CN116640292A - 一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法 - Google Patents
一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法 Download PDFInfo
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Abstract
本发明公开了一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其制备的聚氨酯低游离预聚物能显著提高TDI类弹性体的动态性能，降低预聚体的交联密度，同时具有优异的动态性能。本发明的方法包括以下步骤：在惰性气体保护下，将高活性二异氰酸酯和低活性脂肪族二异氰酸酯混合均匀后，加入酸性物质再混合均匀得到二异氰酸酯混合液；将聚合多元醇加热熔解，脱除多元醇中的水分；再将脱水后的聚合多元醇连续滴加到二异氰酸酯混合液中进行合成反应，结束后加入抗氧剂，脱除气泡得到前端预聚物；将前端预聚物转移到短程分子蒸发器中，脱除游离的二异氰酸酯，得到低交联高性能可低温蒸馏聚氨酯低游离预聚物。
Description
技术领域
本发明涉及一种聚氨酯预聚物的制备方法，更具体地说涉及一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法。
背景技术
聚氨酯(PU)是一类性能优异的高分子材料，具有优异的拉伸强度、撕裂强度、耐磨性、耐剪切性能和耐油、耐臭氧、耐溶剂等出众的综合性能，在工业中有着广泛的用途。聚氨酯预聚物法是将低聚物聚酯或聚醚多元醇与二异氰酸酯在一定条件下合成预聚物，再与扩链剂、交联剂反应制得聚氨酯制品。预聚物法制得聚氨酯制品的结构相对比较规整，在聚氨酯制品研究和开发方面有重要的地位。常规预聚物法制得的预聚物一般都有一定游离的二异氰酸酯单体存在，如常用的TDI型预聚物都含有0.5％-3％游离的TDI单体。游离的TDI在使用时易挥发，气味大，危害环境与人体健康。欧盟正在颁布新的法规，限制非低游离预聚体的使用。在加工工艺方面，常规预聚物与固化剂混合后粘度上升快，脱模时间长，生产效率低，最终对聚氨酯弹性体的性能也有一定影响，尤其对耐热性能与动态力学性能影响明显，这使得制品的使用寿命大大缩短。
现有技术中，国内外众多研究机构和企业尝试使用多种方法来降低预聚物中的游离异氰酸酯单体含量，这些方法包括降低NCO/OH比例的化学反应技术、薄膜蒸发技术、溶剂萃取技术和分子筛吸附技术等。例如，中国专利CN114230742A公开了一种低游离TDI的聚氨酯预聚体及其制备方法，通过在TDI预聚体中加入共沸助剂，来降低预聚体粘度，从而来降低蒸馏难度；该方法虽然将预聚体粘度降低了，但是蒸馏温度没有降低，产物仍有较高的高交联密度的风险，同时采用了沸点接近TDI的共沸助剂为酯类，酯类增塑剂含有一定水分和单醇，这对后期预聚体的品质影响很大。中国专利CN111410728A公开了一种存储稳定的低游离异氰酸酯聚氨酯预聚物的制备方法，通过在预聚体中加入高沸点惰性溶剂，离子络合物等来得到存储稳定的低游离聚氨酯预聚物；该方法能够降低处理温度，缩短处理时间，但是体系中仍然要加入大量的惰性溶剂。中国专利CN102659997B公开了一种低游离异氰酸酯聚氨酯预聚物的分离方法，在酯类溶剂体系中进行预聚反应，反应结束后将溶剂及残留异氰酸酯单体和预聚物分离；虽然最终预聚物中游离异氰酸酯单体含量低于0.5％，但是整个体系中包含有大量的溶剂，相当于用稀释的方法得到了低游离预聚物，同时由于含有溶剂，这种预聚物的使用范围受限，基本只适合于涂料和胶黏剂行业，不适合于弹性体行业。美国专利4061662公开了一种从预聚物中分离未反应的TDI单体的方法，该方法将预聚物缓慢通过含有分子筛的分离柱，从而有效降低预聚物中游离TDI单体的含量；但该方法分离效率低，残留单体回收和分离柱的清洗活化未能得到有效解决。美国专利US5077371公开了一种制备低游离TDI含量预聚物的方法，利用含TDI二聚体的TDI或其他二异氰酸酯与多元醇反应，通过较低的NCO/OH摩尔比例，保持较低的NCO过量率，尽量将多元醇中的OH基团全部反应，使制得的预聚物中游离TDI含量低于0.4％；此方法由于TDI二聚体活性较低，会造成较多的二聚体残留，从而破坏了预聚物的综合性能。
目前我国占份额最大的聚氨酯预聚体是TDI预聚体，TDI预聚物可以和胺类扩链，浇注工艺简单，制品成品率高。但利用TDI预聚物做出来的聚氨酯弹性体也存在不足，即动态性能不好，特别是交联密度大的时候，动态性能更差。现有技术只专注于降低游离异氰酸酯含量，未关注在合成过程中如何降低副反应导致的高交联密度。因此，迫切需要一种能提高TDI类弹性体动态性能和降低交联密度，同时能在低温下蒸馏降低游离异氰酸酯含量的聚氨酯预聚物制备方法。
发明内容
本发明的目的是解决现有技术中存在的问题与不足，提供了一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其制备的聚氨酯低游离预聚物能显著提高TDI类弹性体的动态性能，降低预聚体的交联密度，同时具有优异的动态性能；制备方法绿色环保，简单易行，成本低。
本发明是通过以下技术方案实现的：
本发明的低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法包括以下步骤：
原料预处理：在惰性气体保护下，将高活性二异氰酸酯和低活性脂肪族二异氰酸酯混合均匀后，加入酸性物质再混合均匀得到二异氰酸酯混合液；其中高活性二异氰酸酯和低活性脂肪族二异氰酸酯的质量比为100:5-100:50，酸性物质加入量为5ppm-200ppm；
前端预聚物的合成：将聚合多元醇加热熔解，真空吸入反应釜中，加热至90-110℃，脱除多元醇中的水分至水分含量≤0.03wt％；再将脱水后的聚合多元醇连续滴加到预处理后的二异氰酸酯混合液中进行合成反应，反应结束后加入抗氧剂，搅拌状态下脱除气泡得到前端预聚物；
低游离预聚物的制备：将脱泡后的前端预聚物转移到短程分子蒸发器中，在高温高真空状态下脱除游离的二异氰酸酯，得到游离二异氰酸酯含量<0.1wt％的低交联高性能可低温蒸馏聚氨酯低游离预聚物。
本发明上述的低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其进一步的技术方案是所述的高活性二异氰酸酯为甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯的一种或其组合；所述的低活性脂肪族二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、甲基环已基二异氰酸酯的一种或其组合；所述的酸性物质为氯化氢或乙酸乙酰氯。
本发明上述的低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其进一步的技术方案还可以是所述的聚合多元醇为分子量在400-3000的聚四氢呋喃多元醇、聚酯多元醇、聚已内酯多元醇、聚氧化丙烯醚多元醇中的一种或或其组合；前端预聚物的合成反应时聚合多元醇和二异氰酸酯混合液中二异氰酸酯的摩尔比为1：2-8，合成反应温度为50-70℃下，反应时间为2-4小时；所述的脱除多元醇中的水分时压力在1kPa以下进行。
本发明与现有技术相比具有以下有益效果：
本发明制备方法得到的低交联高性能可低温蒸馏聚氨酯低游离预聚物前期在高酸值环境下反应，可防止副反应的产生，得到交联度低的前端预聚物。后期在蒸馏时，可以去除添加的酸性物质，这对于聚酯类的预聚物来说，体系中不含酸，可以改善抗水解性能，特别是高温环境下，低酸环境可以大大降低酯键水解的速度，提高产品使用寿命。在酸性条件下，酯的羰基的π电子易与氢离子结合，生成羟基。羰基的碳此时因为π电子与氢离子结合，缺电子，所以带正电(+1)，易被亲核试剂(比如说水)进攻，发生水解。同时由于低交联密度，预聚体固化后更容易进行扩链反应，分子量增大可以得到综合性能好的弹性体。同时前端预聚体由于加入了活性很低的脂肪族异氰酸酯，脂肪族异氰酸在聚合阶段几乎不与多元醇反应，在蒸馏阶段却可以降低蒸发温度。由于TDI预聚体在大于100℃的情况下，会快速生成脲基甲酸酯副产物，传统蒸发温度下得到的预聚体含有一定量的交联，这使得低游离预聚体粘度偏高，脱气困难，而且固化的产物物性偏低。加入脂肪族异氰酸酯后，前端预聚物可以在较低的温度下蒸馏，交联度低，可制得动静态物性更加优异聚氨酯弹性体。此外，本发明的方法其蒸馏温度可以降低生产能耗，制备成本低。
具体实施方式
以下通过具体实施例说明本发明，但本发明并不仅仅限定于这些实施例。
实施例1
在氮气保护下，将336g的甲苯二异氰酸酯和35g六亚甲基二异氰酸酯均匀混合，将2.8N氯化氢钢瓶连接气体流量计，通入大约100ppm的HCl气体。打开并搅拌，使得HCL在异氰酸酯中混合均匀。将分子量为2000的聚四氢呋喃二醇1000g和分子量为1000的聚四氢呋喃二醇165g分别在温度95℃，真空度为1kPa条件下脱水至含量水在0.03％以下，然后依次缓慢加入到甲苯二异氰酸酯和六亚甲基二异氰酸酯的混合液中，然后缓慢升温至65℃，保温反应3h。反应结束后，加入抗氧剂BHT，搅拌均匀，脱除产物中的气泡。脱泡后得到待蒸发的前端预聚体。将预聚体转移到短程分子蒸发器的进料罐中，将进料罐温度设定在80℃，分子蒸发器的壁温设定在100℃，冷凝器温度设定在0℃，冷阱温度设定在-30℃，真空度设定在5Pa。打开分子蒸发器，等到所有温度和压力参数稳定后，开始进料，进料速度1000g/hr，利用分子蒸发器脱除过量的甲苯二异氰酸酯和六亚甲基二异氰酸酯。收集的低游离预聚体使用气相色谱检测预聚体中游离异氰酸酯含量在0.1％以下即为合格。上述过程中甲苯二异氰酸酯和多元醇摩尔比为2.9，最终预聚体NCO含量为4.0％。
实施例2
在氮气保护下，将524.4g的甲苯二异氰酸酯和80g六亚甲基二异氰酸酯均匀混合，加入80ppm的乙酸乙酰氯并搅拌均匀。将分子量为1000的聚己二酸丁二醇酯二醇1000g和分子量为2000的聚己二酸丁二醇酯二醇40g分别在温度95℃，真空度为1kPa条件下脱水至含量水在0.03％以下，然后依次缓慢加入到甲苯二异氰酸酯和六亚甲基二异氰酸酯的混合液中，然后缓慢升温至60℃，保温反应3h。反应结束后，加入抗氧剂PDDP，搅拌均匀，脱除产物中的气泡。脱泡后，将物料打入到短程分子蒸发器的进料罐中，将进料罐温度设定在80℃，分子蒸发器的壁温设定在100℃，冷凝器温度设定在0℃，冷阱温度设定在-30℃，真空度设定在5Pa。打开分子蒸发器，等到所有温度和压力参数稳定后，开始进料，进料速度1000g/hr，利用分子蒸发器脱除过量的甲苯二异氰酸酯和六亚甲基二异氰酸酯。收集的低游离预聚体使用气相色谱检测预聚体中游离异氰酸酯含量在0.1％以下即为合格。上述过程中甲苯二异氰酸酯和多元醇摩尔比为2.95，最终预聚体NCO含量为5.39％。
实施例3
在氮气保护下，将609g的甲苯二异氰酸酯和100g六亚甲基二异氰酸酯均匀混合，加入80ppm的乙酸乙酰氯并搅拌均匀。将分子量为1000的聚己内酯二醇1000g和分子量为2000的聚已内酯二醇410g分别在温度95℃，真空度为1kPa条件下脱水至含量水在0.03％以下，然后依次缓慢加入到甲苯二异氰酸酯和六亚甲基二异氰酸酯的混合液中，然后缓慢升温至70℃，保温反应3h。反应结束后，加入抗氧剂BHT，搅拌均匀，脱除产物中的气泡。脱泡后，将物料打入到短程分子蒸发器的进料罐中，将进料罐温度设定在80℃，分子蒸发器的壁温设定在100℃，冷凝器温度设定在0℃，冷阱温度设定在-30℃，真空度设定在5Pa。打开分子蒸发器，等到所有温度和压力参数稳定后，开始进料，进料速度1000g/hr，利用分子蒸发器脱除过量的甲苯二异氰酸酯和六亚甲基二异氰酸酯。上述过程中甲苯二异氰酸酯和多元醇摩尔为2.9，最终预聚体NCO含量为4.85％。
实施例4
在氮气保护下，将336g的甲苯二异氰酸酯和35g六亚甲基二异氰酸酯均匀混合，将2.8N氯化氢钢瓶连接气体流量计，通入大约100ppm的HCl气体。打开并搅拌，使得HCL在异氰酸酯中混合均匀。将分子量为650的聚四氢呋喃二醇1600g和二甘醇90.4克分别在温度95℃，真空度为1kPa条件下脱水在0.03％以下，然后依次缓慢加入到甲苯二异氰酸酯和六亚甲基二异氰酸酯的混合液中，然后缓慢升温至65℃，保温反应3h。反应结束后，加入抗氧剂BHT，搅拌均匀，脱除产物中的气泡。脱泡后得到待蒸发的前端预聚体。将预聚体转移到短程分子蒸发器中的进料罐中，将进料罐温度设定在80℃，分子蒸发器的壁温设定在100℃，冷凝器温度设定在0℃，冷阱温度设定在-30℃，真空度设定在5Pa。打开分子蒸发器，等到所有温度和压力参数稳定后，开始进料，进料速度1000g/hr，利用分子蒸发器脱除过量的甲苯二异氰酸酯和六亚甲基二异氰酸酯。上述过程中甲苯二异氰酸酯和多元醇摩尔比为2.9，最终预聚体NCO含量为9.7％。
对比例1
按与实施例1相同的方案制备预聚物，不同之处在于，反应时，不加入酸性物质氯化氢。其他物料和反应条件一致。
将实施例1与对比例1制得的预聚物分别与3,3’二氯-4,4’-二苯基甲烷二胺(MOCA)固化，预聚物温度为70℃，MOCA温度为114℃，模具温度为100℃。固化后试片在100℃烘箱中后固化16h。性能如表1所示。
表1预聚体性能
| 粘度(70℃)，cps | 拉伸强度，MPa | 伸长率，％ | 裤型撕裂，KN/m | 回弹，％ | |
| 实施例1 | 1076 | 32.2 | 450 | 24.6 | 61 |
| 对比例1 | 1190 | 31.8 | 410 | 19.6 | 54 |
由表1可以看出，加入酸性物质可以使预聚物粘度降低，同时提高固化产物的伸长率、裤型撕裂和回弹。这说明加入酸性物质可以降低预聚物的交联程度。
对比例2
按与实施例2相同的方案制备预聚物，不同之处在于，反应时，不加入脂肪族异氰酸酯六亚甲基二异氰酸酯。脱泡后，将物料打入到薄膜蒸发器中，然后再逐级打入到短程分子蒸发器中，在温度120-140度下，真空度为5-10Pa下脱除过量的甲苯二异氰酸酯和六亚甲基二异氰酸酯。检测预聚体中游离异氰酸酯含量在0.1％以下即为合格。
将实施例2与对比例2制得的预聚物分别与3,3’二氯-4,4’-二苯基甲烷二胺(MOCA)固化，预聚物温度为70℃，MOCA温度为114℃，模具温度为100℃。固化后试片在100℃烘箱中后固化16h。性能如表2所示。
表2预聚物性能
| 粘度(70℃)，cps | 拉伸强度，MPa | 伸长率，％ | 裤型撕裂，KN/m | 回弹，％ | |
| 实施例2 | 1600 | 36.7 | 400 | 58.7 | 34 |
| 对比例2 | 1850 | 37.2 | 360 | 54.1 | 31 |
由表2可以看出，若同样得到游离含量低于0.1％的预聚物，采用加入脂肪族异氰酸酯的方法可以降低预聚物粘度，降低蒸发温度，从而使得最终预聚物交联程度降低，性能提升。
对比例3
按与实施例3相同的方案制备预聚物，不同之处在于，反应时，不加入脂肪族异氰酸酯六亚甲基二异氰酸酯。
表3预聚物粘度和游离度
| 粘度(100℃)，cps | 游离度，％ | |
| 实施例3 | 436 | 0.16 |
| 对比例3 | 420 | 0.28 |
由表3可以看出，采用相同温度蒸发前端预聚物时，不加脂肪族异氰酸酯的工艺所得到的预聚物游离度更高。这说明添加脂肪族异氰酸酯可以降低蒸发温度。
对比例4
按与实施例4相同的方案制备预聚物，不同之处在于，反应时，不加入脂肪族异氰酸酯六亚甲基二异氰酸酯。
表4预聚物粘度和游离度
| 粘度(100℃)，cps | 游离度，％ | |
| 实施例4 | 180 | 0.11 |
| 对比例4 | 170 | 0.3 |
由表4可以看出，对于高NCO含量的预聚物，采用相同温度蒸发前端预聚物时，不加脂肪族异氰酸酯的工艺所得到的预聚物游离度更高。
Claims (3)
1.一种低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其特征在于，包括以下步骤：
原料预处理：在惰性气体保护下，将高活性二异氰酸酯和低活性脂肪族二异氰酸酯混合均匀后，加入酸性物质再混合均匀得到二异氰酸酯混合液；其中高活性二异氰酸酯和低活性脂肪族二异氰酸酯的质量比为100:5-100:50，酸性物质加入量为5ppm-200ppm；
前端预聚物的合成：将聚合多元醇加热熔解，真空吸入反应釜中，加热至90-110℃，脱除多元醇中的水分至水分含量≤0.03wt％；再将脱水后的聚合多元醇连续滴加到预处理后的二异氰酸酯混合液中进行合成反应，反应结束后加入抗氧剂，搅拌状态下脱除气泡得到前端预聚物；
低游离预聚物的制备：将脱泡后的前端预聚物转移到短程分子蒸发器中，在高温高真空状态下脱除游离的二异氰酸酯，得到游离二异氰酸酯含量<0.1wt％的低交联高性能可低温蒸馏聚氨酯低游离预聚物。
2.根据权利要求1所述的低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其特征在于，所述的高活性二异氰酸酯为甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯的一种或其组合；所述的低活性脂肪族二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、甲基环已基二异氰酸酯的一种或其组合；所述的酸性物质为氯化氢或乙酸乙酰氯。
3.根据权利要求1所述的低交联高性能可低温蒸馏聚氨酯低游离预聚物的制备方法，其特征在于，所述的聚合多元醇为分子量在400-3000的聚四氢呋喃多元醇、聚酯多元醇、聚已内酯多元醇、聚氧化丙烯醚多元醇中的一种或或其组合；前端预聚物的合成反应时聚合多元醇和二异氰酸酯混合液中二异氰酸酯的摩尔比为1：2-8，合成反应温度为50-70℃下，反应时间为2-4小时；所述的脱除多元醇中的水分时压力在1kPa以下进行。
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