CN108689394B - 一种纳米磷酸氢钙的制备方法 - Google Patents
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Abstract
本发明涉及一种纳米磷酸氢钙的制备方法。其制备步骤为先将磷酸酯、烷氧基钙、表面活性剂溶于多元醇和去离子水的混合溶剂中制成溶液,然后将该溶液加热至一定温度即可得到纳米磷酸氢钙。与传统的制备方法相比,本方法制得的产品粒径小且分布均匀,作为食品、饲料添加剂,医药载体更易于吸收,能有效提高磷、钙的利用率;作为骨水泥组成成分反应活性更高,可有效提高其强度。
Description
技术领域
本发明涉及一种纳米磷酸氢钙的制备方法。
背景技术
纳米磷酸氢钙可用作高效食品强化剂,饲料添加剂,塑料稳定剂及高强骨水泥的组成成分。目前,纳米磷酸氢钙的制备通常采用均相法或非均相法。均相法通常采用氯化钙、硝酸钙与磷酸钾、磷酸钠等可溶盐为原料,通过原料之间的复分解反应制备磷酸氢钙。如蔡玉荣等公开了一种以氯化钙或硝酸钙为钙源,以磷酸氢钠或磷酸氢二钠为磷源的纳米磷酸氢钙制备技术[蔡玉荣等.一种水热法制备磷酸氢钙纳米线的方法,公开号:CN105314613A]。非均相法通常以石灰和磷酸为反应原料,以表面活性剂为改性剂,在高沸点醇中制备纳米磷酸氢钙。如陈苏等公开了一种利用纳米氢氧化钙为钙源,以磷酸为磷源,以span-80、tritonX-100、聚乙二醇或tween-60为分散剂,在正戊醇、正己醇或环戊醇等溶剂中制备纳米磷酸氢钙的技术[陈苏等.一种纳米氢氧化钙粉体的制备方法,公开号:CN201410070557.2]。基于复分解原理的均相法往往会副产氯化钾、硝酸钾或氯化钠、硝酸钠等可溶盐,得到的产品还要进行洗涤脱盐处理。由于磷酸氢钙的低溶解性,非均相法在采用氢氧化钙作为反应物时容易造成其与磷酸的反应不完全的情况。
发明内容
本发明提供了一种纳米磷酸氢钙的制备方法,即先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照一定比例在常温下混合均匀后制成澄清溶液,然后将该溶液加热升温至一定温度即可得到纳米级的磷酸氢钙。
附图说明
图1为纳米磷酸氢钙的制备方法流程图
即:
1、先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照质量比1∶0.9~1.7∶0.003~ 0.06∶9.8~49.1∶0.3~1.1在常温下混合溶解后制成澄清溶液。
2、然后将该溶液加热升温至80-120℃即可得到纳米级磷酸氢钙。
有益效果:与基于复分解原理的均相制备方法相比,本发明所述制备方法不副产氯化钾、硝酸钾或氯化钠、硝酸钠等可溶盐,得到的产品不须洗涤脱盐处理。与以氢氧化钙为原料的非均相制备方法相比,本发明所述制备方法反应彻底,制备的纳米磷酸氢钙纯度高,在97%以上。本发明所述制备方法所用设备及工艺条件简单、能耗小,产品粒径分布窄,在50~ 160nm之间。
具体实施方式
下面结合具体实施例对本发明做一详细说明:
实施例1.将磷酸二甲酯、甲氧基钙、曲拉通-100、乙二醇和去离子水按照质量比1∶0.9∶0.003∶ 9.8∶0.3在常温下混合均匀后制成澄清溶液,然后将溶液加热升温至85℃即可得到磷酸氢钙沉淀。经离心分离后,利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙,粒度范围为120~160纳米,纯度97%,可用于饲料添加剂。
实施例2.将磷酸二乙酯、乙氧基钙、tween-60、乙二醇和去离子水按照质量比1∶0.8∶ 0.006∶11∶0.4在常温下混合均匀后制成澄清溶液,然后将溶液加热升温至95℃即可得到磷酸氢钙沉淀。经离心分离后,利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙,粒度范围为100~135纳米,纯度97.6%,可用做塑料稳定剂。
实施例3.将磷酸二苯酯、乙氧基钙、OP-10、丙二醇和去离子水按照质量比1∶0.7∶0.01∶12∶0.5在常温下混合均匀后制成澄清溶液,然后将溶液加热升温至115℃即可得到磷酸氢钙沉淀。经离心分离后,利用无水乙醇洗涤3次后即可得到白色粉末状纳米级磷酸氢钙,粒度范围为90~110纳米,纯度98%,可用于高强骨水泥的活性组分。
注:烷氧基钙可由金属钙和相应的无水醇溶剂在加热回流下反应制得(也可直接购置)。
Claims (4)
1.一种纳米磷酸氢钙的制备方法,其特征在于:先将磷酸酯、烷氧基钙、表面活性剂、多元醇和去离子水按照质量比1∶0.9~1.7∶0.003~0.06∶9.8~49.1∶0.3~1.1在常温下混合溶解后制成澄清溶液,然后将该溶液加热升温至85℃-120℃即可得到纳米磷酸氢钙,所述磷酸酯为磷酸二甲酯、磷酸二乙酯、磷酸二苯酯中的一种。
2.根据权利要求1所述的一种纳米磷酸氢钙的制备方法,其特征在于:所述烷氧基钙为甲氧基钙、乙氧基钙中的一种。
3.根据权利要求1所述的一种纳米磷酸氢钙的制备方法,其特征在于:所述表面活性剂为曲拉通-100,tween-60或OP-10中的一种。
4.根据权利要求1所述的一种纳米磷酸氢钙的制备方法,所述多元醇为乙二醇、丙二醇、丁二醇中的一种。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4431630A (en) * | 1981-05-08 | 1984-02-14 | Colgate-Palmolive Company | Dentifrice composition |
JP2783565B2 (ja) * | 1987-11-27 | 1998-08-06 | 株式会社神戸製鋼所 | 燐酸カルシウム化合物顆粒体およびその製造方法 |
CN1308017A (zh) * | 2001-02-27 | 2001-08-15 | 天津化工研究设计院 | 一种生产大颗粒结晶饲料级磷酸氢钙工艺的杂质屏蔽方法 |
CN104220649A (zh) * | 2012-04-09 | 2014-12-17 | 株式会社小糸制作所 | 磷灰石结晶 |
KR20160055253A (ko) * | 2013-09-12 | 2016-05-17 | 할로자임, 아이엔씨 | 변형된 항-상피세포 성장인자 수용체 항체 및 이의 사용 방법 |
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- 2017-09-15 CN CN201710912734.0A patent/CN108689394B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4431630A (en) * | 1981-05-08 | 1984-02-14 | Colgate-Palmolive Company | Dentifrice composition |
JP2783565B2 (ja) * | 1987-11-27 | 1998-08-06 | 株式会社神戸製鋼所 | 燐酸カルシウム化合物顆粒体およびその製造方法 |
CN1308017A (zh) * | 2001-02-27 | 2001-08-15 | 天津化工研究设计院 | 一种生产大颗粒结晶饲料级磷酸氢钙工艺的杂质屏蔽方法 |
CN104220649A (zh) * | 2012-04-09 | 2014-12-17 | 株式会社小糸制作所 | 磷灰石结晶 |
KR20160055253A (ko) * | 2013-09-12 | 2016-05-17 | 할로자임, 아이엔씨 | 변형된 항-상피세포 성장인자 수용체 항체 및 이의 사용 방법 |
Non-Patent Citations (1)
Title |
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Effect of phosphorus precursors on the structure of bioactive calcium;Katalin Sinkó et all.;《Materials Science and Engineering C》;20170106;第73卷;第767-777页 * |
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