鞣剂粒子尺寸、结构演变对胶原性能的影响及新型鞣革方法的构建

It is well known that tanning is the key process from skin to leather; the size scale and microstructure of tanning agent play an important role in process of leather manufacture and properties of resultant leather. In traditional leather-making, the processes for tanning agent preparation and tannage are independent, which results in the shortcoming including hard to penetration, low tanning efficiency and uneven characteristics for final leather. In order to solve this common technical problem, an organic or inorganic tanning agent precursor is introduced into the skin collagen fibers firstly, this precursor can, in-situ, produce metastable state tanning particles under particular triggering condition(such as hydrolysis, oxidation-reduction and polycondensate reaction etc), and these in-situ produced metastable state tanning particles will react chemically with collagen rapidly because of their high activity, as a result, the mechanical properties and hydrothermal stability of skin collagen will be greatly enhanced, finally skin becomes required leather. By means of investigation of introducing method of precursors, in-situ producing method of tanning agent particles, controlling method of particles size and structure together with the effect of the evolvement of size scale and structure of tanning particles on properties of skin collagen, a relationship among evolvement of particles size scale and microstructure of tanning agent，tanning efficiency and collagen properties will be achieved. Under the guidance of these results, a novel tanning method based on in-situ produced organic or inorganic tanning agent will be constructed, this method will be expected to solve the common technical problem mentioned above and eliminate traditional processes of pickling and tanning agent preparation, finally to yield the quantitative reduction of materials and process.

鞣制是生皮转变成革的关键，鞣剂的分子尺寸和结构对鞣革性能产生着至关重要的影响。针对传统鞣剂制备和鞣革过程独立完成使得鞣剂粒子尺寸和结构不易控制，导致鞣剂渗透难，鞣剂利用率低和鞣制均匀性难于控制的共性技术缺陷，本课题借鉴聚合物有机-无机原位（in-situ）复合原理，先将有机、无机等鞣剂前驱体等引入胶原纤维中，然后在适宜条件下诱发前驱体原位反应生成高活性亚稳态鞣剂粒子，利用亚稳态粒子与皮胶原的化学键合作用实现生皮的鞣制。研究鞣剂前驱体的引入方法，鞣剂粒子的原位生成方法，鞣剂粒子结构、尺寸控制方法及鞣剂粒子结构、尺寸演变对皮胶原性能的影响，获得不同鞣剂微观粒子尺寸、结构演变对皮胶原性能影响的一般规律，并在该理论指导下，构建鞣剂原位生成、原位鞣制的新型鞣革方法，从源头解决传统鞣剂难于渗透，鞣剂利用率低和鞣制均匀性难于控制的共性技术难题，减少鞣剂制备和浸酸等工艺过程，实现制革过程和材料使用的减量化

针对传统鞣剂制备和鞣革过程分开完成使得鞣剂粒子尺寸和结构不易调控，导致鞣剂渗透难，鞣剂利用率低和鞣制均匀性难于控制的共性技术缺陷，借鉴聚合物有机-无机原位（in-situ）复合原理，先将有机、无机等鞣剂前驱体引入胶原纤维中，然后在适宜条件下诱发前驱体原位反应生成高活性鞣剂粒子，利用高活性粒子和蛋白质的化学键合实现对生皮的鞣制。研究了铬鞣剂、胺基树脂鞣剂、纳米SiO2鞣剂前驱体的引入方法，三类鞣剂粒子的原位生成方法，以及三类鞣剂粒子结构、尺寸控制方法；研究了三类鞣剂粒子结构、尺寸演变对皮胶原性能的影响，获得了不同鞣剂粒子结构、尺寸演变对鞣制效率和皮胶原性能影响一般规律，并在该理论的指导下，分别构建了胺基树脂鞣剂、纳米SiO2鞣剂以及铬鞣剂粒子原位生成的新型有机鞣、纳米鞣以及铬鞣法和鞣革工艺。该新型鞣革方法解决了长期困扰制革行业的鞣剂难于渗透、鞣制效率低、鞣制的均匀性难于控制的共性技术难题；首次提出的高活性鞣剂粒子原位生成、原位鞣制的有机鞣、纳米鞣以及铬鞣法新型鞣革方法和鞣革工艺，丰富了鞣制化学及工艺学内容。该方法屏弃了传统的“削足适履”式的后工艺平衡模式，减少了制革过程的盲目性和不可控性，并省去了传统鞣剂制备和浸酸等过程，实现了制革过程和材料的减量化，通过研究，发表论文15篇（其中SCI、EI收录12篇），获得专利3项。