CN117304471A - 一种硬泡聚醚多元醇的制备方法 - Google Patents
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Abstract
本发明涉及聚醚多元醇制备技术领域,具体为一种硬泡聚醚多元醇的制备方法,制备步骤为以山梨醇为起始剂,与催化剂加入至反应釜内,经氮气置换、搅拌、升温、脱水处理,向反应釜内加入官能度调节剂,待搅拌均匀后得到复合起始剂;向反应釜内加入环氧丙烷,与所述复合起始剂进行聚合反应,熟化得到山梨醇聚醚多元醇粗品;对所述山梨醇聚醚多元醇粗品进行后处理,得到所述山梨醇基聚醚多元醇产品;本发明合成的聚醚多元醇指标符合硬泡聚醚多元醇的指标要求,粘度较低,具有较好的流动性,与环戊烷具有较好的相容性,适合作为冰箱保冷的发泡材料,增加了起始剂与环氧丙烷的互溶性,提高了反应速度,同时提高了生产效率。
Description
技术领域
本发明涉及聚醚多元醇制备技术领域,具体为一种硬泡聚醚多元醇的制备方法。
背景技术
聚醚多元醇的工业化生产一般以负离子开环催化聚合为主,通常以氢氧化钾或二甲胺为催化剂,以甘油或蔗糖等小分子多元醇或其它含活泼氢化合物如胺、醇胺为起始剂,以氧化丙烯(环氧丙烷,简称PO)或者氧化丙烯和氧化乙烯(环氧乙烷,简称EO)的混合物为单体,在一定的温度及压力下进行开环聚合,得到粗聚醚,再经过中和、精制等步骤,得到聚醚成品。这类聚醚多元醇包括软泡和弹性体用长链聚醚、硬泡用短链多官能度聚醚,已广泛用于聚氨酯泡沫塑料及少量弹性制品。
硬泡聚醚多元醇产品主要应用于绝热保温材料,如管道保温、储罐保温,建筑保温、板材、冰箱、冰柜、热水器等方面,聚氨酯硬质泡沫具有质量轻,导热系数小,机械强度高,粘结性能好等优点。
通常生产硬泡聚醚多元醇主要以丙二醇、二甘醇、丙三醇、季戊四醇、木糖醇、山梨醇、蔗糖等含有活泼氢的为起始剂,在催化剂的作用下与环氧丙烷进行聚合反应。
山梨醇作为一种6官能度起始剂,其合成的硬泡聚醚应用在聚氨酯泡沫上具有尺寸稳定性、机械性能、软化温度及耐油性能方面优于传统的3官能度聚醚。山梨醇常温下是固体,与环氧丙烷的相容性较差,因此在反应初期进料速度很慢,压力较高,因此需要加入合适的调节剂来控制提高前期反应速度,同时可以调节聚醚的官能度。
经检索,中国专利公开号:CN102617848A公开了一种山梨醇聚醚多元醇的制备方法,以结晶山梨醇和环氧丙烷为原料,在催化剂和调节剂的作用下进行聚合反应制备山梨醇聚醚多元醇。但是该方案中选用的调节剂为乙二醇或丙三醇,因为乙二醇或丙三醇对于山梨醇的溶解度有限,因此前期的反应速度依然较慢。
又如,中国专利公开号CN106146823A公开了一种纯结晶山梨醇聚醚多元醇的制备方法,以纯结晶山梨醇为起始剂,以碱金属为催化剂,在一定的温度和压力下,环氧丙烷分三个阶段聚合反应,得到纯结晶山梨醇聚醚多元醇。但是该方案中山梨醇常温为固体,温度上升后山梨醇熔化开启搅拌会出现团结现象,易使搅拌受损,且在熔化状态下与环氧丙烷的互溶性很差,因此在初期反应速度很慢,需要很长一段时间的诱导期;硬泡聚醚的官能度通常在4-4.5之间,通常需要高官能度起始剂和低官能度进行复配,纯山梨醇聚醚多元醇的粘度较大,且流动性较差,直接影响下游应用。
发明内容
(1)要解决的技术问题
针对现有技术的不足,本发明的目的在于提供一种硬泡聚醚多元醇的制备方法,解决现有技术中山梨醇与环氧丙烷互容性很差问题,提升山梨醇与环氧丙烷前期反应速度,提高生产效率。
(2)技术方案
为了解决上述技术问题,本发明提供了这样一种硬泡聚醚多元醇的制备方法,包括以下制备步骤:
S1、以山梨醇为起始剂,与催化剂加入至反应釜内,经氮气置换、搅拌、升温、脱水处理,向反应釜内加入官能度调节剂,待搅拌均匀后得到复合起始剂;
S2、向反应釜内加入环氧丙烷,与所述复合起始剂进行聚合反应,熟化得到山梨醇聚醚多元醇粗品;
S3、对所述山梨醇聚醚多元醇粗品进行后处理,得到所述山梨醇基聚醚多元醇产品;
所述步骤S1中的官能度调节剂为水、乙二醇、丙二醇、二甘醇或三官能度的甘油、三羟甲基丙烷、三羟甲基乙烷中的一种或者两种混合使用,所述官能度调节剂与山梨醇复配后平均官能度在4-4.5之间,优选水作为官能度调节剂。
优选的,所述催化剂为氢氧化钾。
优选的,所述步骤S2中环氧丙烷分两个阶段添加,先缓慢滴加环氧丙烷,待所述反应釜压力开始下降,加快环氧丙烷的滴加速度。
优选的,所述反应釜内的温度为105-120℃,所述反应釜内的压力<0.40Mpa。
优选的,所述步骤S1中的山梨醇为70%的山梨醇水溶液或70%的山梨醇水溶液与部分结晶山梨醇的结合。
优选的,在步骤S3中,所述后处理依次包括水解、中和、吸附、脱水、过滤处理。
(3)有益效果
与现有技术相比,本发明的有益效果在于:
本发明采用价格低廉的水作为起始剂与山梨醇复配合成硬泡聚醚多元醇,控制聚醚官能度在4.0-4.5之间,山梨醇极易溶于水,可以加快起始剂与环氧丙烷的反应速度,控制反应温度105-115℃,压力<0.4Mpa,合成的聚醚多元醇指标符合硬泡聚醚多元醇的指标要求,粘度较低,具有较好的流动性,与环戊烷具有较好的相容性,适合作为冰箱保冷的发泡材料,本制备方法中的原料易得,成本较低,反应操作简单,安全环保,不需要特殊的反应设备,粘度较低,具有较好的流动性,且与环戊烷有较好的相容性,适合冰箱保冷发泡材料,增加了起始剂与环氧丙烷的互溶性,提高了反应速度,同时提高了生产效率。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明的技术方案进行详细的描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施方式,都属于本发明所保护的范围。
实施例与对比例中采用的原料,如果没有特别限定,那么均是现有技术公开的,例如可直接购买获得或者根据现有技术公开的制备方法制得。
本发明提供一种技术方案:
一种硬泡聚醚多元醇的制备方法,包括以下制备步骤:
步骤一、以山梨醇为起始剂,与催化剂加入至反应釜内,经氮气置换、搅拌、升温、脱水处理,向反应釜内加入官能度调节剂,待搅拌均匀后得到复合起始剂;
步骤二、向反应釜内加入环氧丙烷,与复合起始剂进行聚合反应,熟化得到山梨醇聚醚多元醇粗品;
步骤三、对山梨醇聚醚多元醇粗品进行后处理,得到山梨醇基聚醚多元醇产品;
步骤一中官能度调节剂为水、乙二醇、丙二醇、二甘醇或三官能度的甘油、三羟甲基丙烷、三羟甲基乙烷中的一种或者两种混合使用,官能度调节剂与山梨醇复配后平均官能度在4-4.5之间,优选水作为官能度调节剂。
需要说明的是,因为水作为廉价的起始剂,取用非常方便,且山梨醇在水中的溶度大大优于其他醇类,水作为官能度调节剂并非全部参与反应,只有50%左右的水参与反应,因此配方设计时只需要计算参与反应的水的量即可。
进一步地,催化剂为氢氧化钾(KOH)。
进一步地,步骤二中环氧丙烷分两个阶段添加,先缓慢滴加环氧丙烷,待反应釜压力开始下降,加快环氧丙烷的滴加速度。
进一步地,反应釜内的温度为105-120℃,反应釜内的压力<0.40Mpa。
进一步地,步骤一中山梨醇为70%的山梨醇水溶液或70%的山梨醇水溶液与部分结晶山梨醇的结合。
进一步地,在步骤三中,后处理依次包括水解、中和、吸附、脱水、过滤处理。
具体实施案例
实施例1
将70%的山梨醇水溶液241g和3g的KOH加入至2L反应釜,氮气置换3次,搅拌,升温,控制温度在110-120℃下,脱水3小时,加水24.6g,待搅拌均匀后,控制釜内温度在105-115℃下,缓慢滴加819g环氧丙烷,20分钟后压力开始下降,环氧丙烷开始反应,此时可以加快环氧丙烷的滴加速度,控制压力<0.40Mpa,滴加完成后保压反应3小时,压力下降可以补充氮气,熟化完成后需进行水解、中和、吸附、脱水、过滤等后处理,方可得到山梨醇与水复合起始剂聚醚多元醇,羟值391.3mgKOH/g,粘度2563mpa·s,PH值6.1,钾离子8ppm,水分0.05%,满足山梨醇聚醚多元醇指标要求。
实施例2
将70%的山梨醇水溶液82g和111.3g的结晶山梨醇以及3g的KOH加入至2L反应釜,氮气置换3次,搅拌,升温,待搅拌均匀后,控制釜内温度在105-115下,缓慢滴加819g环氧丙烷,18分钟后压力开始下降,环氧丙烷开始反应,此时可以加快环氧丙烷的滴加速度,控制压力<0.40Mpa,滴加完成后保压反应3小时,压力下降可以补充氮气,熟化完成后需进行水解、中和、吸附、脱水、过滤等后处理,方可得到山梨醇与水复合起始剂聚醚多元醇,羟值390.8mgKOH/g,粘度2539mpa·s,PH值6.0,钾离子8ppm,水分0.05%,满足山梨醇聚醚多元醇指标要求。
实施例3
将70%的山梨醇水溶液240g和3g的KOH加入至2L反应釜,氮气置换3次,搅拌,升温,控制温度在110-120℃下,脱水3小时后,加二甘醇73.2g,待搅拌均匀后,控制釜内温度在105-115下,缓慢滴加759g环氧丙烷,40分钟后压力开始下降,环氧丙烷开始反应,此时可以加快环氧丙烷的滴加速度,控制压力<0.40Mpa,滴加完成后保压反应3小时,压力下降可以补充氮气,熟化完成后需进行水解、中和、吸附、脱水、过滤等后处理方可得到山梨醇与水复合起始剂聚醚多元醇,羟值391.3mgKOH/g,粘度3245mpa·s,PH值5.9,钾离子7ppm,水分0.06%。
将上述实施例1至实施例3制造出的山梨醇聚醚多元醇进行发泡对比实验,控制室温25±2℃,料温25±1℃;
测试结果如表1所示:
表1为山梨醇聚醚多元醇发泡对比实验测试结果表
综上所述,从以上实施例可以看出,山梨醇与水作为复合起始剂制备的硬泡聚醚多元醇,指标合格,满足硬泡聚醚的指标要求,且粘度低于以二甘醇作为官能度调节剂的聚醚,具有更好的流动性,下游客户拥有较好的操作空间。
本实施例中的所有技术特征均可根据实际需要而进行自由组合。
上述实施例为本发明较佳的实现方案,除此之外,本发明还可以其它方式实现,在不脱离本技术方案构思的前提下任何显而易见的替换均在本发明的保护范围之内。
Claims (6)
1.一种硬泡聚醚多元醇的制备方法,其特征在于,包括以下制备步骤:
S1、以山梨醇为起始剂,与催化剂加入至反应釜内,经氮气置换、搅拌、升温、脱水处理,向反应釜内加入官能度调节剂,待搅拌均匀后得到复合起始剂;
S2、向反应釜内加入环氧丙烷,与所述复合起始剂进行聚合反应,熟化得到山梨醇聚醚多元醇粗品;
S3、对所述山梨醇聚醚多元醇粗品进行后处理,得到所述山梨醇基聚醚多元醇产品;
步骤S1中所述官能度调节剂为水、乙二醇、丙二醇、二甘醇或三官能度的甘油、三羟甲基丙烷、三羟甲基乙烷中的一种或者两种混合使用,所述官能度调节剂与山梨醇复配后平均官能度在4-4.5之间,优选水作为官能度调节剂。
2.根据权利要求1所述的一种硬泡聚醚多元醇的制备方法,其特征在于,所述催化剂为氢氧化钾。
3.根据权利要求1所述的一种硬泡聚醚多元醇的制备方法,其特征在于,步骤S2中所述环氧丙烷分两个阶段添加,先缓慢滴加环氧丙烷,待所述反应釜压力开始下降,加快环氧丙烷的滴加速度。
4.根据权利要求1所述的一种硬泡聚醚多元醇的制备方法,其特征在于,所述反应釜内的温度为105-120℃,所述反应釜内的压力<0.40Mpa。
5.根据权利要求1所述的一种硬泡聚醚多元醇的制备方法,其特征在于,步骤S1中所述山梨醇为70%的山梨醇水溶液或70%的山梨醇水溶液与部分结晶山梨醇的结合。
6.根据权利要求1所述的一种硬泡聚醚多元醇的制备方法,其特征在于,在步骤S3中,所述后处理依次包括水解、中和、吸附、脱水、过滤处理。
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