Mechanism of Chrome-free Tanning with Tetra-hydroxymethyl Phosphonium Chloride  被引量:10

Mechanism of Chrome-free Tanning with Tetra-hydroxymethyl Phosphonium Chloride

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作  者:邵双喜 史楷岐 蒋岚 马淳安 

机构地区:[1]Institute of Applied Chemistry, Ningbo University of Technology, Ningbo 315016, China [2]Zhejiang University of Technology, Hangzhou 310014, China

出  处:《Chinese Journal of Chemical Engineering》2008年第3期446-450,共5页中国化学工程学报(英文版)

基  金:the National Basic Research Program (2007CB616909);Startup Foundation of Applied Chemistry of the Key Discipline of Zhejiang University of Technology and Zhejiang Provincial Science and Technology Plan (2006C21107)

摘  要:Tetra-hydroxymethyl phosphonium chloride (THPC) has been considered as an important chrome-free tanning agent. To understand the THPC tanning mechanism, the structure, charge distribution, activity and tanning ability of each phosphorous compound in THPC tanning system were studied, by ^31p NMR, FT-IR spectroscopy, differential scanning calorimetry (DSC) and computational chemistry method, etc. When pH raised to 6.0, the decomposition of THPC would take place, which results in a production of free formaldehyde, tri-hydroxymethyl phosphonium (TrHP) and tri-hydroxymethyl phosphine oxide (TrHPO). At pH 9.0, THPC will be converted completely to TrHP and most TrHP is further oxidized into TrHPO. It is possible that, in reaction of phosphorous compounds and collagens, both P-C and C-O bonds would break simultaneously or individually. From molecular charge distribution and bond polar properties, it is deduced that, if P-C bonds break, the activity is in order of TrHPO 〉 THPC 〉 TrHE whereas if C--O bonds break, the order is TrHP 〉 THPC 〉 TrHPO. It is more possible that P--C bonds will break in reaction with collagen, and TrHPO may be more active in the THPC tanning system. The results of tanning and DSC also prove the above conclusion. Furthermore, the fact that the shrinkage temperature of THPC tanned leather was below 70℃ when basified to pH 5.0 or lower suggests that the hydroxymethyl groups of THPC and TrHP are less possible to combine directly with amino groups of collagen.Tetra-hydroxymethyl 磷根氯化物(THPC ) 被看作了一个重要没有铬的晒黑代理人。为了理解在晒黑系统的 THPC 晒黑机制,结构,电荷分布,活动和每磷化合物的晒黑的能力的 THPC ,被学习,由^( 31 ) P NMR ,英尺红外光谱学,微分扫描热量测定( DSC )和计算化学方法, etc.When 最适PH 涨了到 6.0 , THPC 的分解将发生,它导致免费甲醛, tri-hydroxymethyl 磷根( TrHP )和 tri-hydroxymethyl 氧膦( TrHPO )的生产。在最适 PH 9.0, THPC 将完全被变换成 TrHP 和大多数 TrHP 进一步被氧化进 TrHPO.It 是可能的在磷化合物和骨胶原的反应, PC 和公司契约将同时或个别地碎。从分子的电荷分布和契约polar 性质,如果 PC 契约碎,这项活动是有序的,这被推出 TrHP>THPC>TrHP 而如果公司契约碎,顺序是, TrHP>THPC>TrHPO.It 是更可能的 PC 契约将与骨胶原在反应碎,并且 TrHPO 可能在晒黑系统的 THPC 是更活跃的。晒黑和 DSC 的结果也证明上述结论。而且,当时, THPC 的收缩温度晒黑皮革的事实在 70 ° C 下面 basified 到最适 PH 5.0 或更低建议 THPC 和 TrHP 的 hydroxymethyl 组是可能的更少与骨胶原的氨基的组直接结合。

关 键 词:tetra-hydroxymethyl phosphonium chloride chrome-free tannage green chemicals charge distribution tanning mechanism 

分 类 号:O6[理学—化学]

 

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