【作者】 邢铁玲；

【导师】 陈国强；

【作者基本信息】 苏州大学 ， 纺织化学与染整工程， 2009， 博士

【摘要】 本文提出在水介质中采用活性聚合—原子转移自由基聚合(ATRP)法接枝改性真丝,探讨了丙烯酸酯系单体ATRP接枝真丝的反应性及反应条件,并研究接枝真丝的结构与性能,获得具有较好抗菌及抗皱性的真丝。采用2-溴异丁酰溴(BriB-Br)为引发剂,4-二甲氨基吡啶(DMAP)为催化剂,三乙胺(TEA)为缚酸剂,制备了大分子真丝引发剂。探讨了反应条件对真丝大分子引发剂上活性基团Br含量的影响,确定了较佳的制备真丝大分子引发剂的条件。在较佳反应条件下得到的真丝大分子引发剂上溴的相对含量采用能谱法测定在1(Wt%)左右,氧焰燃烧离子色谱法测得的绝对含量在0.032(Wt%)左右;X-射线光电子能谱(XPS)测试表明,Br以共价键方式固定到了真丝织物的表面,成功制备了真丝大分子引发剂。采用甲基丙烯酸二甲氨基乙酯(DMAEMA)、甲基丙烯酸二乙氨基乙酯(DEAEMA)和丙烯酸二甲氨基乙酯(DMAEA)三种含氮丙烯酸酯单体对真丝进行接枝改性,比较了三种单体常规化学引发及ATRP接枝真丝的反应性,发现三种含氮丙烯酸酯单体对真丝的ATRP接枝均比常规接枝反应更易发生,具有更好的接枝效果。从而为某些不适宜用常规化学引发方法接枝真丝的单体开辟了新的可行方法,奠定了部分研究基础。探讨了单体浓度、催化剂和配体的用量及比例、反应温度、反应时间等因素对三种含氮丙烯酸酯单体ATRP接枝真丝的影响,获得了较佳的接枝反应条件。经确证,本文中ATRP接枝具有活性聚合的特征,且真丝ATRP法接枝DMAEMA单体后,可二次引发继续接枝甲基丙烯酰氧乙基二甲基磷酸酯这一具有阻燃功能的单体,从而获得多功能的真丝材料。采用甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟乙酯(HEA)和丙烯酸羟丙酯(HPA)三种含羟基丙烯酸酯单体,对真丝进行接枝改性,比较了三种单体常规化学引发及ATRP接枝真丝的反应性,发现三种含羟基丙烯酸酯单体对真丝ATRP接枝的反应性要差于其常规引发接枝共聚的反应性。对三种单体水介质中ATRP接枝真丝的反应条件进行了探讨,获得了较佳的反应条件。通过对真丝织物ATRP接枝前后的红外光谱及拉曼光谱分析,表明单体已经被接枝到真丝织物上,接枝后的真丝,仍然主要呈β-折叠构象;通过X-射线衍射分析可知,接枝主要发生在真丝纤维的无定形区,而不是晶区;接枝真丝织物的X-射线光电子能谱分析表明,单体已接枝到织物上;从扫描电镜及原子力显微镜图像可得出,随接枝率增加,真丝织物的表面粗糙度增加,但织物表面仍较为平滑、均一。真丝ATRP接枝后的差热分析结果表明,随着接枝率的增加,单体接枝后真丝的热稳定性也随之提高;接枝真丝均随着接枝率的增加,回潮率基本没有变化,白度略有下降,真丝织物的断裂强力亦稍有下降,织物的手感及透气性有所下降,但下降幅度不大,不影响真丝织物的服用及其它功能。三种含氮丙烯酸酯单体接枝真丝季铵化后的定量分析抗菌效果为:DEAEMA单体接枝真丝的抗菌性能最好,DMAEMA接枝真丝次之,DMAEA接枝的稍差,即随着接枝单体季铵盐烷基链长的增加,抗菌性增加;三种单体接枝真丝对金葡球菌的抑菌性能均要好于大肠杆菌;三种含氮丙烯酸酯单体接枝真丝的抗菌效果具有很好的耐久性。三种含羟基单体接枝真丝的干、湿折皱回复性都有所提高,其中湿折皱回复性能提高显著,且随着接枝率的增加,湿折皱恢复性能也提高。更多还原

【Abstract】 In order to improve the properties of silk, silk was grafted using living polymerization, atom transfer radical polymerization(ATRP), in aqueous medium. The reactivity and reaction conditions of acrylate monomers were discussed in silk grafting. The structure and properties of grafted silk were studied and silk with good bacteria repellancy and crease resistance was obtained.Silk macroinitiator was prepared using 2-bromoisobutyryl bromide (BriB-Br) as initiator, 4-dimethylamino-pyridine(DMAP) as catalyst, and triethylamine(TEA) as acid-binding agent. The effects reaction conditions on Br content of silk macroinitiator were discussed and the optimal reaction condition was obtained. Br content of silk macroinitiator measured by energy spectrum was 1 (Wt%),and quantitatively measured by ion chromatography after oxygen flask combustion was measured was 0.032(Wt%). X-ray photoelectron spectroscopy(XPS) indicated that Br was introduced onto the surface of silk by covalent bond and silk macroinitiator was successfully prepared.Silk fabrics were grafted using dimethylaminoethyl methacrylate (DMAEMA), diethylaminoethyl methacrylate (DEAEMA) and dimethylaminoethyl acrylate (DMAEA) as monomers. The reactivity of the three monomers was compared in silk grafting using conventional chemical initiation and ATRP methods. It was found that the three monomers were much easier to be grafted onto silk by ATRP method than by conventional chemical initiation method, and better grafting result could be obtained using ATRP method. Accordingly, a new feasible method was developed for those monomers not suitable for silk grafting by conventional chemical initiation method, and some research bases were established.The effects of monomer concentration, dosage and ratio of catalyst and ligand, reaction temperature and time on silk grafting using three nitrogen containing monomers were discussed and optimum grafting reaction conditions were obtained. It was confirmed that the ATRP grafting displayed“living”characteristics. DMAEMA grafted silk by ATRP method could be re-grafted by a monomer, dimethyl methacryloyloxyethyl phosphate, with flame retardant property. Thus, silk with multi-function could be developed via ATRP method.Silk fabrics were grafted using hydroxyethyl methacrylate(HEMA), hydroxyethyl acrylate(HEA) and hydroxypropyl methacrylate(HPMA) as monomers. The reactivities of the three monomers were compared in silk grafting using conventional chemical initiation and ATRP methods. It was found that the three monomers were much easier to be grafted onto silk by conventional chemical initiation method than by ATRP method. The grafting techniques of the three monomers were discussed and the optimum grafting conditions were obtained.Attenuated total reflectance-Fourier transform infrared spectroscopy(ATR-FTIR) and Raman spectra of grafted silk by ATRP method indicated that the monomers were grafted onto silk fabrics, and the grafted silk still mainly appearedβ-sheet conformation. X-ray diffraction of grafted silk showed that the grafting mainly occurred at amorphous region of silk not crystalline region. XPS of grafted silk indicated that monomers were grafted onto silk fabrics. It could be observed from images of scanning electron microscope(SEM) and atomic force microscope(AFM) that the surface roughness of silk fabric increased with the grafting yields increasing, however, the silk surfaces were still smooth and even.The DSC result showed that the thermal stability of grafted silk increased with the grafting yields increasing. The moisture regain of grafted silk almost didn’t change, whiteness, breaking strength, handle and air permeability of grafted silk slightly decreased, which didn’t affect the wearability and other properties.The bacteria repellancy quantitative analysis result of quaternized silk grafted by three nitrogen containing acrylate monomers wasobtained. The bacteria repellency of DEAEMA grafted silk was the best, the followed was DMAEMA grafted silk, and the worst was DMAEA grafted silk. The bacteria repellency of silk increased with the increase of alkyl chain length of quaternary ammonium monomers. The bacterial inhibition of three monomer grafted silk to S. aureus was better than to E. coli. And the bacteria repellency of three nitrogen containing acrylate monomers grafted silk had good washing durability.The dry and wet crease recovery of three hydroxyl containing monomers grafted silk was both improved, and the wet crease recovery was improved significantly. The wet crease recovery of grafted silk increased with the increase of grafting yields.更多还原