CN110982056B - 一种炔二醇嵌段聚醚的合成方法 - Google Patents
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Abstract
本发明涉及一种嵌段聚醚的合成方法，更具体的讲，是涉及一种炔二醇为起始剂与环氧乙烷和/或环氧丙烷在复合催化剂的作用下反应合成嵌段聚醚的方法。本发明在复合催化剂的作用下，控制反应温度和压力，炔二醇依次与环氧丙烷，环氧乙烷进行聚合反应，得到炔二醇嵌段聚醚。所述的复合催化剂包括选自烷基金属催化剂和有机碱催化剂所组成的混合物。本发明设计合成的炔二醇嵌段聚醚色泽底，且无需后处理，所以生产工艺简单，生产成本低；其次，产品的消泡性能和静态、动态表面张力更突出，应用性能更广。
Description
技术领域
本发明涉及一种嵌段聚醚的合成方法，更具体的讲，是涉及一种炔二醇为起始剂与环氧乙烷和/或环氧丙烷在复合催化剂的作用下反应合成嵌段聚醚的方法。
背景技术
炔二醇双子表面活性剂因其具有两个亲水基团，三键位于碳氢链的中央，在三键的两侧对称的分布乙氧基和羟基，这种特殊的分子结构使其具有良好的降低表面张力的能力、消泡和抑泡的能力等，广泛应用于水性涂料、印刷油墨、粘合剂、建筑材料等领域。专利CN102304029A公开了一种以氢氧化钠、三甲胺或三乙胺等碱为催化剂，在乙醚、苯或甲苯等溶剂中进行反应合成乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇的方法。本方法在溶剂进行反应，溶剂易挥发或易产生污染，工艺繁琐，成本较高。专利CN108517031A公开了以2,4,7,9-四甲基-5-癸炔-4,7-二醇为起始剂，以酸性离子液体1-丁基-3-甲基咪唑磷酸二氢盐、1-丁基-3-甲基咪唑硫酸氢盐或1-丁基-3-甲基咪唑三氟甲烷磺酸盐为溶剂和酸性催化剂，并以有机碱三甲胺、三乙胺等为碱性催化剂进行聚合反应，反应后以醚无水乙醚、四氢呋喃、甲基乙基醚等为萃取剂分离得到乙氧基化2,4,7,9-四甲基-5-癸炔-4,7-二醇。该方法工艺繁琐，成本较高，难以实现工业化生产。
现有技术合成的炔二醇类多功能表面活性剂多是以三乙胺为催化剂，合成的产品色度较高，需后处理，或需在溶剂中进行反应、萃取，工艺繁琐，成本较高，易产生污染；且多是用环氧乙烷进行聚合，产品的渗透性能以及消泡性能与硅酮类或氟类表面活性剂相比还有差距；无论是色泽问题还是性能问题都限制了炔二醇类多功能表面活性剂的应用范围，尤其是在一些要求较高的领域。
发明内容：
为克服现有技术的不足，本发明提供了一种炔二醇嵌段聚醚的合成方法，具体方案如下：
所述的炔二醇嵌段聚醚分子式为：
其中，R1、R4独自选自C3~C10的烷基，R2和R3为甲基或乙基，m取值范围为1～6，n的取值范围为3～15。
一种炔二醇嵌段聚醚的生产工艺，包括如下步骤：
（a）向反应釜中依次加入复合催化剂和预热好的炔二醇起始剂，排氮3～4次，110℃脱水1小时；控制反应温度，缓慢滴加环氧丙烷进行聚醚反应，熟化后，调节温度进行脱气，除掉未反应的环氧丙烷；
（b）控制反应温度，滴加环氧乙烷，进行聚醚反应，并熟化；
（c）反应结束后控温脱气，降温中和（中和选用的酸为磷酸、盐酸、柠檬酸和醋酸中的至少一种，优选醋酸）得到产品。
所述的复合催化剂为烷基金属催化剂和有机碱催化剂的混合物。
所述步骤（a）中的炔二醇起始剂选自4,7-二甲基-5-癸炔-4,7-二醇、2,4,7,9-四甲基-5-癸炔二醇、2,5,8,11-四甲基-6-十二炔-5,8-二醇、2,3,5,8,10,11-六甲基-6-十二炔-5,8二醇或7,10-二醇中一种或多种。
所述炔二醇起始剂:PO:EO=1:1～8:1～20。
所述炔二醇起始剂:PO:EO=1:1～6:3～15.
所述烷基金属催化剂为nBuLi、CaEt2、AlEt3和ZnEt3中的一种或多种的混合物，所述有机碱催化剂为二甲胺、三甲胺、三乙胺和N-甲苯胺中的一种或多种的混合物。
所述复合催化剂为AlEt3和三乙胺按重量比1:1～8的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.01%～2%，
所述复合催化剂为AlEt3和三乙胺按重量比1:1～6的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.05%～1%。
所述步骤（a）的反应温度为60～150℃，优选反应温度为60～130℃。
所述步骤（b）的反应温度为50～120℃，优选55～110℃。
所述步骤（c）的脱气温度为60～120℃，优选100℃～110℃，脱气时间为1小时。
本发明炔二醇嵌段聚醚的合成方法思路为：在复合催化剂的作用下，控制反应温度和压力，炔二醇依次与环氧丙烷，环氧乙烷进行聚合反应，得到炔二醇嵌段聚醚。所述的复合催化剂包括选自烷基金属催化剂和有机碱催化剂所组成的混合物。
炔二醇表面活性剂的应用主要运用了其低泡、抑泡和高表面活性的性质，我们根据表面活性剂性质与结构的关系，设计了一种嵌段共聚物，PO嵌段的引入，使体系泡沫液膜间的空隙增大，排液速率加快，起泡性降低，同时带支链的PO链增强了其渗透性，使其应用性能更加优异；炔二醇表面活性剂色泽深的问题多是因为三乙胺催化剂引起的，我们将适量的烷基金属催化剂与有机碱催化剂进行复配作为复合催化剂，烷基金属催化剂本身活性很低，但与有机碱催化剂混合后可形成稳定的络合物，催化活性提高，催化剂的用量减少，从而合成的炔二醇表面活性剂颜色较浅，解决了炔二醇表面活性剂传统合成工艺中颜色较深需要后处理的问题。本发明中的压力均指表压；本发明中使用量比例均指摩尔比；本发明具体实施中色度的测量方法采用GB/T605-2006；本发明具体实施中产品的羟值测试方法采用GB/T7383-2007(非离子表面活性剂羟值的测定)；本发明具体实施中产品的表面张力和动态表面张力采用泡压法。
与现有的技术相比，本发明设计合成的炔二醇嵌段聚醚色泽底，且无需后处理，所以生产工艺简单，生产成本低；其次，产品的消泡性能和静态、动态表面张力更突出，应用性能更广。
具体实施方式
实施例1
在2.5L压力反应釜中加入1mol（226g）2,4,7,9-四甲基-5-癸炔-4,7-二醇和0.113g的AlEt3与三乙胺（1:3）组成的复合催化剂；开启搅拌，用氮气置换釜内气体3次，升温至110℃左右，真空脱水1小时；将温度控制在100℃～105℃之间，缓缓滴加9mol环氧乙烷，将压力控制在0.35Mpa以下，熟化0.5小时左右，直至反应压力基本不变；然后将反应温度控制在65℃～70℃之间，缓慢滴加1mol环氧丙烷，将压力控制在0.35Mpa以下，并熟化3小时左右，直至反应压力基本不变；反应结束后，将温度控制在100℃左右，真空脱气1小时，除去未反应的环氧乙烷和环氧丙烷或部分催化剂；将温度降到65℃，用醋酸中和，冷却得到炔二醇嵌段聚醚产品，取样进行性能测试。
实施例2～10
其它与实施例1的设置相同，区别在于催化剂的种类、配比和添加量，PO/EO的配比、反应的先后顺序以及相应时段的反应温度，具体相关参数如表1所示。
表1：实施例1～10的工艺参数设置表
为了进一步说明效果，对实施例1～10的静态表面张力、动态表面张力、色泽和羟值进行检测，为便于比较，将其列于表2。
表2：实施例1～10的指标测试表
对比例1～5
对比例1～5与实施例1设置相同，只是催化剂的种类不同，具体测试指标如表3所示。
表3：对比例1～5的指标测试表
本说明书中公开的所有特征，或公开的所有方法或过程中的步骤，除了互相排斥的特征和/或步骤以外，均可以以任何方式组合。
Claims (6)
1.一种炔二醇嵌段聚醚，其特征在于，所述的炔二醇嵌段聚醚分子式为：
其中，R 1 、R 4 独自选自C 3 ～C 10 的烷基，R 2 和R 3 为甲基或乙基，m取值范围为1～6，n的取值范围为3～15；所述炔二醇嵌段聚醚的生产工艺，包括如下步骤：
(a)向反应釜中依次加入复合催化剂和预热好的炔二醇起始剂，排氮，脱水；控制反应温度，缓慢滴加环氧丙烷进行聚醚反应，熟化后，调节温度进行脱气，除掉未反应的环氧丙烷；
(b)控制反应温度，滴加环氧乙烷，进行聚醚反应，并熟化；
(c)反应结束后升温脱气，降温中和得到产品；
所述复合催化剂为AlEt 3 和三乙胺按重量比1:1～8的混合物；复合催化剂用量为炔二醇起始剂物质的量的0.01％～2％；所述步骤(a)的反应温度为60～150℃，所述步骤(b)的反应温度为50～120℃。
2.如权利要求1所述的一种炔二醇嵌段聚醚，其特征在于：所述步骤(a)中的炔二醇起始剂选自4,7-二甲基-5-癸炔-4,7-二醇、2,5,8,11-四甲基-6-十二炔-5,8-二醇、2,3,5,8,10,11-六甲基-6-十二炔-5,8二醇或7,10-二醇中一种或多种。
3.如权利要求1所述的一种炔二醇嵌段聚醚，其特征在于：所述炔二醇起始剂:PO:EO＝1:1～8:1～20。
4.如权利要求1所述的一种炔二醇嵌段聚醚，其特征在于：所述炔二醇起始剂:PO:EO＝1:1～6:3～15。
5.如权利要求1所述的一种炔二醇嵌段聚醚，其特征在于：所述复合催化剂为AlEt 3 和三乙胺按重量比1:1～6的混合物；所述复合催化剂用量为炔二醇起始剂物质的量的0.05％～1％。
6.如权利要求1所述的一种炔二醇嵌段聚醚，其特征在于：所述步骤(a)的反应温度为60～130℃，所述步骤(b)的反应温度为55～110℃。
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| CN107935826A (zh) * | 2017-11-21 | 2018-04-20 | 浙江皇马科技股份有限公司 | 一种低温稳定性好的脂肪醇嵌段聚醚及其制备方法和应用 |
| CN109970964A (zh) * | 2019-03-29 | 2019-07-05 | 浙江皇马科技股份有限公司 | 一种叔炔醇聚醚的制备方法 |
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| CN107935826A (zh) * | 2017-11-21 | 2018-04-20 | 浙江皇马科技股份有限公司 | 一种低温稳定性好的脂肪醇嵌段聚醚及其制备方法和应用 |
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