CN113667150B - 一种高分子土壤改良固体水聚合反应方法 - Google Patents
一种高分子土壤改良固体水聚合反应方法 Download PDFInfo
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- CN113667150B CN113667150B CN202110952708.7A CN202110952708A CN113667150B CN 113667150 B CN113667150 B CN 113667150B CN 202110952708 A CN202110952708 A CN 202110952708A CN 113667150 B CN113667150 B CN 113667150B
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- polylactic acid
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- soil improvement
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Abstract
本发明涉及一种高分子土壤改良固体水聚合反应方法，将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入异氰酸酯后继续反应后、导出冷却获得扩链聚乳酸；将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品，聚合装置包括微波炉膛、设置于微波炉膛内的反应器，以丙烯酸单体、矿物分料、扩链聚乳酸、自制交联剂在微波下交联复合，形成互穿交联网络结构提高吸水率、保水性、凝胶机械强度和耐盐碱性综合性能，简化合成工艺，使固体水用于改良土壤。
Description
技术领域
本发明涉及一种高分子土壤改良固体水聚合反应方法，属于固体水技术领域。
背景技术
固体水是一种具有超吸收性能可生物降解的保湿聚合物，具有高吸水、抗盐碱、改良土壤、可生物降解的特点，可广泛应用于农业、林业、园艺工艺、医疗卫生、荒漠治理等领域。目前的固体水高吸水性竖直一般采用淀粉接枝丙烯腈、丙烯酸、聚氨酯等，采用淀粉糊化后冷却、接枝共聚、加压水解和酸化、中和、干燥成型，高吸水性树脂主链以C-C键构成的聚丙烯盐受阳离子影响离子强度增加而吸水倍率下降，且受在低摩尔质量下才能被生物降解限制，增加了接枝共聚物的分子量控制难度，造成无法被完全降解而引起土壤污染，单一搅拌聚合反应装置在夹套热环境下交联聚合时反应时间长、需加盐促进反应、合成的聚合物中强亲水性基团较少而造成吸水率、保水性和凝胶机械强度综合性能较差。
发明内容
本发明的目的是针对现有技术的缺陷，提供一种高分子土壤改良固体水聚合反应方法，以丙烯酸单体、矿物分料、扩链聚乳酸、自制交联剂在微波下交联复合，形成互穿交联网络结构提高吸水率、保水性、凝胶机械强度和耐盐碱性综合性能，简化合成工艺，使固体水用于改良土壤。
本发明是通过如下的技术方案予以实现的：
一种高分子土壤改良固体水聚合反应方法，其方法如下：
S1:由L-赖氨酸溶于二氯甲烷中，加入丙烯酸循环分散后、加入柠康酸酐、偶氮二异丁腈在聚合装置中在微波下搅拌循环聚合反应制得交联剂；
S2：将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入异氰酸酯后继续反应后、导出冷却获得扩链聚乳酸；
S3：将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品。
进一步地，步骤S1中L-赖氨酸、丙烯酸、柠康酸酐、偶氮二异丁腈的质量比为85-120：75-95：120-200：0.1-0.3，微波功率为20-50W，温度为40-50℃，搅拌速率为80-100r/min反应30-60min制得
进一步地，步骤S2中所述聚乳酸、1,4丁二醇和异氰酸酯的质量比为:55-65:35-45：25-35，聚乳酸的重均分子量≤5000，所述催化剂为质量占聚乳酸、1,4丁二醇总质量0.5％的硫酸钠或氯化亚锡，微波功率为120-230W，温度为120-130℃，搅拌速率为50-60r/min反应30-60min，加入异氰酸酯后升温至140-150℃继续反应1-2h；
进一步地，步骤S3中所述矿物粉体为高岭土、白云石粉、凹凸棒黏土、蒙脱石粉中的一种或多种，所述引发剂为过硫酸铵或过硫酸钾，所述相转移催化剂为苄基三乙基氯化铵或四丁基硫酸氢铵；
中和度为60-70％，所述丙烯酸、交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂的质量比为20-30:0.05-0.1:6-11:5-9：0.05:0.1，微波功率为300-350W，温度为160-170℃，搅拌速率为40-80r/min反应1-2h。
上述一种高分子土壤改良固体水聚合装置，包括微波炉膛、设置于微波炉膛内的反应器，所述反应器内旋转的搅拌器，反应器顶部与底部连接有循环管路，所述循环管路上连接有进料管、出料管和循环泵。
进一步地，所述反应器在微波炉膛内偏心设置，微波炉膛一侧设有相连的变频变压器、磁控管和位于反应器侧顶部的滤导管，所述滤导管端部设有挡板。
进一步地，所述反应器包括与微波炉膛顶部固定的反应罩、与反应罩和微波炉膛可相对旋转的反应体，所述反应罩顶部设有减速电机，反应罩内部设有安装座，所述安装座上设有驱动轴、与搅拌器相连的传动轴、与反应体相连的外齿圈，所述减速电机和驱动轴上均设有皮带轮，皮带轮外设有传动皮带，所述传动轴上设有与外齿圈内部啮合的内齿轮，所述传动轴上设有与内齿轮外部啮合的传动齿，所述驱动轴与反应罩之间、传动轴与安装座之间、反应体与反应罩和微波炉膛之间均设有轴承套和密封圈，所述进料管端部倾斜延伸至反应体内部。
本发明的有益效果为：
(1)L-赖氨酸含有亲水性侧氨基、与丙烯酸/柠康酸酐在引发剂偶氮二异丁腈活化作用下接枝酸化改性，作为交联剂改善可降解固体水的亲水性、溶胀率和生物可降解性、增加反应活性；低分子量聚乳酸、1,4丁二醇、催化剂以羟基端封聚乳酸后以三官能团的异氰酸酯在微波下反应扩链，在C-C骨架上引入杂原子，提高生物可降解性；
(2)以部分中和的丙烯酸作为单体、矿物分料填充、扩链聚乳酸作为单体原料、与自制交联剂、在引发剂相转移催化剂微波下交联复合，形成互穿交联网络结构提高吸水率、保水性、凝胶机械强度和耐盐碱性综合性能，以微波辐射的聚合装置简化了合成工艺，利于规模化生产，使固体水成品达到改良土壤效果。
附图说明
图1为本发明反应装置结构图。
图中标记：微波炉膛1、反应器2，搅拌器3，循环管路4，进料管5、出料管6和循环泵7，变频变压器8、磁控管9和滤导管10，挡板11，反应罩12、反应体13，减速电机14，安装座15，驱动轴16、传动轴17、外齿圈18，皮带轮19，传动皮带20，内齿轮21，传动齿22，轴承套23和密封圈24。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步说明。
实施例1：
一种高分子土壤改良固体水聚合反应方法，其方法如下：
S1:由L-赖氨酸溶于二氯甲烷中，加入丙烯酸循环分散后、加入柠康酸酐、偶氮二异丁腈在聚合装置中在微波下搅拌循环聚合反应制得交联剂，L-赖氨酸、丙烯酸、柠康酸酐、偶氮二异丁腈的质量比为100：85：180：0.2，微波功率为45W，温度为46℃，搅拌速率为90r/min反应30min制得；
S2：将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入甲苯二异氰酸酯(TDI)后继续反应后、导出冷却获得扩链聚乳酸，所述聚乳酸、1,4丁二醇和甲苯二异氰酸酯(TDI)的质量比为:58:42：32，聚乳酸的重均分子量≤5000，所述催化剂为质量占聚乳酸、1,4丁二醇总质量0.5％的硫酸钠或氯化亚锡，微波功率为180W，温度为122℃，搅拌速率为55r/min反应40min，加入甲苯二异氰酸酯(TDI)后升温至140℃继续反应2h；
S3：将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和，中和度为60％后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，所述矿物粉体为高岭土与凹凸棒黏土按质量比1：1组成，所述引发剂为过硫酸铵，所述相转移催化剂为苄基三乙基氯化铵，所述丙烯酸、交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂的质量比为25:0.05:8:6：0.05:0.1，微波功率为320W，温度为165℃，搅拌速率为65r/min反应1h，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品。
实施例2
一种高分子土壤改良固体水聚合反应方法，其方法如下：
S1:由L-赖氨酸溶于二氯甲烷中，加入丙烯酸循环分散后、加入柠康酸酐、偶氮二异丁腈在聚合装置中在微波下搅拌循环聚合反应制得交联剂，L-赖氨酸、丙烯酸、柠康酸酐、偶氮二异丁腈的质量比为105：80：150：0.2，微波功率为40W，温度为48℃，搅拌速率为93r/min反应40min制得；
S2：将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入六亚甲基二异氰酸酯(HDI)后继续反应后、导出冷却获得扩链聚乳酸，所述聚乳酸、1,4丁二醇和六亚甲基二异氰酸酯(HDI)的质量比为:63:42：29，聚乳酸的重均分子量≤5000，所述催化剂为质量占聚乳酸、1,4丁二醇总质量0.5％的氯化亚锡，微波功率为180W，温度为125℃，搅拌速率为55r/min反应50min，加入六亚甲基二异氰酸酯(HDI)后升温至145℃继续反应2h；
S3：将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和，中和度为65％后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，所述矿物粉体为白云石粉，所述引发剂为过过硫酸钾，所述相转移催化剂为四丁基硫酸氢铵，所述丙烯酸、交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂的质量比为28:0.08:10:8：0.05:0.1，微波功率为340W，温度为166℃，搅拌速率为50r/min反应2h，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品。
实施例3
一种高分子土壤改良固体水聚合反应方法，其方法如下：
S1:由L-赖氨酸溶于二氯甲烷中，加入丙烯酸循环分散后、加入柠康酸酐、偶氮二异丁腈在聚合装置中在微波下搅拌循环聚合反应制得交联剂，L-赖氨酸、丙烯酸、柠康酸酐、偶氮二异丁腈的质量比为90：80：165：0.2，微波功率为40W，温度为45℃，搅拌速率为90r/min反应40min制得；
S2：将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入异佛尔酮二异氰酸酯(IPDI)后继续反应后、导出冷却获得扩链聚乳酸，所述聚乳酸、1,4丁二醇和异佛尔酮二异氰酸酯(IPDI)的质量比为:58:42：27，聚乳酸的重均分子量≤5000，所述催化剂为质量占聚乳酸、1,4丁二醇总质量0.5％的硫酸钠，微波功率为180W，温度为122℃，搅拌速率为60r/min反应40min，加入异佛尔酮二异氰酸酯(IPDI)后升温至143℃继续反应1h；
S3：将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和，中和度为70％后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，所述矿物粉体为蒙脱石粉，所述引发剂为过过硫酸钾，所述相转移催化剂为苄基三乙基氯化铵，所述丙烯酸、交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂的质量比为28:0.07:8:7：0.05:0.1，微波功率为320W，温度为163℃，搅拌速率为60r/min反应1h，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品。
上述实施例1-3中的一种高分子土壤改良固体水聚合装置，包括微波炉膛1、设置于微波炉膛1内的反应器2，所述反应器2内旋转的搅拌器3，反应器2顶部与底部连接有循环管路4，所述循环管路4上连接有进料管5、出料管6和循环泵7；
所述反应器2在微波炉膛1内偏心设置，微波炉膛1一侧设有相连的变频变压器8、磁控管9和位于反应器2侧顶部的滤导管10，所述滤导管10端部设有挡板11；
所述反应器2包括与微波炉膛1顶部固定的反应罩12、与反应罩12和微波炉膛1可相对旋转的反应体13，所述反应罩12顶部设有减速电机14，反应罩12内部设有安装座15，所述安装座15上设有驱动轴16、与搅拌器3相连的传动轴17、与反应体13相连的外齿圈18，所述减速电机14和驱动轴16上均设有皮带轮19，皮带轮19外设有传动皮带20，所述传动轴17上设有与外齿圈18内部啮合的内齿轮21，所述传动轴17上设有与内齿轮21外部啮合的传动齿22，所述驱动轴16与反应罩12之间、传动轴17与安装座15之间、反应体13与反应罩12和微波炉膛1之间均设有轴承套23和密封圈24，所述进料管5端部倾斜延伸至反应体13内部。
本发明的机理为：
由循环管上端部倾斜延伸至反应体13内部的进料管5投料，由减速电机14在传动皮带20和皮带轮19减速传动下带动驱动轴16旋转，驱动轴16与反应罩12之间、传动轴17与安装座15之间、反应体13与反应罩12和微波炉膛1之间均设有轴承套23和密封圈24，可相对旋转且提高密封防腐蚀性，驱动轴16旋转时通过内齿轮21驱动外齿圈18带动反应体13相对反应罩12和微波炉腔旋转，提高微波辐射均匀性，并通过内齿轮21与传动齿22啮合驱动安装座15上的传动轴17带动搅拌器3在反应器2内旋转，反应体13相对对接出料管6在微波炉膛1内旋转；
搅拌器3高速旋转、反应体13对向减速旋转增加物料体系对流湍动，出料管6物料经循环泵7和循环管向顶部进料管5循环物料，增加物料循环传质反应效率，并可由循环管连接阀门和取样管取样检测；
由变频变压器8变频。磁控管9在电源激励下产生微波、经滤波管波导耦合至挡板11分散向微波炉膛1内的反应器2提供微波能量，微波频率：2450MHz±50Hz，由延伸至反应体13内的温度探测器检测温度、变频控制反应温度和微波频率；
将实施例1-3制得的固体水与市购高分子吸水树脂SAP(通灵达FMX-6)作为对照品检测比较，检测方法和检测结果如下：
吸水率检测：取0.3g固体水或对照品兑水、静置30min后，湿网滤去过于水分、静置后、再静置至每分钟质量减少在1g以内称重，按照吸水率＝(M3-M2-M1)/M1计算，M3为吸水后筛网与凝胶总重，M2为筛网重量，M1为干重；
保水性检测：将检测吸水率后留置的凝胶与筛网置于干燥箱中在90℃下赶在1.5h，取出冷却后称重，按照保水率(％)＝(M4-M2)/(M1-M2)*100％计算，M4为脱水后筛网与凝胶总重，M2为筛网重量，M1为脱水前筛网与凝胶总重；
吸盐率检测：取0.3g固体水或对照品兑0.9％盐水、静置30min后，湿网滤去过于水分、静置后、再静置至每分钟质量减少在1g以内称重，按照吸水率＝(M3-M2-M1)/M1计算，M3为吸水后筛网与凝胶总重，M2为筛网重量，M1为干重；
降解时间：称取75mg蜗牛酶溶于50nl醋酸和醋酸钠的缓冲溶液中，与40℃下搅拌测量降解速率；
凝胶强度：取1g固体水或吸水树脂完全溶胀后的饱和凝胶以测高仪在50g砝码压力下，记录5min后的抗压形变量＝初始高度-终高度；
| 序号/项目 | 吸水率 | 保水率(％) | 吸盐率 | 降解时间 | 抗压形变量(cm) |
| 实施例1 | 633 | 65.4 | 87 | 55 | 1.7 |
| 实施例2 | 602 | 79.5 | 98 | 48 | 1.9 |
| 实施例3 | 615 | 63.9 | 95 | 51 | 1.5 |
| 对照例 | 365 | 45.1 | 73 | 无法完全降解 | 3.6 |
采用L-赖氨酸含有亲水性侧氨基、与丙烯酸/柠康酸酐在引发剂偶氮二异丁腈活化作用下接枝酸化改性、通过微波搅拌反应热解活化，接枝增加支链、引入乙烯基和羧基不饱和烯烃单体，作为交联剂有效改善可降解固体水的亲水性、溶胀率和生物可降解性、增加反应活性；
采用低分子量重均分子量≤5000的聚乳酸、1,4丁二醇、催化剂硫酸钠或氯化亚锡在微波下搅拌反应，微波功率为120-230W，温度为120-130℃，以羟基端封聚乳酸后以三官能团的异氰酸酯在微波下反应扩链，异氰酸酯包括甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、二环己基甲烷二异氰酸酯(HMDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、1,5-萘二异氰酸酯(NDI)，生成氨基甲酯键和酰胺键，升温至140-150℃避免产物分子量下降或分子量分布变宽、减少副反应，以便在C-C骨架上引入杂原子，容易被微生物完全降解；
以部分中和的丙烯酸作为单体、矿物分料高岭土、白云石粉、凹凸棒黏土、蒙脱石粉中的一种或多种作为填充料，扩链聚乳酸作为单体原料、与自制交联剂、在引发剂过硫酸铵或过硫酸钾、相转移催化剂苄基三乙基氯化铵或四丁基硫酸氢铵在微波下交联复合，矿物分料中的多价金属离子提高了聚合反应速度、交联度和凝胶化、从而增加了吸水倍率和凝胶体强度、且原料价廉易得、增加耐盐碱性、适应不同盐碱度的土壤环境；
矿物分料与扩链聚乳酸复合控制交联度，在微波功率为300-350W，温度为160-170℃，搅拌速率为40-80r/min反应提高产率，形成互穿交联网络结构提高保水性和热稳定性，使表面交联密度大于中心、改良提高吸水率、保水性、凝胶机械强度和耐盐碱性综合性能，取固体水凝胶切碎、烘干、研磨、筛分获得亲水又不溶于水的高分子土壤改良固体水成品，以微波辐射的聚合装置简化了合成工艺，利于规模化生产；
使用时将固体水兑水搅拌形成凝胶后，拌入种子或抛洒于植穴中覆土后浇水或降雨作用，固体水将土壤中多余的水分包括溶于水的肥料吸收保存起来、并在微生物降解作用下缓慢释放，使土壤保持湿润、在反复收缩和吸胀作用下给土壤造成大量孔隙、提高土壤透气性、透水性、改善植物根植环境、从而改良土壤基质、防止土壤板结、盐渍化，达到改良土壤效果。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”等仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”等的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，除非另有说明，“若干”的含义是两个或两个以上。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以通过具体情况理解上述术语在本发明中的具体含义。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (6)
1.一种高分子土壤改良固体水聚合反应方法，其特征在于，其方法如下，将聚乳酸、1,4丁二醇、催化剂置于聚合装置中在微波下搅拌反应、加入异氰酸酯后继续反应后、导出冷却获得扩链聚乳酸；将NaOH与去离子水稀释投入聚合装置中、加入丙烯酸搅拌中和后，加入交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂、在微波下循环反应制得固体水凝胶，取固体水凝胶切碎、烘干、研磨、筛分获得固体水成品；
所述交联剂由L-赖氨酸溶于二氯甲烷中，加入丙烯酸循环分散后、加入柠康酸酐、偶氮二异丁腈在聚合装置中在微波下搅拌循环聚合反应制得。
2.根据权利要求1所述的一种高分子土壤改良固体水聚合反应方法，其特征在于，所述聚乳酸、1,4丁二醇和异氰酸酯的质量比为:55-65:35-45：25-35，聚乳酸的重均分子量≤5000。
3.根据权利要求1所述的一种高分子土壤改良固体水聚合反应方法，其特征在于，所述催化剂为质量占聚乳酸、1,4丁二醇总质量0.5％的硫酸钠或氯化亚锡，微波功率为120-230W，温度为120-130℃，搅拌速率为50-60r/min反应30-60min，加入异氰酸酯后升温至140-150℃继续反应1-2h。
4.根据权利要求1所述的一种高分子土壤改良固体水聚合反应方法，其特征在于，制备交联剂时L-赖氨酸、丙烯酸、柠康酸酐、偶氮二异丁腈的质量比为85-120：75-95：120-200：0.1-0.3，微波功率为20-50W，温度为40-50℃，搅拌速率为80-100r/min反应30-60min制得。
5.根据权利要求1所述的一种高分子土壤改良固体水聚合反应方法，其特征在于，所述矿物粉体为高岭土、白云石粉、凹凸棒黏土、蒙脱石粉中的一种或多种，所述引发剂为过硫酸铵或过硫酸钾，所述相转移催化剂为苄基三乙基氯化铵或四丁基硫酸氢铵。
6.根据权利要求1所述的一种高分子土壤改良固体水聚合反应方法，其特征在于，中和度为60-70％，所述丙烯酸、交联剂、矿物粉体、扩链聚乳酸、引发剂和相转移催化剂的质量比为20-30:0.05-0.1:6-11:5-9：0.05:0.1，微波功率为300-350W，温度为160-170℃，搅拌速率为40-80r/min反应1-2h。
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