CN108794526B - 一种草甘膦·三氯吡氧乙酸水剂的制备方法 - Google Patents
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Abstract
本发明涉及一种草甘膦和三氯吡氧乙酸水剂的制备方法，1、将三氯吡氧乙酸和有机碱反应，制备得到三氯吡氧乙酸的盐；2、然后再添加草甘膦酸，搅拌均匀后缓慢加入有机碱；3、最后加入助溶剂，表面活性剂、消泡剂等助剂，制备成水剂。制备得到的水剂稳定性好，对杂草具有很好的防治效果。
Description
技术领域：
本发明涉及一种草甘膦和三氯吡氧乙酸水剂的制备方法。
技术背景：
草甘膦和三氯吡氧乙酸的组合物对非耕地杂草具有很好的防治效果，现有的涉及草甘膦和三氯吡氧乙酸的组合物的制备方法一般有两种。一是将有效成分混合制备成合适的剂型方便使用，例如专利CN101485310A和CN104957171A中公开的组合物和制备方法中，均是采用将原药混合后制备成组合物，这种混合具有使用方便，操作简单等优点，然而此方法制备的水剂稳定性却不能保证，因此对于产品的货架期会有一定的影响；二是利用三氯吡氧乙酸中的羧酸基团和草甘膦的二甲胺盐反应制备成草甘膦和三氯吡氧乙酸的混合物，例如CN104447862A中所述。然而此工艺操作复杂，需要先制备草甘膦的盐，然后再将制备得到的盐和三氯吡氧乙酸混合，制备成混合液，最后再根据需要制备成固体颗粒剂。在制备过程中会有各物料不好控制的缺陷，例如不容易控制组合物中各有效成分的含量、比例等。基于上述原因，本公司团队经过长期的试验、探索出一种操作简单，制备过程简单的制备草甘膦和三氯吡氧乙酸水剂的方法，进而完成本发明。
发明内容：
一种草甘膦·三氯吡氧乙酸水剂的制备方法，其特征在于1、将三氯吡氧乙酸和有机碱反应，制备得到三氯吡氧乙酸的盐；2、然后再添加草甘膦酸，搅拌均匀后缓慢加入有机碱；3、最后加入助溶剂，表面活性剂等助剂，制备成水剂。在上述步骤1中，反应温度是45-70℃，反应终点为无色至浅黄色澄清透明液体，pH为7.0-8.0；上述步骤2中，草甘膦酸碱反应后，整个体系pH值控制在6.0-6.5左右，溶液呈浅黄色至黄色透明液体，无固体颗粒物存在；上述步骤3中，搅拌至制剂为浅黄色至黄色澄清透明液体，所述表面活性剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、烷基糖苷、牛脂胺聚氧乙烯醚，其中有机碱为三乙胺。
通过进一步的研究，具体的中试过程为：
1)备料
依据产品批次提前1-2天到仓库领取该批生产所需的原料，若有上批生产剩余的产品及收集的设备清洗水一并领取到车间并运到车间分料、备料区域。
分零过程中必须进行完一种原辅材料后才能进行下一种分零，以免漏记、重复记录或者记录失误等情况出现，过程做好分零记录。
2)投加原药
关闭反应釜釜底阀、人孔盖及釜上各管线阀门(放空阀除外)，打开软水管线阀门，通过质量流量计计量，先将总量90％软水通过软水输送泵从软水储罐打入配制釜，开启搅拌，调整搅拌浆转速在900-1350r/min。从人孔投加计量的三氯吡氧乙酸原药，关闭人孔，搅拌至分散均匀。
3)三氯吡氧乙酸成盐反应
开启有机碱高位槽底阀，开启反应釜碱液进口阀，缓慢开启碱液手动控制闸阀，将计量的有机碱液缓慢滴加至反应釜，控制有机碱液流加速度14-17kg/min，进行成盐反应。有机碱液滴加完毕，搅拌约30-60分钟。直至反应终点。
三氯吡氧乙酸成盐反应终点为，溶液呈无色至淡黄色澄清透明液体，无明显颗粒状原药未溶解，溶液pH值为7.0-8.0。如pH值过低，继续缓慢滴加有机碱调整pH值。
过程控制成盐温度在65-75℃，如温度过低，开启热循环水加热；如温度过高，开启乙二醇水冷系统冷却降温。
4)草甘膦酸成盐反应
开启人孔盖，从人孔投加计量的草甘膦酸原药，关闭人孔，搅拌至分散均匀。
开启有机碱高位槽底阀，开启反应釜碱液进口阀，缓慢开启碱液手动控制闸阀，将计量的有机碱液滴加至反应釜，控制有机碱液流加速度14-17kg/min，进行成盐反应。有机碱液滴加完毕，搅拌约30-60分钟。直至反应终点。
草甘膦酸成盐反应终点为，溶液呈淡黄色至黄色透明液体，无明显颗粒状原药未溶解，溶液pH值6.0-6.5。如pH值过低，继续缓慢滴加有机碱调整pH值。
过程控制成盐温度在65-75℃，如温度过低，开启热循环水加热；如温度过高，开启乙二醇水冷系统冷却降温。
5)抽加助剂及补余软水
密封配制釜，启动真空机组并把釜内真空拉到(-0.06)—(-0.08)Mpa，打开抽料管线阀门，计量抽加各表面活性剂、助溶剂，并根据实际投加物料的量，计算需补余的软水量，通过流量计抽加进行补余。搅拌溶解30-60min。
6)循环溶解
开启反应釜顶部产品进口阀，先开启釜底反吹阀使用压缩空气反吹3-5min(目的是将底部为溶解完全的原药吹起，防止堵塞管道篮式过滤器)，后开启反应釜下部产品出口阀，开启循环离心泵，调整转速在1800-2700r/min，进行釜外循环溶解。循环时间60min。关闭产品出口阀，关闭循环离心泵，关闭产品进口阀。
7)釜外过滤循环
开启反应釜顶部产品过滤循环进口阀，开启配制釜下部过滤器出口阀、进口阀，开启釜底产品出口阀，开启循环离心泵，调整转速在1800-2700r/min，进行釜外循环过滤，过程调节离心泵转速，保证过滤器进出口压力在0.2-0.4Mpa，进出口压力表压差在0.05Mpa-0.10Mpa之间。循环时间60min左右。
釜外过滤循环过程时间达到，过程开启过滤器后部的取样阀取样，并检查产品外观澄清度，产品正常外观为淡黄色至黄色澄清透明均相液体。样品外观正常，送检中控分析。
8)过滤转料
中控分析合格，可连接去储罐快接头，进行过滤转料至储罐工序。过滤转料完毕后，关闭各管线阀门，密闭反应釜。检查无误后，关闭设备电源。
9)成品分装及成品分析
开启储罐底阀，开启分装高位槽进料阀，开启物料输送泵，将产品输送至分装高位槽。分装高位槽物料转入完毕，开启各分装机进行成品分装。
过程质检人员抽检，复测重量、标识、成品外观。随机抽取样品送检成品分析。
本发明的水剂具有如下优点：
1、充分利用有效成分，减少废水的处理量，降低处理成本；
2、反应体系中避免使用了无机碱，减少了反应设备的腐蚀；
3、制备得到的水剂质量稳定，防治效果好。
附图说明：图1是本发明的简单工艺流程图
具体实施方式：以下结合附图和具体的实施例对本发明作进一步的详细说明。
实施例1：45％草甘膦三乙胺·三氯吡氧乙酸三乙胺水剂(实验室制备)。
根据反应的需要，称取40％的草甘膦(以酸计)，5％的三氯吡氧乙酸，烷基酚聚氧乙烯醚10％，有机硅消泡剂1％，助溶剂硫酸铵2％，其余为水。
先投加三氯吡氧乙酸于反应装置中，开启搅拌，然后缓慢滴加三乙胺，反应温度70℃，至溶液呈无色至浅黄色澄清透明液体，pH为8.0左右时，反应停止；然后再投加草甘膦酸，搅拌均匀后缓慢加入三乙胺，整个体系pH值控制在6.0-6.5左右，溶液呈浅黄色至黄色透明液体，无固体颗粒物存在，最后加入助溶剂硫酸铵，表面活性剂烷基酚聚氧乙烯醚及消泡剂有机硅，搅拌至制剂为浅黄色至黄色澄清透明液体时既得，反应完后，水补足100％，搅拌均匀既得。
实施例2：45％草甘膦三乙胺·三氯吡氧乙酸三乙胺水剂(中试实验制备)
原料和实施例1相同，不同之处在于制备过程进行了放大。
草甘膦三乙胺·三氯吡氧乙酸三乙胺水剂小试生产包括备料、投加原药、成盐反应、补余助剂、溶解循环、过滤循环、中控分析、过滤储存、产品分装、成品分析以及环境保护所需的三废收集处理。
1)备料
提前1-2天到仓库领取该批生产所需的原料备料。
2)投加原药
关闭反应釜釜底阀、人孔盖及釜上各管线阀门(放空阀除外)，打开软水管线阀门，通过质量流量计计量，先将总量90％软水通过软水输送泵从软水储罐打入配制釜，开启搅拌，调整搅拌浆转速在1000r/min。从人孔投加计量的三氯吡氧乙酸原药，关闭人孔，搅拌至分散均匀。
3)三氯吡氧乙酸成盐反应
开启有机碱高位槽底阀，开启反应釜碱液进口阀，缓慢开启碱液手动控制闸阀，将计量的有机碱液缓慢滴加至反应釜，控制有机碱液流加速度15kg/min，进行成盐反应。有机碱液滴加完毕，搅拌约45分钟。直至溶液呈无色至淡黄色澄清透明液体，无明显颗粒状原药未溶解，溶液pH值控制在7.0-8.0。如pH值过低，继续缓慢滴加有机碱调整pH值。
过程控制成盐温度在65-75℃，如温度过低，开启热循环水加热；如温度过高，开启乙二醇水冷系统冷却降温。
4)草甘膦酸成盐反应
开启人孔盖，从人孔投加计量的草甘膦原药，关闭人孔，搅拌至分散均匀。
开启有机碱高位槽底阀，开启反应釜碱液进口阀，缓慢开启碱液手动控制闸阀，将计量的有机碱液滴加至反应釜，控制有机碱液流加速度15kg/min，进行成盐反应。有机碱液滴加完毕，搅拌约45分钟。直至溶液呈淡黄色至黄色透明液体，无明显颗粒状原药未溶解，溶液pH值6.0-6.5。如pH值过低，继续缓慢滴加有机碱调整pH值。
过程控制成盐温度在65-75℃，如温度过低，开启热循环水加热；如温度过高，开启乙二醇水冷系统冷却降温。
5)抽加助剂及补余软水
密封配制釜，启动真空机组并把釜内真空拉到(-0.06)—(-0.08)Mpa，打开抽料管线阀门，计量抽加各表面活性剂、助溶剂，并根据实际投加物料的量，计算需补余的软水量，通过流量计抽加进行补余。搅拌溶解50min。
6)循环溶解
开启反应釜顶部产品进口阀，先开启釜底反吹阀使用压缩空气反吹3-5min(目的是将底部为溶解完全的原药吹起，防止堵塞管道篮式过滤器)，后开启反应釜下部产品出口阀，开启循环离心泵，调整转速在1800-2700r/min，进行釜外循环溶解。循环时间60min。关闭产品出口阀，关闭循环离心泵，关闭产品进口阀。
7)釜外过滤循环
开启反应釜顶部产品过滤循环进口阀，开启配制釜下部过滤器出口阀、进口阀，开启釜底产品出口阀，开启循环离心泵，调整转速在2000r/min，进行釜外循环过滤，过程调节离心泵转速，保证过滤器进出口压力在0.2-0.4Mpa，进出口压力表压差在0.05Mpa-0.10Mpa之间。循环时间60min左右。
釜外过滤循环过程时间达到，过程开启过滤器后部的取样阀取样，并检查产品外观澄清度，产品正常外观为淡黄色至黄色澄清透明均相液体。样品外观正常，送检中控分析。
8)过滤转料
中控分析合格，可连接去储罐快接头，进行过滤转料至储罐工序。过滤转料完毕后，关闭各管线阀门，密闭反应釜。检查无误后，关闭设备电源。
9)成品分装及成品分析
开启储罐底阀，开启分装高位槽进料阀，开启物料输送泵，将产品输送至分装高位槽。分装高位槽物料转入完毕，开启各分装机进行成品分装。
表1本发明的水剂主要技术指标
注：对比例1为CN104957171A实施例3的水剂，对比例2为CN104447862A中实施例10制备得到的水剂。
从表1可以看出，本发明的组合物制备的水剂在稳定性和水不溶物等指标均优于对比例，这在水剂中是至关重要的，有效成分不分解可以延长产品的货架期。
实施例3：田间药效试验
供试药剂：实施例1-2的水剂，对比例1-2。
对照药剂：46％草甘膦异丙胺盐水剂(对照药剂1)，45％三氯吡氧乙酸水剂(对照药剂2)。
试验方法：试验于非耕地内进行，每个组别处理3次重复，处理面积约为50m2，按照试验小区的面积，准确称量好各种药剂，苗前喷雾处理。统计给药后30d杂草死亡情况，比较各种药剂的除草活性，结果见表2。
表2本发明的水剂药后30d除草效果
大田试验结果表明，本发明中实施例1-2和对比例1-2的制剂，在防治杂草方面效果相当，略优于对比例1-2，明显的优于单剂，具有一定的增效作用。
综上所述，本发明的制剂在稳定性等方面优于现有技术中的制剂，在生产过程中避免使用了无机碱，对设备有了很好的保护作用，更利于大批量的生产。
最后，需要说明的是：在不偏离本发明精神的基础上所做的修改或改进，对本领域技术人员来说是显而易见的，因此应均属于本发明要求保护的范围。
Claims (1)
1.一种草甘膦·三氯吡氧乙酸水剂的制备方法，包含以下步骤：
(1)、将三氯吡氧乙酸和有机碱反应，制备得到三氯吡氧乙酸的盐；
(2)、然后再添加草甘膦酸，搅拌均匀后缓慢加入有机碱；
(3)、最后加入助溶剂，表面活性剂、消泡剂助剂，制备成水剂；所述表面活性剂为烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、牛脂胺聚氧乙烯醚；所述有机碱为三乙胺；所述助溶剂为硫酸铵；
步骤(1)中，反应温度控制在45-75℃，反应终点为无色至浅黄色澄清透明液体，pH为7.0-8.0；
步骤(2)中，草甘膦酸碱反应后，整个体系pH值控制在6.0-6.5，溶液呈浅黄色至黄色透明液体，无固体颗粒物存在；步骤(3)中，搅拌至制剂为浅黄色至黄色澄清透明液体。
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