有机酸蒙囿铝（Ⅲ）配合物特性及与胶原反应性的研究
摘要
应用pH滴定、反滴定以及Ferron计时比色法，从平衡态和动力学的角度，系统研究了有机酸蒙囿铝(Ⅲ)配合物溶液在有机酸盐种类和用量、铝盐种类、pH值及陈放时间等因素不同时，溶液中铝(Ⅲ)配合物的耐碱性、配聚性、酸降解性、存在形态及组份分布状况。通过GFC及LPIC等手段，分析了有机酸盐的种类和用量、铝盐的种类、pH值等因素不同时，溶液中铝(Ⅲ)配离子的大小及分布变化、有机酸根离子参与配位的情况，以及不同GFC分离流份中Al~(3+)与参与配位的有机酸根离子浓度比值的变化规律。在此基础上，通过GFC分离制备及IR、~(27)Al NMR、XRD等方法，进一步研究了有机酸蒙囿铝(Ⅲ)配合物溶液的组成及组份结构，并通过皮粉鞣制实验考察了pH值、有机酸的用量等因素不同时，以及不同GFC分离流份中的铝(Ⅲ)配合物与皮胶原的反应特性。主要结论有：
(1)有机酸蒙囿铝(Ⅲ)配合物在溶液中主要有3种存在形态，它们在8hs左右基本达到动态平衡，即：单核铝(Ⅲ)配离子2-4核低聚配离子“Al_(13)族”配离子。
(2)在与实际铝鞣相近的溶液环境中，铝(Ⅲ)配离子主要以“Al_(13)族”多核离子的形态存在，这是一类由N个(N大约在9～30范围内)八面体铝(Ⅲ)配离子围绕1个[AlO_4]~(5-)四面体配离子，通过共用1个或2个氧配原子而形成的具有刚性结构的球状离子团，随Al~(3+)数目的不同，其直径约在8～16范围内变化。
(3)在有机酸蒙囿的铝(Ⅲ)配合物溶液中，参与配位的有机酸根离子只占加入量的少部分或极少部分，这与溶液中铝(Ⅲ)的主要存在形态——“Al_(13)族”配离子特殊的结构密切相关。溶液中铝(Ⅲ)配离子的存在形态及组成分布主要受pH值的影响，且在pH=3～4之间有一突变点。有机酸根离子的作用主要在于它们参与配位后，能一定程度上阻止鞣液中“Al_(13)族”配离子在pH值升高时进一步配聚，而在低pH值条件下又更易降解。
(4)有机酸蒙囿的铝(Ⅲ)配合物与胶原的反应性既具有金属鞣革配合物的通性，又具有其自身的特点。这也是由于铝(Ⅲ)配合物在溶液中的主要存在方式—“Al_(13)族”多核配离子的特性决定的。了解了鞣液中铝(Ⅲ)配合物的存在形态及组成分布在各种不同溶液条件下的变化规律之后，就不仅可以对铝(Ⅲ)配合物与胶原反应过程中的各种实验结果作出比较合理的解释，而且为进一步研究铝鞣及铝结合鞣的机理奠定了基础。
From the aspects of equilibrium state and dynamics, pH potential titration,anti - potential titration and Ferron time - analysis were applied to research the characteristics of organic acid masked aluminum complexes solutions systematically, including alkli - resistence, poly - coordination , acid - decomposition, exsisting states and composition distributions, when the solution conditions such as the kinds of organic acid salts and their dose, kinds of aluminum salts,pH value of solutions and storage time were varied.
Gel filter chromatography (GFC) and low pressure ion chromatography (LPIC) were applied to analyze the changing laws of aluminum complexes' size, composition distribution and the coordination of organic acid anions with Al3+ nucleus, varying with the solution conditions such as kinds of organic acid salts and their dose, kinds of aluminum salts and pH values; the changing laws of the ratio between the concentrations of aluminum(Ⅲ) and organic acid anions binding with A13+ necleus in different GFC fractions were studied also. Moreover, GFC preparation method and IR,27Al NMR,XRD were used to research the composition distributions and the structures of organic acid masked aluminum complexes in solutions, and the reaction properties of complexes to collagen with different tanning pH values,different dose of organic acid salts and different GFC fractions. The main conclusions were:
(1) Organic acid masked aluminum complexes were active complexes which existed in three different states in solutions and could reach equilibrium state within 8 hours or so, i. e.:
mono - nuclear complexes ---- 2 - 4 nucleus polymeric complexes ----"Al13 like" complexes
(2) In the solution conditions similar to aluminum tanning practice, the main exsisting state of aluminum complexes was "Al13 like" complexes, which had a stiff sphere structure constructed by one [AlO4]5- tetrahedron arrounded with N(N≈9
- 30) octahedral aluminum complexes by means of "mono - oxygen - bridge" or "di - oxygen - bridge". Their diameters were 8 - 16A or so.
(3) In organic acid masked aluminum complexes solutions, most or almost of the adding organic acid anions were in "free" state and did not coordinate with A13 + necleus. This result was closely related to the special structure of "Al13 like" complexes. The existing states and composition distributions of aluminum complexes were mainly influenced by pH values of the solutions. The test results indicated that there was a mutation point between pH = 3 - 4. The masking function of coordinating organic acid anions mainly lay on their preventing "Al13 like" complexes to further polymerize with other aluminum(Ⅲ) complexes when the pH value rised, and the "Al13 like" complexes could be easily decomposed in lower pH value solutions, i. e. , the coordinating organic acid anions endow the "Al13 like" complexes with the property of "alkli - resistant and acid - senstive".
(4) The reaction property of organic acid masked aluminum (Ⅲ) complexes with collagen not only had the common feature of metal tanning complexes, but had its own characteristics also. This was determined by the characteristics of "Al13 like" complexes - the main exsisting state of aluminum (Ⅲ) complexes in solutions. Having known the changing laws of the exsisting states and composition distributions of aluminum complexes in different solution condutions, a rational explanation for many experiment results of aluminum tanning process could be given, a foundation for the mechanistic study of aluminum tanning and aluminum cooperating- tanning was laid also.
(1)有机酸蒙囿铝(Ⅲ)配合物在溶液中主要有3种存在形态，它们在8hs左右基本达到动态平衡，即：单核铝(Ⅲ)配离子2-4核低聚配离子“Al_(13)族”配离子。
(2)在与实际铝鞣相近的溶液环境中，铝(Ⅲ)配离子主要以“Al_(13)族”多核离子的形态存在，这是一类由N个(N大约在9～30范围内)八面体铝(Ⅲ)配离子围绕1个[AlO_4]~(5-)四面体配离子，通过共用1个或2个氧配原子而形成的具有刚性结构的球状离子团，随Al~(3+)数目的不同，其直径约在8～16范围内变化。
(3)在有机酸蒙囿的铝(Ⅲ)配合物溶液中，参与配位的有机酸根离子只占加入量的少部分或极少部分，这与溶液中铝(Ⅲ)的主要存在形态——“Al_(13)族”配离子特殊的结构密切相关。溶液中铝(Ⅲ)配离子的存在形态及组成分布主要受pH值的影响，且在pH=3～4之间有一突变点。有机酸根离子的作用主要在于它们参与配位后，能一定程度上阻止鞣液中“Al_(13)族”配离子在pH值升高时进一步配聚，而在低pH值条件下又更易降解。
(4)有机酸蒙囿的铝(Ⅲ)配合物与胶原的反应性既具有金属鞣革配合物的通性，又具有其自身的特点。这也是由于铝(Ⅲ)配合物在溶液中的主要存在方式—“Al_(13)族”多核配离子的特性决定的。了解了鞣液中铝(Ⅲ)配合物的存在形态及组成分布在各种不同溶液条件下的变化规律之后，就不仅可以对铝(Ⅲ)配合物与胶原反应过程中的各种实验结果作出比较合理的解释，而且为进一步研究铝鞣及铝结合鞣的机理奠定了基础。
From the aspects of equilibrium state and dynamics, pH potential titration,anti - potential titration and Ferron time - analysis were applied to research the characteristics of organic acid masked aluminum complexes solutions systematically, including alkli - resistence, poly - coordination , acid - decomposition, exsisting states and composition distributions, when the solution conditions such as the kinds of organic acid salts and their dose, kinds of aluminum salts,pH value of solutions and storage time were varied.
Gel filter chromatography (GFC) and low pressure ion chromatography (LPIC) were applied to analyze the changing laws of aluminum complexes' size, composition distribution and the coordination of organic acid anions with Al3+ nucleus, varying with the solution conditions such as kinds of organic acid salts and their dose, kinds of aluminum salts and pH values; the changing laws of the ratio between the concentrations of aluminum(Ⅲ) and organic acid anions binding with A13+ necleus in different GFC fractions were studied also. Moreover, GFC preparation method and IR,27Al NMR,XRD were used to research the composition distributions and the structures of organic acid masked aluminum complexes in solutions, and the reaction properties of complexes to collagen with different tanning pH values,different dose of organic acid salts and different GFC fractions. The main conclusions were:
(1) Organic acid masked aluminum complexes were active complexes which existed in three different states in solutions and could reach equilibrium state within 8 hours or so, i. e.:
mono - nuclear complexes ---- 2 - 4 nucleus polymeric complexes ----"Al13 like" complexes
(2) In the solution conditions similar to aluminum tanning practice, the main exsisting state of aluminum complexes was "Al13 like" complexes, which had a stiff sphere structure constructed by one [AlO4]5- tetrahedron arrounded with N(N≈9
- 30) octahedral aluminum complexes by means of "mono - oxygen - bridge" or "di - oxygen - bridge". Their diameters were 8 - 16A or so.
(3) In organic acid masked aluminum complexes solutions, most or almost of the adding organic acid anions were in "free" state and did not coordinate with A13 + necleus. This result was closely related to the special structure of "Al13 like" complexes. The existing states and composition distributions of aluminum complexes were mainly influenced by pH values of the solutions. The test results indicated that there was a mutation point between pH = 3 - 4. The masking function of coordinating organic acid anions mainly lay on their preventing "Al13 like" complexes to further polymerize with other aluminum(Ⅲ) complexes when the pH value rised, and the "Al13 like" complexes could be easily decomposed in lower pH value solutions, i. e. , the coordinating organic acid anions endow the "Al13 like" complexes with the property of "alkli - resistant and acid - senstive".
(4) The reaction property of organic acid masked aluminum (Ⅲ) complexes with collagen not only had the common feature of metal tanning complexes, but had its own characteristics also. This was determined by the characteristics of "Al13 like" complexes - the main exsisting state of aluminum (Ⅲ) complexes in solutions. Having known the changing laws of the exsisting states and composition distributions of aluminum complexes in different solution condutions, a rational explanation for many experiment results of aluminum tanning process could be given, a foundation for the mechanistic study of aluminum tanning and aluminum cooperating- tanning was laid also.
引文
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82 何先祺，陆傲霜，Cr-Zr-Al鞣液的组成研究(Ⅱ)．皮革科学与工程．1992，(2)：1～9．
83 单志华．水溶液中RE~(3+)与Al~(3+)异多核羟合物存在可能性的研究．皮革科学与工程1999，9(1)：9～11．
84 K.Takenouchi, K. Kondo, F. Nakamura. Composition of Complexes in Citrate Masked Aluminum Solutions and Their Affinity for Collagen. XXI Congress of the IULTCS. Philedelphia. USA. 1990.
85 E. Takata, Y. Maeda, T. Y. Zhang, et al. A Trial to Estimate the Reactivity of Masking Aluminum Complexes to Collagen by HPLC. 皮革科学(日). 1994, 39(4):259～263.
86 G.A. Webb. Annual Reports on NMR Spectroscopy. Volume 9. Norwich, Great Britain: 161～173.
87 R. W. Smith. The State of Al(Ⅲ) in Aqueous Solution and Adsorption of Hydrolysis Products on Al_2O_3. Ph. D. Thesis (Stanford Univ., Palo Alto, CA, 1969).
88 R. W. Smith, J. D. Hem. Effect of Aging on Aluminum Hydroxide Complexes in Dilute Aqueous Solutions. U. S. Geological Survey Water Supply paper. 1972, 1827-D.
89 D. A. Riesgraf, M. L. May. Infrared Spectra of Aluminum Hydroxide Chlorides. Applied Spectroscopy. 1978, 32(4): 362～366.
90 J.W. Akitt. ~(27)Al NMR Studies of the Hydrolysis and Polymerization of the Hexa- Aquo- Aluminum(Ⅲ)Cation. J. Chem. Soc. Dalton Trans. 1972:604.
91 J.W.Akitt, A. Farthing. Aluminum -~(27) NMR Studies of the Hydrolysis of Aluminum (Ⅲ), Part 2. 1981. J. Chem. Soc. Dalton Trans. 1981: 1606～1608.
92 R.E.Nelson. Enhanced Efficacy Actives for Aerosol Antiperspirant Products. Aerosol Age. October, 1985:26～29.
93 党淑琴．Al—ATP配合物的~(27)Al、~1H和~(31)P NMR研究．第四届全国波谱学学术会议论
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94 高剑新，翟纯，陆婉珍．~(27)Al NMR法研究羟基配位铝溶液。第四届全国波谱学学术会议论文集摘要．中国物理学会波谱专委会．昆明，1986：357～358．
95 姚重华，孙尧俊，赵丕裕．水中稀释对聚合氯化铝形态及分布的影响．环境化学．1991，10(2)：1～2．
96 姚重华，亚煦世，孙尧俊等．聚合氯化铝的~(27)Al NMR研究．环境科学学报．1989，9(1)：116～119．
97 T.Y.Zhang, Y. Ishii, K. Shirai et. al. Size- Exclusion Chromatography and the Determination of Combined Acid/Aluminum Ratio of the Fractions JALCA. 1996, 91:89 ～94.
98 T.Y.Zhang, E. Takata, K. Shirai. Evaluation of the Stability of Organic Acid - Masked Aluminum Complexes by Size. Exclusion Chromatography. JALCA. 1996, 91:95～99.
99 施良和著．凝胶色谱法．北京：科学出版社，1980：172．
100 张新申，将小萍．低压离子色谱在皮革化学中的应用．国际皮革科学技术会议论文集．中国·成都，1992：419～422．
101 成都科技大学．西北轻工业学院编．皮革分析检验．北京：轻工业出版社，1987，344～346．
102 俞从正译．含胶原物质的羟基脯氨酸的测定．皮革科技．1981，(9)：43～44．
103 吴宁生，蔡春平，李碧林．色谱峰面积的计算．分析化学．1990，18(3)：243～245．
104 胡恒亮，穆相牟著．X-射线衍射技术．北京：纺织工业出版社．1979：244．
105 四川大学，华西医科大学等编．现代仪器分析与测试(下册)．成都：四川科学技术出版社．1987：478～510，
106 [美]L．鲍林著．卢嘉锡、黄耀曾、曾广植等译校．化学键的本质．中国：上海科学技术出版社．1984：504．
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52 E. Heidemann. The Foundmentals of Leather Manufacturing. Eduard Roether KG, 1993.
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54 成都科技大学，西北轻工业学院编．制革化学及工艺学(上册)．北京：轻工业出版社，1987：213．
55 张铭让，用络合物化学的价键理论解释Cr~(3+)，Zr~(4+)，Al~(3+)，Ti~(4+)，Fe~(3+)，稀土等络合物鞣剂的鞣性差异．中国皮革学报，1984，3(1)：23～33．
56 张铭让．用配位场理论解释Cr~(3+)，Zr~(4+)，Al~(3+)，Ti~(4+)，Fe~(3+)稀土等络合物鞣剂的鞣性差异．中国皮革学报，1984，3(2)：19～28．
57 张铭让，陈武勇编．鞣制化学(上册)．北京科学出版社，1999．
58 陈智．过渡元素化学．北京：原子能出版社，1986：266．
59 彭必雨，何先祺．钛鞣剂、钛鞣法及鞣革机理的研究(Ⅰ)．中国皮革，1999，28(13)：7～10．
60 戴安邦著．配位化学．北京：科学出版社，1987．
61 [美]D．吉伯斯著，祝振鑫等译．溶液中的金属离子．北京：原子能出版社，1978：271～292．
62 A.D.Covington, R. A. Hancock, I. A. Ioannidis. Mechanistic Studies of Mineral Tanning- part Ⅰ. JSLTC. 1989, 73(1): 1～8.
63 A.D.Covington, G. S. Lampard, R. A. Hancock. Studies on the Origin of Hydrothermal Stability: A New Theory of Tanning. JALCA. 1998, 93:107～120.
64 单志华，何先祺．结合鞣机理研究——多支撑框架稳定结构。第四届亚洲国际皮革科学技术会议论文集．北京：1998：86～88．
65 N.P.Slabert. Chrominum (Ⅲ) Complexes Which Constituents Chrominum Sulfate Tanning Solutions. Proeeding of the XIV Congress of the IULCTS, VolⅠ. 1975:240.
66 K. Takenouehi. Composition of Complexes in Glucose- Reduced Chrome Tanning Liquors and Their Affinity to Collagen.JALCA. 1980, 75:150～166.
67 K. Takenouchi. Stability of Complexes in Chromium Sulfate Solutions and Their Affinity for Collagen. JALCA. 1981, 76:343～359.
68 K. Takenouchi. Stability of Complexes Separated From Masked Chromium Chloride Solutions, 皮革化学(日). 1986:32(3):133～143.
69 K. Takenouchi, K. Kondo, F. Nakamura. Changes in the Chromium Complex Composition Affinity of Various Complexes for Collagen. JSLTC. 1991, 75(6):190～196.
70 李国英，程劲，张铭让．硫酸铬鞣液组成的研究，中国皮革．1992，21(10)：8～19．
71 李国英，程劲，张铭让．氯化铬鞣液组成的研究．中国皮革．1993，22(2)：18～24．
72 李国英，程劲，张铭让．硝酸铬鞣液组成的研究．中国皮革．1993，22(5)：18～23．
73 李国英，程劲，张铭让．高氯酸铬鞣液组成的研究．中国皮革．1993，22(9)：17～23．
74 王秀荣，张铭让，有机酸铬鞣液组成与鞣革性质．中国皮革．1996，25(9)：4～13．
75 成都科技大学．西北轻工业学院编．制革化学及工艺学(上册)，北京轻工业出版社，1987：251．
76 H.P. Cermann. Chrome Tannage from the Viewpoint of Ecology. JSLTC.1995,79(3):82～85.
77 王远亮．软硬酸碱理论与皮革化学的研究．国际皮革科学技术会议论文集．中国·成都，1992：314～318．
78 张铭让，蒋维祺，李志强．溶液中Cr-Zr-Al异金属多核铬合物形成的研究(Ⅰ)．皮革科技．1981，(5)：1～19．
79 张铭让，蒋维祺，李志强．溶液中Cr-Zr-Al异金属多核铬合物形成的研究(Ⅱ)．皮革科技．1981，(6)：1～13．
80 何先祺，郭祖龄，用GFC分离Al-Zr鞣液．皮革科学与工程，1991，(2)：1～9．
81 何先祺，陆傲霜。Cr-Zr-Al鞣液的组成研究(Ⅰ)．皮革科学与工程．1992，(1)：1～12．
82 何先祺，陆傲霜，Cr-Zr-Al鞣液的组成研究(Ⅱ)．皮革科学与工程．1992，(2)：1～9．
83 单志华．水溶液中RE~(3+)与Al~(3+)异多核羟合物存在可能性的研究．皮革科学与工程1999，9(1)：9～11．
84 K.Takenouchi, K. Kondo, F. Nakamura. Composition of Complexes in Citrate Masked Aluminum Solutions and Their Affinity for Collagen. XXI Congress of the IULTCS. Philedelphia. USA. 1990.
85 E. Takata, Y. Maeda, T. Y. Zhang, et al. A Trial to Estimate the Reactivity of Masking Aluminum Complexes to Collagen by HPLC. 皮革科学(日). 1994, 39(4):259～263.
86 G.A. Webb. Annual Reports on NMR Spectroscopy. Volume 9. Norwich, Great Britain: 161～173.
87 R. W. Smith. The State of Al(Ⅲ) in Aqueous Solution and Adsorption of Hydrolysis Products on Al_2O_3. Ph. D. Thesis (Stanford Univ., Palo Alto, CA, 1969).
88 R. W. Smith, J. D. Hem. Effect of Aging on Aluminum Hydroxide Complexes in Dilute Aqueous Solutions. U. S. Geological Survey Water Supply paper. 1972, 1827-D.
89 D. A. Riesgraf, M. L. May. Infrared Spectra of Aluminum Hydroxide Chlorides. Applied Spectroscopy. 1978, 32(4): 362～366.
90 J.W. Akitt. ~(27)Al NMR Studies of the Hydrolysis and Polymerization of the Hexa- Aquo- Aluminum(Ⅲ)Cation. J. Chem. Soc. Dalton Trans. 1972:604.
91 J.W.Akitt, A. Farthing. Aluminum -~(27) NMR Studies of the Hydrolysis of Aluminum (Ⅲ), Part 2. 1981. J. Chem. Soc. Dalton Trans. 1981: 1606～1608.
92 R.E.Nelson. Enhanced Efficacy Actives for Aerosol Antiperspirant Products. Aerosol Age. October, 1985:26～29.
93 党淑琴．Al—ATP配合物的~(27)Al、~1H和~(31)P NMR研究．第四届全国波谱学学术会议论
文集摘要．中国物理学会波谱专委会．昆明，1986：281～282．
94 高剑新，翟纯，陆婉珍．~(27)Al NMR法研究羟基配位铝溶液。第四届全国波谱学学术会议论文集摘要．中国物理学会波谱专委会．昆明，1986：357～358．
95 姚重华，孙尧俊，赵丕裕．水中稀释对聚合氯化铝形态及分布的影响．环境化学．1991，10(2)：1～2．
96 姚重华，亚煦世，孙尧俊等．聚合氯化铝的~(27)Al NMR研究．环境科学学报．1989，9(1)：116～119．
97 T.Y.Zhang, Y. Ishii, K. Shirai et. al. Size- Exclusion Chromatography and the Determination of Combined Acid/Aluminum Ratio of the Fractions JALCA. 1996, 91:89 ～94.
98 T.Y.Zhang, E. Takata, K. Shirai. Evaluation of the Stability of Organic Acid - Masked Aluminum Complexes by Size. Exclusion Chromatography. JALCA. 1996, 91:95～99.
99 施良和著．凝胶色谱法．北京：科学出版社，1980：172．
100 张新申，将小萍．低压离子色谱在皮革化学中的应用．国际皮革科学技术会议论文集．中国·成都，1992：419～422．
101 成都科技大学．西北轻工业学院编．皮革分析检验．北京：轻工业出版社，1987，344～346．
102 俞从正译．含胶原物质的羟基脯氨酸的测定．皮革科技．1981，(9)：43～44．
103 吴宁生，蔡春平，李碧林．色谱峰面积的计算．分析化学．1990，18(3)：243～245．
104 胡恒亮，穆相牟著．X-射线衍射技术．北京：纺织工业出版社．1979：244．
105 四川大学，华西医科大学等编．现代仪器分析与测试(下册)．成都：四川科学技术出版社．1987：478～510，
106 [美]L．鲍林著．卢嘉锡、黄耀曾、曾广植等译校．化学键的本质．中国：上海科学技术出版社．1984：504．
107 J. W. Harlon, S. H. Feairheller. Chemistry of Crosslinking of Collagen during tanning. JALCA. 1979, 74:117～120.
108 李英，刘白玲．鞣制过程中胶原的交联化学(Ⅰ)．皮革科技．1981，(5)：20～22．
109 李英，刘白玲．鞣制过程中胶原的交联化学(Ⅱ)．皮革科技．1981，(6)：14～19．
110 M.Komanowsky. Thermodynamic Analysis of Thermal Denaturation of Hide and Leather. JALCA. 1992, 87:52～67.