聚合温度对聚磷酸钙聚合度及结构的影响

doi:10.3724/SP.J.1077.2012.00174

无机材料学报 ›› 2012, Vol. 27 ›› Issue (2): 174-178.DOI: 10.3724/SP.J.1077.2012.00174 CSTR: 32189.14.SP.J.1077.2012.00174

聚合温度对聚磷酸钙聚合度及结构的影响

吴航^1,2, 张丽芳¹, 白威¹, 马驰^1,2, 熊成东¹

(1. 中国科学院成都有机化学研究所, 成都610041; 2. 中国科学院研究生院, 北京100049)

收稿日期:2011-02-28 修回日期:2011-04-26 出版日期:2012-02-10 网络出版日期:2012-01-05
作者简介:吴航(1983-), 男, 博士研究生. E-mail: whjob2010@yahoo.cn
基金资助:
中国科学院“西部之光”基金 West Light Foundation of the Chinese Academy of Sciences

Effect of Polymerization Temperature on Polymerization Degree and Structure of Calcium Polyphosphate

WU Hang^{1, 2}, ZHANG Li-Fang¹, BAI Wei¹, MA Chi^{1, 2}, XIONG Cheng-Dong¹

(1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China; 2. Graduated University of the Chinese Academy of Sciences, Beijing 100049, China)

Received:2011-02-28 Revised:2011-04-26 Published:2012-02-10 Online:2012-01-05
About author:WU Hang. E-mail: whjob2010@yahoo.cn

摘要/Abstract

摘要：

聚合度作为一个重要影响因素对聚磷酸钙的性能必然产生影响. 采用磷酸二氢钙作为原料, 在不同聚合温度下制备了聚磷酸钙. 采用³¹P核磁共振波谱测定聚磷酸钙的聚合度, 评价聚合温度对聚合度及结构的影响, 结合磷酸二氢钙差示扫描量热-热失重分析结果, 提出了磷酸二氢钙缩聚反应的机理. 结果表明, 磷酸二氢钙缩聚产物以聚磷酸钙为主, 当聚合温度低于1000℃时, 升高聚合温度有利于聚合度的增大, 1000℃以上则反之; 此外, 升高聚合温度促进环状结构(偏磷酸钙)的生成, 其含量随聚合温度的升高而增大且1000℃以上增幅较大.

关键词: 生物陶瓷, 聚磷酸钙(CPP), 聚合度, 聚合温度

Abstract:

The properties of calcium polyphosphate (CPP) were greatly affected by its polymerization degree. A series of CPP with different polymerization degree were prepared by polymerization of calcium phosphate monobasic monohydrate (MCP) at different temperatures. Polymerization degree was analyzed by liquid state ³¹P nuclear magnetic resonance (³¹P-NMR). The effect of different temperature on polymerization degree and structure of CPP was discussed. MCP was analyzed by differential scanning calorimetry-thermmogravimetry (DSC-TGA) and possible mechanism of the polymerization reaction was proposed. The results show that polymerization of MCP mainly produces CPP. When the elevation temperature is below 1000℃, polymerization degree increases; however the opposite is true when the polymerization temperature exceeds 1000℃. Additionally, the formation of a ring-structure phosphate, namely calcium metaphosphate (CMP), is also promoted with increasing polymerization temperature. The CMP content increases with increasing polymerization temperature and significantly increases when the polymerization temperature is above 1000℃.

Key words: bioceramic, calcium polyphosphate (CPP), polymerization degree, polymerization temperature

中图分类号:

O613

吴航, 张丽芳, 白威, 马驰, 熊成东. 聚合温度对聚磷酸钙聚合度及结构的影响[J]. 无机材料学报, 2012, 27(2): 174-178.

WU Hang, ZHANG Li-Fang, BAI Wei, MA Chi, XIONG Cheng-Dong. Effect of Polymerization Temperature on Polymerization Degree and Structure of Calcium Polyphosphate[J]. Journal of Inorganic Materials, 2012, 27(2): 174-178.

图/表 7

图1 制备聚磷酸钙的反应

Fig. 1 Reaction for forming calcium polyphosphate

图2 聚磷酸钙的31P-NMR图谱

Fig. 2 31P-NMR spectra of calcium polyphosphate

图3 温度对聚磷酸钙聚合度的影响

Fig. 3 Effect of temperature on polymerization degree of calcium polyphosphate

图4 温度对聚磷酸钙中偏磷酸钙含量的影响

Fig. 4 Effect of temperature on calcium metaphosphate content in the calcium polyphosphate

图5 1200℃下制备的聚磷酸钙的31P核磁共振图谱

Fig. 5 31P-NMR spectra of calcium polyphosphate prepared at 1200℃

图6 磷酸二氢钙的DSC-TGA曲线(10 ℃/min)

Fig. 6 The DSC-TGA curves of calcium phosphate monobasic monohydrate (10 ℃/min)

图7 磷酸二氢钙缩聚的机理

Fig. 7 Mechanism of polymerization of calcium phosphate monobasic monohydrate

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聚合温度对聚磷酸钙聚合度及结构的影响

Effect of Polymerization Temperature on Polymerization Degree and Structure of Calcium Polyphosphate

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