阻抗为155657Ω,涂覆20μm厚聚酰胺薄膜的T301钢片的阻抗为361505Ω,涂覆40μm厚聚酰胺薄膜的T301钢片的阻抗为684423Ω,随着涂膜厚度的增大,阻抗值明显增大,涂覆80μm膜厚的铁片阻抗值为T301钢片的39倍,证明了聚合物具有良好的防腐效果。
以上数据证实了采用本发明所述方法成功的制备了目标产物,并证实其具有和聚苯胺相似的电化学活性,其防腐性能随着苯胺四聚体含量的增多而得到提高,在盐水中具备较好的金属防腐效果。
具体实施方式
实施例1
将双胺单体M 6.8428g、二酐单体N1(3,3’,4,4’-二苯醚四酸二酐(ODPA))3.1001g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应9小时,将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,再用无水乙醇洗涤产物2次,将产物在40℃的真空烘箱中干燥24h,得到聚酰胺聚合物C1,产率为92%。
实施例2
将双胺单体M 6.8428g、二酐单体N1(3,3’,4,4’-二苯醚四酸二酐(ODPA))3.1001g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取3.662g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C2,产率为91%。
实施例3
将双胺单体M 6.8428g、二酐单体N1(3,3’,4,4’-二苯醚四酸二酐(ODPA))3.1001g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取7.324g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C3,产率为90%。
实施例4
将双胺单体M 6.8428g、二酐单体N2(3,3’,4,4’-联苯四酸二酐(s-BPDA))2.9402g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应9小时,将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,再用无水乙醇洗涤产物2次,将产物在40℃的真空烘箱中干燥24h,得到聚酰胺聚合物C4,产率为91%。
实施例5
将双胺单体M 6.8428g、二酐单体N2(3,3’,4,4’-联苯四酸二酐(s-BPDA))2.9402g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时,后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取3.662g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C5,产率为89%。
实施例6
将双胺单体M 6.8428g、二酐单体N2(3,3’,4,4’-联苯四酸二酐(s-BPDA))2.9402g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时,后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取7.324g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C6,产率为87%。
实施例7
将双胺单体M 6.8428g、二酐单体N3(3,3’,4,4’-二苯酮四酸二酐(BTDA))3.2201g加入到50gDMAc中,注意所有原料全部无水,氮气保护下搅拌反应9小时,将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,再用无水乙醇洗涤产物2次,将产物在40℃的真空烘箱中干燥24h,得到聚酰胺聚合物C7,产率为90%。
实施例8
将双胺单体M 6.8428g、二酐单体N3(3,3’,4,4’-二苯酮四酸二酐(BTDA))3.2201g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时,后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取3.662g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C68产率为87%。
实施例9
将双胺单体M 6.8428g、二酐单体N3(3,3’,4,4’-二苯酮四酸二酐(BTDA))3.2201g加入到50g DMAc中,注意所有原料全部无水,氮气保护下搅拌反应6小时,后放入冰水浴中,称取120mg DMAP溶于0.6g DMAC中,将此溶液缓慢滴加到反应瓶中,保持温度在0℃;滴加完毕后撤掉冰水浴使反应体系恢复室温,另取7.324g苯胺四聚体和2.4g DCC溶于48g DMAC中,将此溶液缓缓滴加到反应瓶中,氮气保护下室温反应9h。将混合物倾入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3次,用无水乙醇洗涤2次,再用二氯甲烷洗涤产物2次,将产物在40℃真空干燥24h,得到聚酰胺聚合物C8,产率为88%。
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Claims (5)
1.一种侧链型电活性聚酰胺聚合物,其结构式如下所示:
其中,
为
n为正整数,n表示聚合度,x、y、z为0到1之间的任意值,且x+y+z=1。
2.权利要求1所述的侧链型电活性聚酰胺聚合物的制备方法,其步骤如下:
(1)将无水的双胺单体M、二酐单体N等当量加入到有机溶剂中,反应体系固含量为10~20%,氮气保护下搅拌反应8~10h小时;
(2)将步骤(1)所得混合物倾倒入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3~4次,用无水乙醇洗涤2~3次,将洗涤产物在40~50℃、真空条件下干燥24~30h,得到结构式如(Ⅰ)所示的侧链型电活性聚酰胺聚合物;
或,
(1)将无水的双胺单体M、二酐单体N等当量加入到有机溶剂中,反应体系固含量为10~20%,氮气保护下搅拌反应8~10h小时;
(2)在0~5℃条件下向步骤(1)得到的溶液中缓缓滴加4-二甲氨基吡啶DMAP溶液得到混合溶液1,DMAP的加入量为步骤(1)得到的聚合物中羧基摩尔量的1.05~1.1倍;待混合溶液1恢复到室温后,将苯胺四聚体溶液和二环己基碳二亚胺DCC溶液组成的混合溶液2缓缓滴入混合溶液1中,苯胺四聚体的用量为步骤(1)中得到的聚合物中羧基摩尔量的0.1~1倍,DCC的摩尔用量为DMAP摩尔量的0.1~0.13倍,氮气保护下室温反应8~10h;用于溶解4-二甲氨基吡啶DMAP、苯胺四聚体和DCC的有机溶剂与步骤(1)使用的有机溶剂相同;
(3)将步骤(2)所得混合物倾倒入蒸馏水中,搅拌析出沉淀后,用蒸馏水洗涤沉淀3~4次,用无水乙醇洗涤2~3次,再用二氯甲烷洗涤1~2次,将洗涤产物在40~50℃、真空条件下干燥24~30h,得到结构式如(Ⅰ)所示的侧链型电活性聚酰胺聚合物;
其中,双胺单体M的结构式
二酐单体N结构式
苯胺四聚体结构式:
4-二甲氨基吡啶结构式
二环己基碳二亚胺的结构式
3.如权利要求2所述的侧链型电活性聚酰胺聚合物的制备方法,其特征在于:有机溶剂为N-甲基吡咯烷酮、N,N-二甲基乙酰胺或二甲基亚砜。
4.权利要求1所述的侧链型电活性聚酰胺聚合物在防腐方面的应用。
5.如权利要求4所述的侧链型电活性聚酰胺聚合物在防腐方面的应用,其特征在于:是在盐水条件下对钢铁材料的防腐应用。
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