CN115073702A - 一种有机硅改性聚氨酯侧链大单体及其合成方法 - Google Patents
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Abstract
一种有机硅改性聚氨酯侧链大单体及其合成方法，本发明公开了一种有机硅改性聚氨酯侧链大单体。所述合成方法是将有机硅改性聚氨酯预聚体降温，加入三乙胺和水，剪切后，加入乙二胺，进行扩链反应，减压抽挥发物质，得有机硅改性聚氨酯侧链大单体。本发明有机硅改性聚氨酯侧链大单体的稳定性好，分子量适合，可制备出吸附性、减水率、保坍性和稳定性俱佳的减水剂。本发明方法工艺简单，成本低，适宜于工业化生产。
Description
技术领域
本发明涉及一种聚氨酯侧链大单体及其合成方法，具体涉及一种有机硅改性聚氨酯侧链大单体及其合成方法。
背景技术
聚羧酸（PCE）作为新一代混凝土减水剂，具有分子设计自由度大、原料来源范围广、减水率较高等优点，普通聚羧酸的结构如下所示：
分子设计中，侧链大单体结构对聚羧酸的吸附性、减水率、保坍性等性能和作用机理有着至关重要的影响，应重点考虑。
以下是普通氨脂类聚羧酸的反应式，是由丙烯酸（主链）聚合之后，聚氨酯接枝进入主链的侧链大单体，此类大单体为氨脂类大单体，没有碳碳双键，因此缩合进入。
还有一种醚类大单体，有双键，可以直接脱去双键，进入主链。
现有方法合成的聚氨酯，一般也就是简单的合成，这样合成的聚氨酯用于聚羧酸主链的聚合，最多也就是单纯的聚氨酯接入，而一般合成的聚羧酸对硅酸盐水泥的水化有延迟影响。因此，现有聚氨酯合成的聚羧酸在应用于减水剂时，其吸附性、减水率、保坍性和稳定性等性能均欠佳。
发明内容
本发明所要解决的技术问题是，克服现有技术存在的上述缺陷，提供一种稳定性好，分子量适合，可制备出吸附性、减水率、保坍性和稳定性俱佳的减水剂的有机硅改性聚氨酯侧链大单体。
本发明进一步要解决的技术问题是，克服现有技术存在的上述缺陷，提供一种工艺简单，成本低，适宜于工业化生产的有机硅改性聚氨酯侧链大单体的合成方法。
本发明解决其技术问题所采用的技术方案如下：一种有机硅改性聚氨酯侧链大单体，所述有机硅改性聚氨酯侧链大单体的结构式为：
，m=1～30；其中，R4为
，k=1～30，l=1～30，其中，R1为
，R2为
，i =1～30，R3为
，j=1～30。通过有机硅改性后的聚氨酯接入聚羧酸主链后，可极大提高聚羧酸的吸附性、减水率、保坍性和稳定性等性能。
本发明进一步解决其技术问题所采用的技术方案如下：一种有机硅改性聚氨酯侧链大单体的合成方法，将有机硅改性聚氨酯预聚体降温，加入三乙胺和水，剪切后，加入乙二胺，进行扩链反应，减压抽挥发物质，得有机硅改性聚氨酯侧链大单体。由于采用了有机硅改性聚氨酯预聚体，使得合成的聚氨酯侧链大单体的分子量更大，接枝进入聚羧酸后，所得减水剂的性能更好。
本发明合成方法的反应方程式如下所示：
优选地，所述有机硅改性聚氨酯预聚体、三乙胺、水和乙二胺的质量比为1:0.01～0.11:1.0～2.0:0.02～0.10。
优选地，所述降温至≤40℃。
优选地，所述剪切的速率为300～2000r/min，时间为4～6h。
优选地，所述扩链反应的温度为40～80℃，压力为0.10～0.12MPa，时间为0.5～1.0h。
优选地，所述减压至0.01～0.10MPa。
优选地，所述有机硅改性聚氨酯预聚体的合成方法，包括以下步骤：
1）将聚醚二醇滴入异佛尔酮二异氰酸酯中，得混合溶液A；
2）将步骤1）所得混合溶液A滴入二羟甲基丙酸的N-甲基吡咯烷酮溶液中，得混合溶液B；
3）将步骤2）所得混合溶液B滴入端羟基聚硅氧烷的1,4-丁二醇溶液中，得混合溶液C；
4）先后将二乙胺、三乙胺滴入步骤3）所得混合溶液C中，得混合溶液D；
5）将十二烷基苯磺酸钠加入步骤4）所得混合溶液D中，乳化，得有机硅改性聚氨酯预聚体。
所述有机硅改性聚氨酯预聚体的合成方法的反应方程式如下所示：
优选地，步骤1）中，所述聚醚二醇与异佛尔酮二异氰酸酯的质量比为2.0～2.5:1。所述聚醚二醇的分子量为200～2000。
优选地，步骤1）中，所述聚醚二醇中含有1～4滴二月桂酸二丁基锡/25g聚醚二醇。
优选地，步骤1）中，所述滴入的时间为0.5～4.0h。
优选地，步骤2）中，所述混合溶液A与二羟甲基丙酸的质量比为1:0.01～0.07。
优选地，步骤2）中，所述二羟甲基丙酸与N-甲基吡咯烷酮溶液的质量体积比（g/mL）为1:2.0～3.6。
优选地，步骤2）中，所述滴入的时间为0.5～4.0h。
优选地，步骤3）中，所述混合溶液B中二羟甲基丙酸与端羟基聚硅氧烷的质量比为1:3～5。所述端羟基聚硅氧烷的分子量为1000～3000。
优选地，步骤3）中，所述端羟基聚硅氧烷与1,4-丁二醇的质量体积比（g/mL）为1:0.2～0.4。
优选地，步骤3）中，所述滴入的时间为0.5～4.0h。
优选地，步骤4）中，所述二乙胺、三乙胺与混合溶液C的质量体积比（g/g/mL）为0.01～0.10:0.01～0.20:1。
优选地，步骤4）中，所述滴入的时间为3～30min。
优选地，步骤5）中，所述十二烷基苯磺酸钠与混合溶液D的质量体积比（g/mL）为0.001～0.010:1。
优选地，步骤5）中，所述乳化的转速为300～2000r/min，至游离-NCO百分含量≤16%为止。
本发明的有益效果如下：
（1）本发明有机硅改性聚氨酯侧链大单体稳定性好，分子量适合，为聚羧酸的合成做重要准备；减水剂在水泥中的作用，主要是静电斥力和空间位阻这两类，采用这样的侧链大单体合成聚羧酸，空间位阻效应很好，合成的减水剂性能很好，因此，本发明有机硅改性聚氨酯侧链大单体特别适用于聚羧酸减水剂的合成；
（2）本发明合成方法工艺简单，成本低，适宜于工业化生产。
附图说明
图1是本发明实施例1有机硅改性聚氨酯侧链大单体的红外光谱图；
图2是本发明实施例2有机硅改性聚氨酯侧链大单体的红外光谱图。
具体实施方式
下面结合实施例和附图对本发明作进一步说明。
本发明实施例所使用的原料或化学试剂，如无特殊说明，均通过常规商业途径获得。
有机硅改性聚氨酯预聚体的合成方法参考例1
1）将25g聚醚二醇1000（含有2滴二月桂酸二丁基锡）以滴入的时间为1h，滴入11.1g异佛尔酮二异氰酸酯中，得36.1g混合溶液A；
2）将步骤1）所得36.1g混合溶液A以滴入的时间为1.5h，滴入二羟甲基丙酸（2.2g）的N-甲基吡咯烷酮溶液（5mL）中，得混合溶液B；
3）将步骤2）所得混合溶液B以滴入的时间为1.5h，滴入端羟基聚硅氧烷2000（6.6g）的1,4-丁二醇溶液（2mL）中，得50mL混合溶液C；
4）先后将2g二乙胺、1.5g三乙胺以滴入的时间分别为4min、3min，滴入步骤3）所得50mL混合溶液C中，得55mL混合溶液D；
5）将0.16g十二烷基苯磺酸钠加入步骤4）所得55mL混合溶液D中，在1000r/min下，乳化至游离-NCO百分含量为16%为止，得有机硅改性聚氨酯预聚体。
一种有机硅改性聚氨酯侧链大单体实施例1
所述有机硅改性聚氨酯侧链大单体的结构式为：
，m =10～20；其中，R4为
，k=10～20，l=10～20，其中，R1为
，R2为
，i=10～20，R3为
，j=10～20。
一种有机硅改性聚氨酯侧链大单体的合成方法实施例1
将参考例1所得20g有机硅改性聚氨酯预聚体降温至≤40℃，加入0.5g三乙胺和20g水，在速率为500r/min下，剪切4h后，加入1.2g乙二胺，在50℃，压力为0.1MPa下，进行扩链反应0.5h，减压至0.05MPa抽挥发物质，得有机硅改性聚氨酯侧链大单体。
如图1所示，3315 cm-1处的吸收峰为-N-H键的伸缩振动吸收峰；2950cm-1处的吸收峰为-CH3与-CH2的振动吸收峰；1720cm-1处的吸收峰为羰基的振动吸收峰；1601 cm-1处的吸收峰为苯环的振动吸收峰；1537 cm-1处出现的吸收峰为-N-H和C-N振动吸收峰的合频；1450cm-1处的吸收峰为-CH2-振动吸收峰；1231 cm-1处的吸收峰为C-O振动吸收峰；1069 cm-1处的吸收峰Si-O-Si 振动吸收峰；795cm-1处的吸收峰为Si原子上-CH3的振动吸收峰。以上红外光谱图表明：应在2273 cm-1处出现的异氰酸酯基特征吸收峰消失了，说明已经反应完全；1069 cm-1出现Si-O-Si振动吸收峰，表明端羟基硅氧烷已经成功嵌入到聚氨酯链段中。
一种有机硅改性聚氨酯侧链大单体实施例2
所述有机硅改性聚氨酯侧链大单体的结构式为：
，m=15～25；其中，R4为
，k=15～25，l=15～25，其中，R1为
，R2为
，i=15～25，R3为
，j=15～25。
一种有机硅改性聚氨酯侧链大单体的合成方法实施例2
将参考例1所得15g有机硅改性聚氨酯预聚体降温至≤35℃，加入0.3g三乙胺和30g水，在速率为1000r/min，剪切5h后，加入0.6g乙二胺，在40℃，压力为0.1MPa下，进行扩链反应1h，减压至0.02MPa抽挥发物质，得有机硅改性聚氨酯侧链大单体。
如图2所示，3355 cm-1处的吸收峰为-N-H键的伸缩振动吸收峰；2885 cm-1处的吸收峰为-CH3与-CH2的振动吸收峰；1730 cm-1处的吸收峰为羰基的振动吸收峰；1611 cm-1处的吸收峰为苯环的振动吸收峰；1539 cm-1处出现的吸收峰为-N-H和C-N振动吸收峰的合频；1455 cm-1处的吸收峰为-CH2-振动吸收峰；1235 cm-1处的吸收峰为C-O振动吸收峰；1077cm-1处的吸收峰Si-O-Si 振动吸收峰；804cm-1处的吸收峰为Si原子上-CH3的振动吸收峰。以上红外光谱图表明：应在2273 cm-1处出现的异氰酸酯基特征吸收峰消失了，说明已经反应完全；1077 cm-1出现Si-O-Si振动吸收峰，表明端羟基硅氧烷已经成功嵌入到聚氨酯链段中。
Claims (9)
1.一种有机硅改性聚氨酯侧链大单体，其特征在于：所述有机硅改性聚氨酯侧链大单体的结构式为：
，m=1～30；其中，R4为
，k=1～30，l=1～30，其中，R1为
，R2为
，i =1～30，R3为
，j=1～30。
2.一种如权利要求1所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：将有机硅改性聚氨酯预聚体降温，加入三乙胺和水，剪切后，加入乙二胺，进行扩链反应，减压抽挥发物质，得有机硅改性聚氨酯侧链大单体。
3.根据权利要求2所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：所述有机硅改性聚氨酯预聚体、三乙胺、水和乙二胺的质量比为1:0.01～0.11:1.0～2.0:0.02～0.10；所述降温至≤40℃；所述剪切的速率为300～2000r/min，时间为4～6h；所述扩链反应的温度为40～80℃，压力为0.10～0.12MPa，时间为0.5～1.0h；所述减压至0.01～0.10MPa。
4.根据权利要求2或3所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：所述有机硅改性聚氨酯预聚体的合成方法，包括以下步骤：
1）将聚醚二醇滴入异佛尔酮二异氰酸酯中，得混合溶液A；
2）将步骤1）所得混合溶液A滴入二羟甲基丙酸的N-甲基吡咯烷酮溶液中，得混合溶液B；
3）将步骤2）所得混合溶液B滴入端羟基聚硅氧烷的1,4-丁二醇溶液中，得混合溶液C；
4）先后将二乙胺、三乙胺滴入步骤3）所得混合溶液C中，得混合溶液D；
5）将十二烷基苯磺酸钠加入步骤4）所得混合溶液D中，乳化，得有机硅改性聚氨酯预聚体。
5.根据权利要求4所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：步骤1）中，所述聚醚二醇与异佛尔酮二异氰酸酯的质量比为2.0～2.5:1；所述聚醚二醇中含有1～4滴二月桂酸二丁基锡/25g聚醚二醇；所述滴入的时间为0.5～4.0h。
6.根据权利要求4或5所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：步骤2）中，所述混合溶液A与二羟甲基丙酸的质量比为1:0.01～0.07；所述二羟甲基丙酸与N-甲基吡咯烷酮溶液的质量体积比为1:2.0～3.6；所述滴入的时间为0.5～4.0h。
7.根据权利要求4或5所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：步骤3）中，所述混合溶液B中二羟甲基丙酸与端羟基聚硅氧烷的质量比为1:3～5；所述端羟基聚硅氧烷与1,4-丁二醇的质量体积比为1:0.2～0.4；所述滴入的时间为0.5～4.0h。
8.根据权利要求4或5所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：步骤4）中，所述二乙胺、三乙胺与混合溶液C的质量体积比为0.01～0.10:0.01～0.20:1；所述滴入的时间为3～30min。
9.根据权利要求4或5所述有机硅改性聚氨酯侧链大单体的合成方法，其特征在于：步骤5）中，所述十二烷基苯磺酸钠与混合溶液D的质量体积比为0.001～0.010:1；所述乳化的转速为300～2000r/min，至游离-NCO百分含量≤16%为止。
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