中文论文文摘

    丙烯酸类聚合物鞣剂是一类广泛使用的复鞣剂，能够赋予皮革多种特性，而且吸尽率高，鞣制后的废液无毒易处理，对于减少甚至避免传统复鞣工艺中铬鞣剂的使用，更合理地利用有限的铬资源，减少制革过程中的铬污染都具有积极的意义。弹性是皮革的重要物理机械性能，在皮革制品的加工、使用过程中具有极大的作用与意义，但是皮革弹性的表征至今仍然依靠感官评判，没有非常明确的评价指标，关于提高皮革弹性的丙烯酸类聚合物鞣剂的研究也鲜见报道。
   在皮革性能表征方面，本论文建立了皮革弹性的表征方法；在合成方面，以丙烯酸（AA）为主单体，分别以甲基丙烯酸(MAA)、醋酸乙烯酯(VAc)、丙烯酸甲酯(MA)、丙烯酸乙酯（EA）、丙烯酸丁酯(BA)、丙烯酰胺(AM)、丙烯酸羟乙酯（HEA）、亚甲基丁二酸(IA)为共单体制备了不同系列的丙烯酸类复鞣剂，考察了共单体用量及种类对皮革弹性及其它物理机械性能的影响；选出三种共单体优化了其细化用量，讨论了复鞣革样的杨氏模量与共聚物粘度的关系，采用X射线衍射(XRD)考察了共单体对聚合物结晶度的影响；考察了引发剂用量对共聚物黏度、结晶度及复鞣革样杨氏模量的影响；采用傅立叶红外光谱（FT-IR）、示差扫描量热（DSC）对应用效果较好的共聚物进行了结构表征；通过正交试验优化了该共聚物用于蓝湿革复鞣的工艺条件，并将该共聚物与铬粉、RST复鞣剂进行了复鞣应用对比，对革样进行了扫描电镜(SEM)观察；在此基础上合成了三元聚合物及四元聚合物，优化了引入的单体的用量，并对筛选得到的三种共聚物进行了FT-IR、XRD及凝胶渗透色谱（GPC）表征，将其进行了工厂应用试验对比并对革样进行了扫描电镜观察。
    结果表明：拉伸曲线上弹性形变范围内的杨氏模量可以作为考察革样物理机械性能的单独物理量，并用来表征皮革弹性；不同丙烯酸类共单体用量对革样弹性的影响不同：除MA外，MAA、VAc、EA、BA、AM、HEA、IA的少量引入均使其与丙烯酸的共聚物比丙烯酸均聚物复鞣革样的杨氏模量降低，皮革的弹性提高；一定用量的叔碳氢被甲基取代的单体（MAA、IA）的加入可以使革样的杨氏模量降低，用量过大杨氏模量升高；其它单体的加入使其对应革样的杨氏模量均随着共单体用量的增加而增大；软性共单体对皮革的弹性贡献较大，硬性单体相对较小；不同丙烯酸类共单体的加入及用量对革样其它物理机械性能的影响也有一定的规律性变化。
    EA、BA、VAc与AA共聚用作复鞣剂的最优用量（占单体总物质的量的比例）分别为：EA用量9%、BA用量2%、VAc用量7.5%；与AA均聚物相比，共单体EA、BA、VAc的加入使聚合物分子链更加柔软，聚合物的结晶度有一定程度的下降；对于共单体（EA、BA、VAc）不同用量的共聚物，其黏度越大，对应革样的杨氏模量越小；固定共单体用量，共聚物的黏度随引发剂用量的增加而降低，对应共聚物的结晶度越大；BA用量为单体总物质的量的2%，引发剂用量为单体总质量的10%时制备的AA/BA共聚物为两种单体的共聚物，其复鞣革样的弹性在二元共聚物中最好；AA/BA共聚物用作山羊蓝湿革复鞣的最佳应用条件为：共聚物用量为蓝湿革质量的1.5%（以固含量计），时间30min，复鞣温度30℃，m(水):m(蓝湿革)=1:1；AA/BA共聚物用于山羊蓝湿革复鞣对革纤维分散作用明显。
    多元共聚物的应用结果表明，在二元共聚物基础上将VAc、EA引入三元共聚物的合成中，其较优用量（占单体总物质的量的比例）分别为0.5%、8%，其中AA/BA/EA共聚物应用效果相对较好；在三元共聚物基础上将HEA、VAc引入四元共聚物的合成中，其较优用量（占单体总物质的量的比例）分别为5%、5%，第四元单体的引入使聚合物结晶度进一步降低。AA/BA/EA共聚物、AA/BA/EA/HEA共聚物、AA/BA/EA/VAc共聚物分子量较大，分子量分布较宽，工厂对比应用试验表明：AA/BA/EA/HEA共聚物、AA/BA/EA/VAc共聚物复鞣革样比R556复鞣革样弹性更好，比R83稍差。扫描电镜观察表明三个样品对纤维分散作用明显。

外文论文文摘

    Retanning is critical to attaining the required physical properties for leather products, during which acrylic polymers are commonly used.  Acrylic polymer retanning agents have proliferated worldwide because they are products with low cost but high performance.  Besides, it can reduce the dosage of chrome in leather process, which is of little quantity on the earth and can cause severe pollution.  Elasticity is an important property of leather products.  There is a lack of information, however, regarding performance of acrylic polymer retanning agents in terms of elasticity of the resultant leather.  Nor is much known regarding effective methods to measure the elasticity.  Most of the researchers dealing with acrylic retanning agents concerned on the preparation of a new polymer which endow leather with a special property.  But few of them studied the effect of different acrylic monomers and its dosage on leather properties, especially on elasticity.
    The way to measure leather elasticity was discussed.  Different acrylic polymer retanning agents were synthesized with acrylic acid as the primary monomer and eight other acrylate monomers (MAA-methyl acrylic acid, EA-ethyl acrylate, BA- butyl acrylate, VAc-vinyl acetate, MA-methyl acrylate, AM-acrylamide, IA-Itaconic acid, HEA- 2-Hydroxyethyl acrylate) as co-monomers.  The eight copolymers were applied in the retanning process separately and elasticity and other properties of the resultant leather was determined.  Three comonomers were selected from eight of them and their dosage was discussed.  XRD analysis was occupied to explain the crystallinity of copolymers.  The effect of dosage of initiator on viscosity, crystallinity and Young’s modulus of resultant leather.  FT-IR and DSC analysis were occupied to explain the structure of the selected copolymer.  The factors in retanning process were determined by orthogonal tests.  The polymer was compared with chrome tannage and RST retanning agent, and TEM was introduced to scan the resultant leather.  Copolymers containing three or four monomers were synthesised and the dosage of copolymer was discussed and they were characterized by FT-IR, DSC and XRD.  Three samples were selected was they were used in a plant; the resultant leather was also scanned under SEM.
The results showed that leather elasticity could be tested by calculating Young’s modulus of the elastic deformation, which was a variable region on the load-displacement curve, and Young’s modulus of the elastic deformation could serve as an independent parameter in characterizing leather’s physical properties.  The relation between the elasticity and the dosage of copolymer was determined, and it revealed that every co-monomer had an optimum dosage at which level the resultant leather showed the lowest Young’s modulus.  Then the effects of the eight co-monomers on leather elasticity were compared under the same condition.  It showed that the soft co-monomers, BA and EA, contributed more in leather elasticity than other selected co-monomers.  It also showed some orderliness on other leather properties. 
    The dosage of these three were analysed and the results showed that they revealed best elasticity when the dosage was 9%, 2%, 7.5%.  XRD analysis showed that the crystallinity reduced with the introduction of the comonomers.  The higher viscosity the copolymers had, the lower Young’s modulus the resultant leather would be when the ration of base monomer and comonomer was changed.  The higher dosage of initiator, the higher crystallinity the copolymer had, while the viscosity was lower.  The results showed the best application result occurred when the dosage of BA and initiator were 2% and 10% respectively.  The higher dosage of initiator, the higher crystallinity the copolymer had, while the viscosity was lower.  FTIR and DSC analysis showed the polymer was a copolymer of two monomers and its best application dosage, time, liquid ratio, temperature was 1.5%, 30min, 1:1, 30℃. The comparision revealed the copolymer had a similar effect in leather elasticity with the other two. The TEM showed the fiber bundles processed by the copolymer was dispersed sufficiently.
    The optimum dosage of VAc and EA was 0.5% and 8% respectively when Copolymers containing three monomers were synthesised and the AA/BA/EA polymers showed a better result.  HEA and VAc were introduced into further study and the proper dosage was 5% and 5% respectively.  AA/BA/EA polymer, AA/BA/EA/HEA polymer, AA/BA/EA/VAc polymer samples were used in a plant and the last to showed better effect than R556, while they showed no better than R83.  THE SEM showed the fibers were scattered thoroughly.