CN101479282B - 一种含有n-烷基硫代磷酸三胺的组分及其用途 - Google Patents
一种含有n-烷基硫代磷酸三胺的组分及其用途 Download PDFInfo
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Abstract
本发明目的是制备一种含N-烷基硫代磷酸三胺溶液的溶剂体系，这种溶剂体系为包含了一个或多个通式(I)的乙二醇醚。其中R1是氢或甲基，R2为C1-C5烷基，C3-C5异烷基，C4-C6叔烷基的组分中的其中之一，n＝2-4，并且，可以进一步任意地选择辅助添加物质来提高溶液的稳定性和应用性。本发明进一步目的是包含N-烷基硫代磷酸三胺的组分，该组分含有至少一种N-烷基硫代磷酸三胺和本发明的溶剂体系；还有该含有N-烷基硫代磷酸三胺的组分的用途。
Description
技术领域
本发明涉及一种含有N-烷基硫代磷酸三胺的组分(composition)以及其用途。
背景技术
在农业上，广泛将尿素作为氮肥使用，占到它在全球总消费量的46％。然而，当尿素施用于土壤之后，其部分水解成氨气和二氧化碳。由某些细菌和真菌产生的脲酶可以催化这一过程。由水解反应产生的气体产物(氨气和二氧化碳)挥发到大气中，因此施用在土地上的氮大量的流失了。
通过同时使用脲酶抑制剂和尿素，该水解过程可以被相当程度地减缓。在所有的脲酶抑制剂中最有效的是美国专利号4,530,714中揭示的硫代磷酸三胺化合物，尤其是正丁基硫代磷酸三胺(N-(n-butyl)thiophosphoric triamide)(NBPT)。实验已经验证了NBPT的效用，目前该化合物已经可以产业化的应用于农业领域了。(沃森，C.J.(2005)Proc.国际的(Internat).肥料(Fertiliser)Soc.454，1-38)。
工业级别的正丁基硫代磷酸三胺(NBPT)是一种固体、蜡白色的化合物，它会因为温度的升高和湿气的作用而分解，由于它的浓度，将其直接应用在尿素颗粒上是非常困难的。在技术上使用溶于适当溶剂中的NBPT溶液更具有优势。这种溶剂需要满足一些基本的要求：高的溶解度，NBPT在溶剂中的稳定性高，在低温下防止NBPT溶液晶化，浓缩的NBPT溶液具有低黏度，低毒性，挥发性和易燃性，溶剂可以从市场上直接购买且水含量低，成本低。
在美国专利号5,698,003中描述了正丁基硫代磷酸三胺(NBPT)和脂肪族二醇和脂肪族三醇或他们的酯类。表明：正丁基硫代磷酸三胺(NBPT)的含量可以高达50wt.％，较佳地为20-30wt.％。这些混合物适宜于注入颗粒状的尿素，但是只有在15℃以上时这些混合物才是液体的。在15℃以下的情况下，这些混合物会凝固或者晶化。这个不理想的性质给在生产期间对溶液的使用和其在尿素颗粒上的应用带来了麻烦，特别是在一年中最冷的那段时间，那时温度可能会下降到0℃以下。美国专利号5,698,003中介绍了一种称为“液体酰胺”的添加剂(例如10wt.％N-甲基吡咯烷酮)。将这种添加剂添加到这些溶剂中能够将凝结温度下调至0℃。但这种“液体酰胺”是对人体有害的(N-甲基吡咯烷酮通常被归类为致癌、致畸的成分)，并且通过这种方法获得的较低的凝结温度对于在低温或冰点温度下的使用仍然是不够的。
对于市场上能买到的二醇和三醇，另一个受关注的地方是产品质量和吸湿性。它们通常包含百分之零点几的水分，并且由于溶剂的吸湿性，在储存期间水分的含量会进一步提高。在长期储存中NBPT降解的主要原因是，在较长的储存期间，水的存在会使正丁基硫代磷酸三胺(NBPT)分解成失活组分。例如，众所周知，NBPT由于水解而有不稳定的特性，因此NBPT很少被用在湿润的土壤上。
根据我们的这项发明制备得到的溶剂体系可以解决以上所述的缺点。
本发明的目的是提供一种含正丁基硫代磷酸三胺的组分，该组分包含正丁基硫代磷酸三胺和包含了一个或多个如通式I的化合物的溶剂体系
其中R1是氢或甲基，R2是C1-C6烷基，n＝2-4。
N-烷基硫代磷酸三胺的烷基基团选自具有1至8个碳原子的线性或枝状烷基链和具有3至8个碳原子的环烷基链组成的群。
如通式1所示的化合物，较佳地，可以为二乙二醇甲醚，二丙二醇甲醚，三乙二醇甲醚和二乙二醇丁醚。更佳地，溶剂是二乙二醇甲醚。
在一个优选的实施例中，溶剂体系还包括聚乙烯吡咯烷酮或N-甲基吡咯烷酮。
较佳地，聚乙烯吡咯烷酮的浓度范围是0.01-5wt％。这一化合物没有毒性，在相似的浓度下还在诸如医药领域用作滴眼液的添加剂。
为了显示由N-烷基硫代磷酸三胺溶液制得的固体尿素肥料(例如：粒状尿素)涂层的均匀性，通常将农业中或食品中使用的着色剂添加至该溶剂体系。
为了使固体尿素肥料(例如：粒状尿素)的表面有足够多的由N-烷基硫代磷酸三胺制得的涂层，可将农业中普遍使用的表面活化剂添加至该溶剂体系中。
在一个较佳的实施例中，该N-烷基硫代磷酸三胺是正丁基硫代磷酸三胺。
较佳地，本发明的组分包含1-50wt.％的正丁基硫代磷酸三胺。
更佳地，本发明的组分包含10-40wt.％的正丁基硫代磷酸三胺。
最佳地，本发明的组分包含20-30wt.％的正丁基硫代磷酸三胺。
本发明更进一步的目的是在含有尿素的肥料中，用一种含有N-烷基硫代磷酸三胺的组分作为脲酶的抑制剂。该含有尿素的肥料可以是固态的，然后可以将本发明的组分添加至该用于生产这些肥料或肥料微粒(例如颗粒)的混合物中，或者可以在混合物中注入本发明的组分。在本发明的另一实施例中，含有尿素的肥料可以是液态的，然后将这种液态的肥料与本发明的组分混合。
在农业领域的应用上，本发明的溶剂体系表现出的性质具有以下优点：在本发明溶剂体系中，可以制得高浓度正丁基硫代磷酸三胺(NBPT)的溶液；在本发明的溶剂体系中，溶液中的正丁基硫代磷酸三胺具有稳定性。
与现有技术的溶剂体系相比，即使在很低的温度下(如-20℃)，本发明的溶剂体系还是表现出高抗固化性和抗晶化性。它们可以与水混溶，无毒，表现出低挥发性和不易燃性。由于使用的溶剂和化学特性，本发明的溶剂体系适合于注入到尿素微粒中去。更进一步的优势是，本发明中的溶剂体系的商业上可获得的技术级的组分包含最低水含量(通常只有百分之几)而且价格低廉。
本发明由下列实施例进一步阐述，但本发明并不限于此。
实施例1
具体实施方式
与现有技术的其他溶剂体系不同，本发明溶剂体系中的正丁基硫代磷酸三胺(NBPT)溶液具有在非常低的温度下仍能维持液态的特性。该特性取决于溶剂的化学性质，并且由于溶液中作为晶化抑制剂的聚乙烯吡咯烷酮的 存在而被进一步改善。在本实施例中，与现有技术中揭示的体系相比，本发明溶剂体系的使用，提高了NBPT浓缩溶液的流动性、降低了NBPT的晶化温度。
技术级的NBPT在溶液中的浓度为25wt％。选择-20℃作为测试温度，这样就能够直接评估溶液在与一年中低温月的温度动态相对应的贮藏条件下的性能了。在储存四个月后对溶液进行测试。结果如表1所示。流动性被分为下列各项等级：极好、好、不好。另外，溶液中是否存在NBPT晶体被分为：是、否。如果溶液中存在晶体，流动性将不作评估。
选择以下四类乙二醇醚进行测试：
二丙二醇甲醚(MDPG)
二乙二醇甲醚(MDGE)
三乙二醇甲醚(MTGE)
二乙二醇丁醚(BDGE)
将聚乙烯吡咯烷酮(PVP)和N-甲基吡咯烷酮(NMP)作为晶化抑制剂。作为与现有技术的对比，混合物中丙二醇(PG)作为溶剂，并且使用美国专利No，5,698,003中提到的含量为10wt％的N-甲基吡咯烷酮作为晶化抑制剂。
结果表明对于NBPT在低温下溶液的稳定性，MDGE是最好的溶剂。在-20℃的情况下，溶液中NBPT也没有晶化。在这种溶液中，晶化抑制剂的存在对于维持NBPT不是必需的，不过它的使用不会对溶液的流动性产生不利的影响。
MDPG作为溶剂对于聚乙烯吡咯烷酮具有正面的影响。在浓度为1wt.％的情况下完全抑制了晶化。
另一种适合的溶剂是MTGE，在此时，聚乙烯吡咯烷酮浓度为0.1wt.％，NBPT在-20℃的条件下也不发生晶化。
表1：在-20℃下，溶剂体系中不同组分对NBPT溶液流动性和溶液中NBPT晶化性的影响
N/A未测定
实施例2
本实例中揭示了，在5℃的条件下，用本发明的溶剂体系来提高浓缩的正丁基硫代磷酸三胺(NBPT)溶液流动性和NBPT的晶化温度。
技术级的NBPT在溶液中的浓度为25wt.％。经过四个月的储存，将溶液进行测试。结果如表2所示。流动性被分为三个等级：极好、好、不好。另外，溶液中是否存在正丁基硫代磷酸三胺(NBPT)晶体被分为：是、否。如果溶液中存在晶体，流动性将不作评估。
选择以下四类乙二醇醚进行测试：
二丙二醇甲醚(MDPG)
二乙二醇甲醚(MDGE)
三乙二醇甲醚(MTGE)
二乙二醇丁醚(BDGE)
将聚乙烯吡咯烷酮(PVP)和N-甲基吡咯烷酮(NMP)作为晶化抑制剂。作为与背景技术的对比，将丙二醇(PG)作为溶剂，并且使用美国专利No，5,698,003中提到的含量为10wt％N-甲基吡咯烷酮(NMP)作为抑制剂。
结果表明-5℃条件下的获得的结果与-20℃(实施例1)条件下获得的结 果几乎完全一致。当用MDPG作为溶剂时，聚乙烯吡咯烷酮在浓度为0.75wt.％时就抑制了晶化。当用BDGE作为溶剂时，在-5℃时没有发生晶化，而且溶液的流动性很好。
表2：在-5℃下，溶剂体系中不同组分对NBPT溶液流动性和溶液中正丁基硫代磷酸三胺(NBPT)晶化性的影响
N/A未测定
实施例3
溶液随时间的稳定性
在溶剂体系中的高稳定性的正丁基硫代磷酸三胺(NBPT)是溶液长时间储存的关键影响因素。在长期的储存过程中，NBPT的降解的主要原因是由于在较长的储存过程中的水的存在使正丁基硫代磷酸三胺(NBPT)分解成失效物质。
本发明涉及的是对于正丁基硫代磷酸三胺(NBPT)更稳定的溶剂体系。在这个实例中使用的所有乙二醇醚都具有很高的纯度(quality)。(水含量不超过0.05wt.％)。然而，为了确认溶剂稳定性，人为的将水分含量提升到1wt.％。调整溶剂体系来模拟潮湿气氛对正丁基硫代磷酸三胺(NBPT)的影响。(通常潮湿气氛的水分含量小于1wt.％)。
为了验证正丁基硫代磷酸三胺(NBPT)在含水1wt.％的乙二醇醚溶液中的长期稳定性，选择以下乙二醇醚进行测试：
二丙二醇甲醚(MDPG)
二乙二醇甲醚(MDGE)
三乙二醇甲醚(MTGE)
在这些溶剂中的正丁基硫代磷酸三胺(NBPT)溶液浓度为20wt.％(重量百分比)，将其密封在透明玻璃的小瓶子里在室温和日光下储存。
用装备了紫外检测器的反相高效液相色谱仪来检测每个独立的体系中NBPT的含量。反相高效液相色谱的可移动相中含有25％体积的乙腈和75％体积的浓度为0.005M的乙酸胺。在波长为193nm处用色谱进行检测。移动相流速为1ml/min，色谱柱温度为40℃。注入的体积为5μL。用表面的标准刻度线法进行评估。结果如表3所示。
表3：在t＝0(新制备的溶液)，t1＝1周后，t2＝12周后NBPT的含量(wt.％)，圆括号内是给出的可信的分析区间。
结果显示，即使在水含量为1wt.％的情况下，本发明涉及的溶剂体系对于正丁基硫代磷酸三胺(NBPT)还是具有很高的稳定性。储存12周后，在任何溶剂正丁基硫代磷酸三胺(NBPT)中的活性组分没有明显的下降。(所用的方法至少可以确定1％的变化。)
产业应用性
本发明涉及的溶剂体系，这种体系中的N-烷基硫代磷酸三胺溶液能够长期储存，用来注入到固体的含有尿素的肥料中。比如，尿素颗粒、加入到生产含有尿素的固体肥料的混合物中或加入到液相的含有尿素的肥料中。
Claims (12)
1.一种包含正丁基硫代磷酸三胺的组分，其特征在于，所述组分包含正丁基硫代磷酸三胺以及一个含有一个或多个如通式I的化合物的溶剂体系
其中，R1是氢或者甲基；R2是C1-C6烷基，n＝2-4。
2.如权利要求1所述组分，其特征在于，所述化合物选自二乙二醇甲醚，二丙二醇甲醚，三乙二醇甲醚和二乙二醇丁醚组成的群。
3.如权利要求2所述组分，其特征在于，所述化合物为二乙二醇甲醚。
4.如权利要求1所述组分，其特征在于，所述溶剂体系进一步包括聚乙烯吡咯烷酮或N-甲基吡咯烷酮。
5.如权利要求4所述组分，其特征在于，所述组分包含的聚乙烯吡咯烷酮的浓度范围是0.01-5wt.％。
6.如权利要求1所述组分，其特征在于，所述组分包含1-50wt.％的正丁基硫代磷酸三胺。
7.如权利要求6所述组分，其特征在于，所述组分包含10-40wt.％的正丁基硫代磷酸三胺。
8.如权利要求7所述组分，其特征在于，所述组分包含20-30wt.％的正丁基硫代磷酸三胺。
9.包含如权利要求1-8任一项所述的正丁基硫代磷酸三胺的组分在含有尿素的肥料中作为脲酶抑制剂的用途。
10.如权利要求9所述用途，所述含有尿素的肥料是固体的。
11.如权利要求10所述用途，所述含有尿素的固体肥料是颗粒状的。
12.如权利要求9所述用途，所述含有尿素的肥料是液体的。
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| CZ20060422A CZ301509B6 (cs) | 2006-06-28 | 2006-06-28 | Rozpouštedlová soustava pro prípravu roztoku N-alkyltriamidu kyseliny thiofosforecné, kompozice s obsahem N-alkyltriamidu kyseliny thiofosforecné a její použití |
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| PCT/CZ2007/000047 WO2008000196A1 (en) | 2006-06-28 | 2007-06-07 | Solvent system for the preparation of n-alkyl thiophosphoric triamide solutions, composition containing n-alkyl thiophosphoric triamide and the use thereof |
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