【作者】 高党鸽；

【导师】 马建中；

【作者基本信息】 陕西科技大学 ， 皮革化学与工程， 2009， 博士

【摘要】 二烯丙基二烷基季铵盐是一种含有两个不饱和双键的阳离子型季铵盐有机分子,具有高效无毒、正电荷密度高等优点。目前,此类单体中二烯丙基二甲基季铵盐已工业化,其理论和应用研究居多,相比之下,其它季铵盐的研究相对较少。本研究以二烯丙基二甲基季铵盐单体为基础,合成了系列二烯丙基甲基烷基季铵盐（CCx）、二烯丙基双烷基季铵盐（CxCx）、二甲基双十六烷基季铵盐[2(CH₃C₁₆)]和烯丙基甲基双十二烷基季铵盐(SC₁₂C₁₂)等单体,其中x代表烷基数,分别为12、14、16、18;采用元素分析、核磁共振（NMR）、有机质谱（MASS）、傅里叶变换红外光谱（FT-IR）等手段对单体进行了表征。结果表明:制备了纯度较高的系列单体。利用合成的系列单体分别进行了改性蒙脱土研究,采用X-射线衍射（XRD）、热重分析（TGA）、FT-IR等方法对有机改性蒙脱土进行了表征。XRD结果表明:CCx、CxCx均能顺利进入蒙脱土层间,对蒙脱土进行改性;结合TGA结果表明:CCx、CxCx分别改性蒙脱土的层间距与TGA中有机物的分解量之间呈非线性关系,这可能是由于CCx、CxCx的部分链段仅仅是在蒙脱土片层周围,并没有完全进入蒙脱土片层中。FT-IR结果表明:采用CxCx、CCx分别改性蒙脱土后,有机蒙脱土表面对水的吸附能力相对于二烯丙基二甲基季铵盐改性蒙脱土明显降低,这是受有机物含量及有机物疏水性两方面影响;924cm^-1、2854cm^-1处烷基中C-H伸缩振动峰的强度变化与TGA中有机物含量变化基本一致。采用CCx与甲基丙烯酸在水体系中制备了pH响应性聚二烯丙基甲基烷基季铵盐-甲基丙烯酸（PCCx-MAA）凝胶,疏水链段CCx的存在能够影响凝胶的溶胀性能。溶胀动力学研究表明,疏水链段能够明显降低凝胶的溶胀率,这是由于疏水链段间的物理交联对聚合物链段的松弛有一定的抑制作用。在酸碱条件下,水在凝胶中的扩散系数不同,表明水在凝胶中的释放机理不同。采用二烯丙基十六烷基氯化铵(HC₁₆)和甲基丙烯酸制备聚二烯丙基十六烷基氯化铵.甲基丙烯酸(PHC₁₆-MAA)共聚凝胶,并与PCC₁₆-MAA共聚凝胶溶胀性能进行了对比,考察N⁺的存在对凝胶溶胀性能的影响。结果表明:N⁺离子间的静电斥力作用,使得共聚凝胶的溶胀度增加。DSC结果表明:PCC₁₆-MAA共聚凝胶易在侧链上发生结晶。凝胶的溶胀性能与凝胶的交联程度、羧酸根含量、N⁺离子含量、环境pH以及疏水链段含量等多个因素有关。通过单因素实验设计法分别对聚二烯丙基二甲基氯化铵（PDM）、聚二烯丙基二甲基氯化铵-丙烯酰胺（PDM-AM）、聚二烯丙基二甲基氯化铵-丙烯酰胺-乙二醛（PDM-AM-GL）的合成条件进行了研究;分别制备了系列蒙脱土含量的聚二烯丙基二甲基氯化铵/蒙脱土（PDM/MMT）、聚二烯丙基二甲基氯化铵-丙烯酰胺/蒙脱土（PDM-AM/MMT）、聚二烯丙基二甲基氯化铵-丙烯酰胺-乙二醛/蒙脱土（PDM-AM-GL/MMT）纳米复合材料;探索了蒙脱土用量对单体转化率、聚合物特性黏度和体系旋转黏度的影响。研究表明:随着MMT用量的增加,系列纳米复合材料中单体转化率、聚合物特性黏度和体系旋转黏度均呈先增加再减小的变化趋势;单体的转化率和聚合物的特性黏度与纳米复合材料中蒙脱土的层间距变化规律一致。蒙脱土的存在对PDM的分子质量具有一定的影响,对聚合物的五元环结构无影响。将制备的系列分子质量为～5500Mn、～6000Mn、～8500Mn和～20000Mn的PDM-AM分别直接插层蒙脱土,结果表明:提纯后聚合物能够顺利插层蒙脱土,聚合物中未反应单体的存在不利于聚合物大分子插层蒙脱土,聚合物是否进行质子化处理对其插层蒙脱土效果无明显影响;随着聚合物用量的增加,聚合物改性蒙脱土后蒙脱土的层间距呈非线性变化,这是由于疏水链段在蒙脱土层间聚集受限而引起,这一现象类似于表面活性剂的聚集。将制备的系列纳米复合材料分别配合2%铬粉应用于皮革鞣制,应用结果表明:PDM/MMT纳米复合材料配合2%铬粉对坯革的增强效果最明显,但对坯革透水汽性负面影响较大;使用PDM-AM/MMT纳米复合材料配合2%铬粉鞣制后坯革的各项性能均不如2%铬粉鞣制后的坯革;PDM-AM-GL/MMT纳米复合材料配合2%铬粉鞣制后,坯革的耐湿热稳定性、填充性均优于2%铬粉鞣制的坯革。本论文为二烯丙基二烷基季铵盐的工业化提供了基础,此类单体在pH响应性高分子和纳米复合材料中的研究开拓了该类单体的应用方向。更多还原

【Abstract】 Diallyldimethyl quaternary ammonium salt（DM） is a cationic organic molecule with double unsaturated bond.It has many advantages such as high efficiency,high density of positive charge,and so on.Thus it has been industrialization.However,other quaternary ammonium salt has not been extensive investigated.Based on DM,a series of diallyldialkyl ammonium bromide（CxCx）, diallylmethyl alkyl ammonium bromide（CCx）,dimethyldihexadecyl ammonium bromide[2(CH₃C₁₆)]and allylmethyldidodecyl ammonium bromide (SC₁₂C₁₂) were synthesized.Here,X is alkyl’s chain length,represents 12,14, 16 and 18 respectively.They were characterized by element analysis,nuclear magnetic resonance（NMR）,mass spectrometer（MASS） and fourier transform infrared spectrometry（FT-IR）.The results indicate that a series of purified monomer are obtained.The obtained monomers were used to modify montmorillonite（MMT）.The organically modified MMT were characterized by XRD,TGA,FT-IR and so on. The results of MMT modified by monomer show that monomer could intercalate into MMT’s layer.It is nonlinearity relationship between organic MMT’s layer distance in XRD and organic decompound weight in TGA.FT-IR results indicate that the water absorption on the surface of MMT is influenced by content and hydrophobic of organic.The peaks at 924 cm^-1 and 2854 cm^-1 from the C-H stretching vibration are changed consistent with the organic weight in TGA.Hydrophobic modified gel（PCCx-MAA） was prepared by using CCx and methacrylic acid（MAA） in water.Polymer diallylmethyl alkyl ammonium bromide-methacrylic acid(PHC₁₆-MAA) was prepared using diallylmethyl alkyl ammonium chloride and MAA.Contract to PCCx-MAA gel,the effect of N⁺ on gel’s swelling was studied.The results show that pH responsive behavior of PCCx-MAA is in line with polymer methacrylic acid（PMAA） gel.The equilibrium swellling time of PCC₁₆-MAA gel is more than polymer gel prepared using CC₁₂,CC₁₄ and CC₁₈ respectively.The swelling kinetics indicate that the hydrophobic alkyl chain units can slow down the swelling rate of the gels.Diffusion exponent of gels in acidic or alkaline media is controlled by content of hydrophobic chain.The crystallization capacity of PCC₁₆-MAA gels is easier than PHC₁₆-MAA in side-chain.This should be a consequence of PCC₁₆-MAA hydrogel consist of carboxylic acid,nitrogen positive ion and hydrophobic alkyl chain’s content.Polymer diallyldimethyl ammonium chloride（PDM）,polymer diallyldimethyl ammonium chloride -acrylamide（PDM-AM） and polymer diallyldimethyl ammonium chloride-acrylamide -glyoxal（PDM-AM-GL） were prepared via free radical polymerization respectively.Series of PDM/ montmorillonite nanocomposites（PDM/MMT）,PDM-AM/ montmorillonite nanocomposites（PDM-AM/MMT） and PDM-AM-GL/montmorillonite nanocomposites（PDM-AM-GL/MMT） were prepared respectively.The nanocomposites were studied by using monomer conversion,characteristic viscosity of the polymer and system rotational viscosity of nanocomposites respectively.The results of nanocomposites show that monomer conversion, polymer intrinsic viscosity and system rotational viscosity are consistent with the change of MMT’s layer distance.The effect of MMT’s dosage on cyclopolymerization of PDM was studied. The distance of MMT’s layer was measured by XRD.The monomer and polymer structure were characterized by FT-IR,proton and carbon-13 nuclear magnetic resonance as well as DEPT techniques.The structure of polymer dimethyldiallyl ammonium chloride separated from nanocomposites is still kept five-ring structure.The molecular weight of PDM separated from PDM/MMT is influenced by dosage of MMT.Series of molecular weight of PDM-AM was prepared.The MMT was modified by purified,unpurified and protonized PDM-AM respectively,and measured by XRD.The results of MMT modified by PDM-AM indicate that purified polymer can intercalate into MMT’s layer.Unreaction monomer in polymer is not advantaged for polymer intercalation into MMT’s layer.It is not influenced MMT modified by protonized.It was not linearity relationship between organic MMT’s layer distance and dosage of MMT,which similar to assemble phenomena of surfactant.Nanocomposites with 2%chromate were applied in leather process. Application results show that PDM/MMT can increase leather tensile strength and tear strength,compared with 2%chromate tanned leather.The tannage effect of PDM-AM and PDM-AM/MMT on leather is not good.The properity of wetting stability and fillness tanned by PDM-AM-GL/MMT is better than leather tanned by 2%chromate.It is provided industrial foundation for diallyldialkyl quaternary ammonium salts.It is exploit a new research field for diallyldialkyl quaternary ammonium salts that study on pH responsive and nanocomposites.更多还原