CN105131250B - 单组分自交联水性聚氨酯缓控释包膜材料 - Google Patents

单组分自交联水性聚氨酯缓控释包膜材料 Download PDF

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CN105131250B
CN105131250B CN201510541094.8A CN201510541094A CN105131250B CN 105131250 B CN105131250 B CN 105131250B CN 201510541094 A CN201510541094 A CN 201510541094A CN 105131250 B CN105131250 B CN 105131250B
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Abstract

本发明公开了一种单组分自交联水性聚氨酯缓控释包膜材料及其制备工艺，属于高分子材料制备技术领域，特征在于先由二异氰酸酯、蓖麻油、低聚物多元醇、扩链剂制备水性聚氨酯，然后将其与用亚硫酸氢钠封闭的聚氨酯交联剂混匀，即得到单组份自交联水性聚氨酯缓控释包膜材料。通过本发明得到的包膜材料以水为载体，不含有机溶剂，对环境友好无污染，通过调节蓖麻油含量和软硬段比例可以调控包膜材料的交联度和亲水性，进而控制养分的释放速率，而包膜材料中的羧基等活性基团可以活化土壤中的磷元素，提高磷的利用率，固定土壤中钾离子，从而大幅度提高肥料利用率。

Description

单组分自交联水性聚氨酯缓控释包膜材料
技术领域
本发明涉及一种高分子材料的制备技术领域，具体涉及到一种单组分自交联水性聚氨酯缓控释包膜材料及其制备工艺。
背景技术
我国是农业大国，化肥在农业生产中具有十分重要的作用，目前我国的化肥以速效肥料为主，由于在土壤中发生淋溶、挥发等原因，造成大量营养元素的丢失，农民为提高作物产量不得不大幅度提高化肥施用量，从60年代平均亩施肥几公斤到现在的40kg/亩的施肥量，短短的几十年里亩施肥量增长了6倍多，40kg/亩的施肥量是国际上化肥允许施用量的上限15kg/亩的2倍多。 据统计，我国肥料利用率只有20-30%，而发达国家肥料利用率可以达到50-60%。肥料利用率低不仅给社会带来巨大的经济损失，还引起了诸如湖泊富营养化、饮用水中硝酸盐超标等严重的环境污染问题。研制和开发缓控释肥料是提高肥料利用率的重要途径，通过肥料中养分缓控释技术可以降低肥料的溶解速度，使肥料在溶解过程中陆续为作物提供养分，从而达到提高肥料利用率和增产的目的。
目前市场上的缓控释肥料主要有以下三类：1、添加脲酶抑制剂、硝化抑制剂的稳态性肥料，该类肥料可延缓尿素的水解、降低铵态氮转化为硝态氮的速度，但对肥料利用率的提高效果不明显；2、无机矿物盐类包膜肥料，如包硫尿素，由于该类包膜材料封闭性差，膜层较脆、易脱落，因此缓控释效果不佳，另外长期使用包硫尿素容易造成土壤酸化；3、聚合物包膜肥料，主要以脲醛树脂、环氧聚酯、聚苯乙烯、聚乙烯、聚氯乙烯等为包衣剂，其中以脲醛树脂包膜技术最成熟，应用最广泛，但该树脂在土壤中会分解出甲醛，易对作物和土壤造成伤害，同时上述几种包膜材料在使用前都要用一定量的有机溶剂溶解，且在土壤中不易降解，因此对环境易造成污染，长期使用容易破坏土壤结构。综上所述，开发出一种性能优良、成本低廉、易于降解和对环境友好的包膜材料已势在必行。
发明内容
本发明的目的在于提出一种单组分自交联水性聚氨酯缓控释包膜材料及其制备工艺，以克服现有技术上的缺陷，通过本方法制备的缓控释包膜材料具有抗机械损伤能力强、韧性好、成本低、易降解等优点。
该发明是通过如下技术方案实现的：
一种单组分自交联水性聚氨酯缓控释包膜材料，其制备工艺包括如下步骤：
A、水性聚氨酯的制备：以水性聚氨酯中非水组分和非溶剂组分的质量为基准，将占6~35wt%的蓖麻油多元醇、10~40wt%低聚物多元醇和10~40wt%的二异氰酸酯于70~90℃反应1~2h，再加入2.5~6wt%的亲水性扩链剂、0~10wt%的扩链剂、0~0.5wt%的催化剂和10~100wt%的溶剂，于50~75℃继续反应2~4h，采用标准二正丁胺滴定法测定NCO含量，直至其达到理论值，降温至20~40℃，在800~8000转/分钟的高速剪切下，加入0.5~2.5wt%的中和剂和100~500wt%的去离子水进行乳化，减压脱除溶剂；
B、 交联剂的制备：以交联剂中非水组分和非溶剂组分的质量为基准，将占20-65%的聚乙二醇、30-60%的二异氰酸酯、0~15wt%的扩链剂、20~200wt%的溶剂于70-90℃反应2~4h，至NCO含量达到采用标准二正丁胺滴定法确定的理论值，降温至25℃以下，在1000~8000转/分钟的高速剪切下，先后加入100~500%的冰水混合物，10~40%浓度为10~30%的亚硫酸氢钠溶液，减压脱除溶剂；
C、 将水性聚氨酯与交联剂按一定比例混合均匀，即得到单组分自交联水性聚氨酯缓控释包膜材料。
其中：
所述低聚物多元醇为数均分子量1000~4000的聚酯二醇、聚醚二醇。
所述亲水性扩链剂选自二羟甲基丙酸、二羟甲基丁酸。
所述二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯。
所述扩链剂选自1，4-丁二醇、乙二醇、一缩二乙二醇、己二醇。
所述溶剂选自丙酮、丁酮、N，N-二甲基甲酰胺。
所述催化剂选自辛酸亚锡、二丁基锡二月桂酸酯。
所述聚乙二醇数均分子量为200~1000。
与现有技术相比，本发明具有以下优点：
1、本发明使用蓖麻油作为部分软段，其优点如下：①蓖麻油属于可再生资源，价格低，可生物降解，因而一方面可降低肥料成本，另一方面可避免包膜材料对环境的二次污染；②蓖麻油平均官能度2.7，能够提高聚氨酯包膜材料的交联度，且蓖麻油中含有较长的脂肪酸链，具有一定的疏水性，因此通过调节聚氨酯链段中蓖麻油的含量可以调节包膜材料的交联度和吸水率，进而调控肥料的释放速率。
2、本发明使用亚硫酸氢钠封闭的多异氰酸酯作为交联剂，解封温度低，单组份，使用方便。
3、包膜材料中含有大量的羧基等活性基团，能够活化土壤中被固定的磷，增加土壤有效磷的含量，提高磷肥利用率，同时可固定土壤中钾离子，防止钾的流失。
4、聚氨酯材料软硬可调，韧性好，抗机械损伤能力强。
5、以水为载体，对环境友好无污染。
附图说明
附图1为单组份自交联水性聚氨酯缓控释包膜材料合成工艺图。
附图2为包膜材料水接触角与蓖麻油含量关系图。图中水接触角采用上海中晨公司JC2000C1型静滴接触角测定仪测定。测试方法如下：取一定量的乳液均匀涂在载玻片上，在一定的温度下于烘箱中烘烤一段时间后取出，冷却，去离子水滴于薄膜表面，在25℃进行测试。从图中可以看出：蓖麻油的加入能够显著提高材料的疏水性。
具体实施方式
下面结合具体实施例，对本发明作进一步阐述。
实施例1：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）36g、羟值等于163mgKOH/g的蓖麻油多元醇30g、真空脱水后的羟值等于55mgKOH/g的聚氧化丙烯二醇（PPG）20g，在机械搅拌下于90℃恒温反应1.5h；降温至80℃，加入二羟甲基丙酸（DMPA）4.2g、丙酮20ml继续反应1h，得到亲水改性的PU预聚体；加入40ml丙酮，待体系降温至40℃左右，加入一缩二乙二醇（DEG）10.0g，二丁基锡二月桂酸酯3滴，于60℃反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺3.7g中和2min，分多次加入去离子水约150g，搅拌2min，然后减压下脱除溶剂丙酮，即得到固含量为40%，PH≈7的水性聚氨酯；
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）28g、数均分子量等于500的聚乙二醇40g，1，4-丁二醇3.2g，丙酮60ml，于80℃反应2.5h，降温至室温，在1500转/分高剪切力作用下先后加入400g0℃的冰水混合物及浓度25%的亚硫酸氢钠（SBS）水溶液60g，乳化5min，减压下脱除丙酮，即得到固含量为25% 的交联剂；
将水性聚氨酯和交联剂按10:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。
实施例2：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）35g、羟值等于163mgKOH/g的蓖麻油多元醇40g、真空脱水后的羟值等于55mgKOH/g的聚己二酸丁二醇酯二醇（PBA）40g，在机械搅拌下于90℃恒温反应1.5h；降温至80℃，加入二羟甲基丙酸（DMPA）4.8g、丙酮20ml继续反应1h，得到亲水改性的PU预聚体；加入40ml丙酮，待体系降温至40℃左右，加入1,4-丁二醇（BDO）5.5g，二丁基锡二月桂酸酯3滴，于60℃反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺3.5g中和2min，分多次加入去离子水约160g，搅拌2min，然后减压下脱除丙酮，即得到固含量为45%，PH≈7的水性聚氨酯；
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）75g、数均分子量等于400的聚乙二醇90g，1，4-丁二醇7.5g，丙酮100ml，于80℃反应1.5h，降温至室温，在1500转/分高剪切力作用下先后加入410g冰水混合物及浓度25%的亚硫酸氢钠（SBS）水溶液130g，乳化5min，即得到固含量为25%的交联剂；
将水性聚氨酯和交联剂按5:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。
实施例3：单组分自交联水性聚氨酯缓控释包膜材料
在500ml带有回流冷凝管和温度计的三口瓶中，加入二苯基甲烷二异氰酸酯（MDI）91g、羟值等于163mgKOH/g的蓖麻油多元醇50g、真空脱水后的羟值等于110mgKOH/g的聚氧化丙烯二醇（PPG）50g，在机械搅拌下于70℃恒温反应1.5h；降温至60℃，加入二羟甲基丙酸（DMPA）7.1g、丙酮20ml继续反应1h，得到亲水改性的PU预聚体；加入40ml丙酮，待体系降温至40℃左右，加入1，4-丁二醇（BDO）9.0g，于60℃反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺5.3g中和2min，分多次加入去离子水约400g，搅拌2min，然后减压下脱除丙酮，即得到固含量为45%，PH≈7的水性聚氨酯；
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）68g、数均分子量等于200的聚乙二醇40g， 乙二醇5.0g，丙酮80ml，于65℃反应2.5h，降温至室温，在1500转/分高剪切力作用下先后加入350g的冰水混合物及浓度15%的亚硫酸氢钠（SBS）水溶液180g，乳化5min，即得到交联剂；
将水性聚氨酯和交联剂按8:1的比例混合即得到缓控释肥料包膜用交联聚氨酯乳液。
实施例4：单组分自交联水性聚氨酯缓控释包膜材料
在500ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）73g、羟值等于163mgKOH/g的蓖麻油多元醇50g、真空脱水后的羟值等于110mgKOH/g的聚氧化丙烯二醇（PPG）50g，在机械搅拌下于90℃恒温反应1.5h；降温至80℃，加入二羟甲基丙酸（DMPA）7.5g、丙酮20ml继续反应1h，得到亲水改性的PU预聚体；加入40ml丙酮，待体系降温至40℃左右，加入一缩二乙二醇（DEG）15.0g，二丁基锡二月桂酸酯2滴，辛酸亚锡1滴，于60℃反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺5.6g中和2min，分多次加入去离子水约320g，搅拌2min，然后减压下脱除溶剂丙酮，即得到固含量为45%，PH≈7的水性聚氨酯组分；
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）40g、数均分子量等于500的聚乙二醇40g， 1，4-丁二醇7.2g，丙酮60ml，于65℃反应2.5h，降温至室温，在1500转/分高剪切力作用下先后加入220g冰水混合物及浓度20%的亚硫酸氢钠（SBS）水溶液150g，乳化5min，即得到交联剂；
将水性聚氨酯和交联剂按15:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。
实施例5：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）36g、羟值等于163mgKOH/g的蓖麻油多元醇12g、真空脱水后的羟值等于110mgKOH/g的聚氧化丙烯二醇（PPG）45g、二羟甲基丙酸（DMPA）3.6g、一缩二乙二醇（DEG）7.8g、丙酮20ml，在机械搅拌下于80℃恒温反应2.5h；加入二丁基锡二月桂酸酯3滴、丙酮40ml，继续反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺2.7g中和2min，分多次加入去离子水约150g，搅拌2min，然后减压下脱除丙酮，即得到固含量为45%，PH≈7的水性聚氨酯组分；
在250ml带有回流冷凝管和温度计的三口瓶中，加入六亚甲基二异氰酸酯（HDI）40g、数均分子量等于500的聚乙二醇85g, 丙酮100ml于80℃反应2.5h，降温至室温，在1500转/分高剪切力作用下先后加入300g冰水混合物及浓度30%的亚硫酸氢钠（SBS）水溶液90g，乳化5min，即得到交联剂；
将水性聚氨酯和交联剂按6:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。
实施例6：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）36g、羟值等于163mgKOH/g的蓖麻油多元醇30g、真空脱水后的数均分子量为2000、羟值等于55mgKOH/g的聚氧化丙烯二醇（PPG）20g，在机械搅拌下于90℃恒温反应1.5h；降温至80℃，加入二羟甲基丁酸（DMBA）3.9g、丙酮20ml继续反应1h，得到亲水改性的PU预聚体；加入40ml丙酮，待体系降温至40℃左右，加入一缩二乙二醇（DEG）10.0g，二丁基锡二月桂酸酯3滴，于60℃反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺2.7g中和2min，分多次加入去离子水约150g，搅拌2min，然后减压下脱除溶剂丙酮，即得到固含量为45%，PH≈7的水性聚氨酯；
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）27g、数均分子量等于500的聚乙二醇40g，一缩二乙二醇4.0g，丙酮40ml，于80℃反应1.5h，降温至室温，在1500转/分高剪切力作用下先后加入220g冰水混合物及浓度30%的亚硫酸氢钠（SBS）水溶液70g，乳化5min，即得到交联剂；
将水性聚氨酯和交联剂按20:1的比例混合即得到缓控释肥料包膜用交联聚氨酯乳液。
实施例7：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入异佛尔酮二异氰酸酯（IPDI）60g、羟值等于163mgKOH/g的蓖麻油多元醇35g、真空脱水后的羟值等于55mgKOH/g的聚己二酸丁二醇酯二醇（PBA）50g、二羟甲基丁酸（DMBA）7.6g、一缩二乙二醇（DEG）10.0g、丙酮20ml，在机械搅拌下于80℃恒温反应2.5h；加入二丁基锡二月桂酸酯3滴、辛酸亚锡1滴、丙酮40ml，继续反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺5.2g中和2min，分多次加入去离子水约210g，搅拌2min，然后减压下脱除丙酮，即得到固含量为45%，PH≈7的水性聚氨酯组分；
在250ml带有回流冷凝管和温度计的三口瓶中，加入六亚甲基二异氰酸酯（HDI）40g、数均分子量等于500的聚乙二醇55g、一缩二乙二醇（DEG）8.0g，丙酮50ml于80℃反应3h，降温至室温，在1500转/分高剪切力作用下先后加入220g冰水混合物及浓度25%的亚硫酸氢钠（SBS）水溶液100g，乳化5min，减压下脱除丙酮，即得到交联剂；
将水性聚氨酯和交联剂按6:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。
实施例8：单组分自交联水性聚氨酯缓控释包膜材料
在250ml带有回流冷凝管和温度计的三口瓶中，加入甲苯二异氰酸酯（TDI）42g、羟值等于163mgKOH/g的蓖麻油多元醇25g、真空脱水后的羟值等于110mgKOH/g的聚氧化丙烯二醇（PPG）45g、二羟甲基丙酸（DMPA）4.3g、1,4丁二醇（BDO）8.7g、丙酮20ml，在机械搅拌下于80℃恒温反应2.5h；加入二丁基锡二月桂酸酯3滴、丙酮40ml，继续反应至NCO含量达到理论值（采用标准二正丁胺滴定法确定）；降温至30℃左右，在1800转/分高剪切力作用下加入三乙胺3.4g中和2min，分多次加入去离子水约190g，搅拌2min，然后减压下脱除溶剂丙酮，即得到固含量为45%，PH≈7的水性聚氨酯；
在250ml带有回流冷凝管和温度计的三口瓶中，加入六亚甲基二异氰酸酯（HDI）36g、数均分子量等于500的乙二醇（EG）55g、1,4丁二醇（BDO）5.8g，丙酮90ml于80℃反应3h，降温至室温，在1500转/分高剪切力作用下先后加入320g冰水混合物及浓度25%的亚硫酸氢钠（SBS）水溶液80g，乳化5min，即得到交联剂；
将水性聚氨酯和交联剂按8:1的比例混合即得到单组分自交联水性聚氨酯缓控释包膜材料。

Claims (8)

1.一种单组分自交联水性聚氨酯缓控释包膜材料，其制备工艺包括如下步骤：
①水性聚氨酯的制备：以水性聚氨酯中非水组分和非溶剂组分的质量为基准，将占6~35wt%的蓖麻油多元醇、10~40wt%低聚物多元醇和10~40wt%的二异氰酸酯于70~90℃反应1~2h，再加入2.5~6wt%的亲水性扩链剂、0~10wt%的扩链剂、0~0.5wt%的催化剂和10~100wt%的溶剂，于50~75℃继续反应2~4h，采用标准二正丁胺滴定法测定NCO含量，直至其达到理论值，降温至20~40℃，在800~8000转/分钟的高速剪切下，加入0.5~2.5wt%的中和剂和100~500wt%的去离子水进行乳化，减压脱除溶剂；
②交联剂的制备：以交联剂中非水组分和非溶剂组分的质量为基准，将占20-65wt %的聚乙二醇、30-60wt%的二异氰酸酯、0~15wt%的扩链剂、20~200wt%的溶剂于70-90℃反应2~4h，至NCO含量达到采用标准二正丁胺滴定法确定的理论值，降温至25℃以下，在1000~8000转/分钟的高速剪切下，先后加入100~500%的冰水混合物，10~40%浓度为10~30wt%的亚硫酸氢钠溶液，减压脱除溶剂；
③将水性聚氨酯与交联剂按5~20:1的比例混合均匀，即得到单组分自交联水性聚氨酯缓控释包膜材料。
2.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述低聚物多元醇为数均分子量1000~4000的聚酯二醇、聚醚二醇。
3.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述亲水性扩链剂选自二羟甲基丙酸、二羟甲基丁酸。
4.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述二异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯。
5.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述扩链剂选自1，4-丁二醇、乙二醇、一缩二乙二醇、己二醇、三羟甲基丙烷。
6.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述溶剂选自丙酮、丁酮、N，N-二甲基甲酰胺。
7.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述催化剂选自辛酸亚锡、二丁基锡二月桂酸酯。
8.根据权利要求1所述的一种单组分自交联水性聚氨酯缓控释包膜材料，其特征在于：所述聚乙二醇数均分子量为200~1000。
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