CN111349229A - 稳定分散剂及其在制备共聚物多元醇中的应用 - Google Patents
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Abstract
本发明提供一种稳定分散剂及其在制备共聚物多元醇中的应用,所述稳定分散剂的制备方法包括:1)将多元醇与二酐化合物接触反应,制得加合物;2)将步骤1)所得加合物与环氧化合物进行开环加成反应,制得所述稳定分散剂;其中,所述二酐化合物中不含有能与烯属不饱和单体共聚的双键,所述环氧化合物中含有能与烯属不饱和单体共聚的双键;所述多元醇为聚酯多元醇和/或聚醚多元醇,优选为聚醚多元醇。通过这种制备方法得到的稳定分散剂,具有多活性位点锚固功能,将其应用于共聚物多元醇的合成中,能够获得较为单一粒径尺寸的共聚物多元醇。
Description
技术领域
本发明涉及共聚物多元醇制备技术领域,特别涉及一种新型稳定分散剂的合成及其在共聚物多元醇中的应用。
背景技术
在制造聚氨酯泡沫塑料过程中经常会使用共聚物多元醇提高改进承载性和其它性能,所述共聚物多元醇是聚合物在多元醇中的分散体。常用的类型有,乙烯基聚合物颗粒多元醇(苯乙烯-丙烯腈的分散体),聚脲颗粒分散体(PHD多元醇),多异氰酸酯加聚物(PIPA多元醇,聚氨酯-聚脲颗粒的分散体)。目前商业化较广泛的是苯乙烯/丙烯腈共聚物在多元醇中的分散体(简称共聚物多元醇或是聚合物分散体,简写为POP)。
其稳定性多借助于不饱和化合物的聚合物与多元醇分子间形成的接枝或加成产物的稳定效应。现有技术采用的稳定剂均为单活性位点的,如图6所示。
通常的方法为向多元醇中引入少量的不饱和度。如US3652639、US3823201所公开的,采用具有特定反应性不饱和度的稳定分散剂用于制备共聚物多元醇,但是制备的共聚物多元醇固含量偏低。稍后的专利US5196476、EP0786480公开了预制稳定剂法制备POP的方法,首先,自由基聚合引发剂和稳定分散剂及烯键式不饱和单体反应制备预制稳定剂,然后,在聚醚存在下预制稳定剂继续与烯属不饱和单体聚合制备POP,该方法存在着稳定分散剂使用量大,粘度偏高的缺陷。
发明内容
有鉴于此,本发明提供一种新型稳定分散剂,该稳定分散剂特别适用于在共聚物多元醇制备中的应用,该稳定分散剂具有更多活性位点,具有相对较低的粘度,且能够制得粒径尺寸较为单一的共聚物多元醇。
本发明为达到其目的,采用的技术方案如下:
本发明一方面提供一种稳定分散剂的制备方法,所述制备方法包括如下步骤:1)将多元醇与二酐化合物接触反应,具体为酸酐开环反应,得到加合物;2)将步骤1)所得加合物与环氧化合物发生开环加成反应,制得所述稳定分散剂;
其中,所述二酐化合物中不含有能与烯属不饱和单体共聚的双键,所述环氧化合物中含有能与烯属不饱和单体共聚的双键;所述多元醇为聚醚多元醇和/或聚酯多元醇,优选为聚醚多元醇。通过这种制备方法得到的稳定分散剂,具有多活性位点锚固功能,将其应用于共聚物多元醇的合成中,能够获得较为单一粒径尺寸的共聚物多元醇,同时具有较好的稳定分散性。
在一些优选实施方式中,所述二酐化合物优选含有除酸酐环状结构以外的环状结构(称之为非二酸酐环的环状结构);在一些优选实施方式中,所述二酐化合物选自但不限于均苯四甲酸二酐、二苯酮四甲酸二酐、联苯四甲酸二酐、二苯醚四甲酸二酐、六氟四甲酸二酐、三苯双醚四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、环丁烷四甲酸二酐、双酚A二醚四甲酸二酐、萘-1,4,5,8-四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-三苯双醚四甲酸二酐、1,2,3,4-环戊烷四甲酸二酐化合物中的一种或两种以上的组合,进一步优选均苯四甲酸二酐和环丁烷四甲酸二酐中的一种或两种。
本发明在制备稳定分散剂时,所用的环氧化合物可以是任何含有能与烯属不饱和单体聚合的双键(烯属双键)的环氧化物,优选是1,2-环氧化物。在一些优选实施方式中,所述环氧化合物选自但不限于缩水甘油醚、丙烯酸缩水甘油酯及其衍生物中的一种或两种以上的组合,优选烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯中的一种或两种以上的组合,更优选甲基丙烯酸缩水甘油酯。所述烯属不饱和单体的具体种类并无限制,例如为制备共聚物多元醇可以适用的各种烯属不饱和单体。
在一些优选实施方式中,所述多元醇特别是聚醚多元醇与所述二酐化合物的摩尔比为0.2-4∶1,优选1.5-2.5∶1;所述二酐化合物与所述环氧化合物的摩尔比为0.1-2∶1,优选0.3-8∶1。
本发明在制备稳定分散剂时,在步骤2)中可以使用催化剂来促进反应的进行。催化剂的用量优选为所述多元醇质量的0.01-0.5%(w/w)。优选的,所述催化剂为有机膦化合物、有机胺化合物和三级胺中的一种或两种以上的组合;进一步优选的,所述催化剂选自有机磷卤化物、四甲基氢氧化膦中的一种或两种以上的组合;所述有机胺化合物选自咪唑或咪唑衍生物中的至少一种;所述三级胺选自三乙胺、二乙烯三胺、三丙胺和三丁胺中的一种或两种以上的组合;更进一步优选的,所述有机磷卤化物选自四甲基碘化膦、四甲基溴化膦、三甲基苄基溴化膦、三甲基苄基氯化膦、乙基三苯基碘化膦、乙基三(对甲苯基)溴化膦、乙基三(对甲苯基)氯化膦中的一种或两种以上的组合。
在一些优选实施方式中,步骤1)中,所述多元醇的数均分子量为2500-15000,优选5000-14000;平均官能度为2.0以上,优选2.5-6.0。
在制备稳定分散剂时所用的多元醇优选采用聚醚多元醇(通常也称聚氧化烯多元醇),该类聚醚多元醇是通过使具有活性氢原子的起始化合物与一种或多种环氧化合物反应而得到,所述环氧化合物如环氧乙烷、环氧丙烷、环氧丁烷中的一种或多种。
步骤1)和步骤2)的反应在有溶剂或无溶剂存在下进行;优选所述溶剂为不含质子的极性溶剂,以能够溶解所述二酐化合物和所述环氧化合物为佳,例如丙酮、四氢呋喃、甲乙酮中的一种或几种。
本发明在制备所述稳定分散剂时,优选步骤1)和步骤2)的反应温度分别为60-150℃,更优选80-130℃。步骤1)和步骤2)的反应在常压下进行即可。
本发明在制备所述稳定分散剂时,任选的(即可添加也可不添加),在步骤2)反应体系中还添加有阻聚剂,例如所述阻聚剂包括但不限于对苯二酚、对叔丁基邻苯二酚、对羟基苯甲醚、甲基氢醌、吩噻嗪和二苯胺中的一种或多种。所述阻聚剂的用量为所述多元醇总质量的0~1.5%,优选30~2000ppm。
具体的,在一些实施方式中,制备所述稳定分散剂的反应示意图如图1所示;另一些实施方式中,制备所述稳定分散剂的反应示意图如图2所示。为了便于理解,一些实施方式得到的稳定分散剂的结构示意图如图7所示,具有双活性位点,该图所示的是一种具有双聚醚链段的“Gemini”型稳定分散剂。
本发明提供的稳定分散剂特别适合在制备共聚物多元醇时使用。共聚物多元醇的制备为本领域所周知的,由至少一种烯属不饱和单体和基础聚醚多元醇在稳定分散剂的存在下,经引发剂引发聚合而得。优选反应温度为80-150℃,更优选90-120℃,反应压力为0-1Mpa,优选常压-0.5Mpa。
制备共聚物多元醇时,所用的基础聚醚多元醇的选择是由共聚物多元醇的最终用途决定的,本领域技术人员可以根据需要而具体选择。例如共聚物多元醇用于块状聚氨酯软泡的生产,就选用通用聚氨酯软泡用聚醚多元醇,一般羟值为54~58mgKOH/g的三官能度的基础聚醚多元醇;用于高回弹泡沫的生产,就选用高回弹泡沫用聚醚多元醇,一般羟值为33.5~36.5mgKOH/g的高活性的三官能度的基础聚醚多元醇。较佳的,本发明优选采用的基础聚醚多元醇,为羟值54~58mgKOH/g的三官能度的聚醚多元醇。
在一些优选实施方式中,所述烯属不饱和单体的用量为所述基础聚醚多元醇、所述烯属不饱和单体和所述稳定分散剂的总质量的20-55wt%。
在一些优选实施方式中,所述稳定分散剂的用量为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.3%~10%,进一步优选2%~5%。
本发明制备共聚物多元醇所用的烯属不饱和单体,可以采用本领域所允许使用的各种烯属不饱和单体,对此不作特别限定;包括但不限于脂肪族共轭二烯、乙烯基芳族化合物、α,β-烯属不饱和腈、α,β-烯属不饱和腈酰胺、α,β-烯属不饱和羧酸、α,β-烯属不饱和羧酸酯、乙烯基酯、乙烯基醚、乙烯基酮、乙烯基和亚乙烯基卤化物中的一种或多种;优选乙烯基芳香化合物和烯属不饱和腈。更优选采用苯乙烯和丙烯腈中的一种或两种,所述苯乙烯和丙烯腈的摩尔比为50∶50-100∶0。
在制备共聚物多元醇时,烯属不饱和单体的聚合通过引发剂引发而进行;在一些优选实施方式中,所述引发剂的用量为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.01-5wt%;引发剂的具体种类不作特别限定,采用本领域所常用的聚合引发剂均可,例如选自过氧化物和偶氮化合物中的一种或两种以上的组合;过氧化物比如有过氧化二苯甲酰、过氧化月桂酰、叔丁基过氧化氢、过氧化苯甲酰和过氧化二叔丁基等中的一种或几种;偶氮化合物比如有偶氮二异丁腈(AIBN)、偶氮异戊腈(AMBN)、偶氮二异丁酸二甲酯(V601)等中的一种或几种。
本发明中,烯属不饱和单体的聚合优选在链转移剂存在下进行;其用量优选为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.1-6wt%,更优选0.2-5wt%。链转移剂的具体种类不作特别限定,例如1-丁醇、2-丁醇、异丙醇、乙醇、甲醇、水、环己烷和硫醇,如十二烷硫醇、乙硫醇、1-庚硫醇、2-辛硫醇和甲苯硫醇等中的一种或几种。
共聚物多元醇制备过程中还可以根据需要而使用其他化合物,如促进各组分混合的化合物,具有粘度降低效果的化合物和/或能使一种或多种所用组分更好地溶于反应介质中的化合物。具有粘度降低效果,因而使各组分更好混合的化合物例如甲苯、二氯甲烷等中的一种或几种。
本发明中,共聚物多元醇的制备工艺可以为间歇的或是连续操作完成。共聚物多元醇制备完毕后,一般需要经过未反应单体和链转移剂脱除处理,这是本领域所熟知的,本领域内的常见脱除手段有蒸馏、闪蒸、刮板或薄膜蒸发等化工单元操作,对此不作一一赘述。
本发明提供的共聚物多元醇非常适合于聚氨酯泡沫材料的合成,聚氨酯泡沫材料,可通过使包含上文所述的制备方法得到的共聚物多元醇和多异氰酸酯的组合物进行发泡而得到软质聚氨酯泡沫。聚氨酯泡沫的制备过程是本领域内已知的,在共聚物多元醇和多异氰酸酯的发泡体系中,根据需要可添加有聚氨酯催化剂、交联剂、发泡剂、泡沫稳定剂、助剂等。
在制备共聚物多元醇时,一些实施方式中,所使用的聚氨酯催化剂例如为有机金属化合物,如辛酸亚锡、油酸亚锡、二月桂酸二丁基锡、乙酸二丁基锡和二乙酸二丁基锡;或例如为有机胺类催化剂,如二(2,2′-二甲氨基)乙基醚,三甲胺,三乙胺,三亚乙基二胺和二甲基乙醇胺。在制备共聚物多元醇时,所使用的发泡剂例如包括水、丙酮、二氧化碳、卤代烃、脂族烷烃和脂环族烷烃等。合适的交联剂例如为二乙醇胺(DEOA)等。合适的泡沫稳定剂例如为有机聚硅氧烷表面活性剂等。另外,在聚氨酯泡沫的制备过程中还常用到如阻燃剂、填料、光稳定剂、抗氧剂等助剂。
本发明提供的技术方案具有如下有益效果:
本发明制备的稳定分散剂不需要经过精制或分离,可以直接用于后续反应。本发明稳定分散剂的制备过程为常压反应,不涉及使用EO封端。另外制备的稳定分散剂粘度低,在制备共聚物多元醇时,与聚合反应体系中的物料混合操作简便。同时,因为本发明提供的稳定分散剂中含有较多活性位点,合成的共聚物多元醇具有较好的稳定分散性,制备的共聚物多元醇能够获得较为单一的粒径尺寸,应用于下游泡沫制品可以获得优异的开孔性能和匀泡特性。
附图说明
图1是一种实施方式中制备稳定分散剂的反应示意图;
图2是另一种实施方式中制备稳定分散剂的反应示意图;
图3是实施例3所得共聚物多元醇SEM检测结果;
图4是实施例4所得共聚物多元醇SEM检测结果;
图5是对比例所得共聚物多元醇SEM检测结果。
图6是现有技术稳定剂的结构示意图;
图7本发明一些实施方式得到的稳定分散剂的结构示意图。
具体实施方式
为了更好的理解本发明的技术方案,下面结合实施例进一步阐述本发明的内容,但本发明的内容并不仅仅局限于以下实施例。
下面对实施例或对比例中涉及的检测方法进行如下说明:
羟值:GB 12008.3-2009塑料聚醚多元醇第3部分:羟值的测定;
黏度:GB 12008.7-2010塑料聚醚多元醇第7部分:黏度的测定;
不饱和度:GB 12008.6-2010塑料聚醚多元醇第6部分:不饱和度的测定;
固含:GB/T 31062-2014聚合物多元醇;
如无特殊说明,本实施例反应压力均为常压反应,反应涉及过程均为氮气保护下进行反应;
聚醚多元醇A:使用山梨醇为起始剂,催化剂(KOH)浓度为环氧丙烷(PO)质量的0.3wt%%(w/w),控制反应温度在110±5℃左右,压力低于0.15MPa进行反应,待PO投料结束后老化继续反应2h,脱气1h。脱气结束后开始投环氧乙烷(EO),控制反应温度在110±5℃左右,压力低于0.15MPa进行反应,投料结束后老化继续反应2h,脱气1h,此时反应阶段结束。控制温度在85-90℃,加入软水和磷酸中和,脱水,过滤,降温出料。其中山梨醇/EO/PO的质量比为1.08/4.95/93.97,羟值为约28mgKOH/g,GPC测定数均分子量为12001。
聚醚多元醇B:使用三羟甲基丙烷为起始剂,催化剂(KOH)浓度为环氧丙烷(PO)质量的0.3wt%%(w/w),控制反应温度在110±5℃左右,压力低于0.15MPa进行反应,待PO投料结束后老化继续反应2h,脱气1h。脱气结束后开始投环氧乙烷(EO),控制反应温度在110±5℃左右,压力低于0.15MPa进行反应,投料结束后老化继续反应2h,脱气1h,此时反应阶段结束。控制温度在85-90℃,加入软水和磷酸中和,脱水,过滤,降温出料。其中三羟甲基丙烷/EO/PO的质量比为1.91/9.81/88.26,羟值24.0mgKOH/g,粘度:858cp(25℃),GPC测定数均分子量为7003。
对比稳定剂:将3000克聚醚多元醇B与马来酸酐30.6g,加热至120℃,氮气保护下反应12h。然后加入50g环氧乙烷(EO),继续反应4h,脱除未反应的EO,得到产物,为透明的棕黄色液体,粘度4100cp(25℃),不饱和度0.032meq/g。
OA-12:氧化二甲基十二烷基叔胺,经脱水、干燥后得到黏稠状液体。
B-8715LF2:泡沫稳定剂,高施密特化工有限公司。
以下实施例中的涉及的其他原料,如无特殊说明,均采购自阿拉丁试剂。
实施例1
稳定分散剂1的制备(反应示意图可参考图2):
将3000克聚醚多元醇A、40.3g环丁烷四甲酸二酐、180g丙酮混合均匀,升温至100℃,搅拌回流16h。然后,加入3.1g乙基三苯基碘化膦搅拌溶解后,再加入40.3g甲基丙烯酸缩水甘油酯(GMA)和1.78g对苯二酚,在120℃下反应过夜,所得产物为透明的浅黄色液体,粘度为2580mPa.s,不饱和度为
0.076meq/g,具有比对比稳定剂更高的不饱和度,说明其具有更多活性位点。
实施例2
稳定分散剂2的制备(反应示意图可参考图2):
将3000克聚醚多元醇B、41.9g均苯四甲酸二酐混合均匀,加热至120℃,氮气保护下反应18h。然后加入3.0g乙基三苯基碘化膦(ETPPI)搅拌溶解后,再加入36.1g丙烯酸缩水甘油酯(GA)0.90g对苯二酚,在120℃下反应过夜,所得产物为透明的浅黄色液体,粘度为1780mPa.s,不饱和度为0.092meq/g,具有比对比稳定剂更高的不饱和度,说明其具有更多活性位点。
实施例3
共聚物多元醇1制备:
500ml四口瓶装有搅拌器、加热装置、温控装置以及加料器作为反应器。在反应器中加入基础聚醚多元醇55.4g(万华3156)、3.6g稳定分散剂1,氮气置换后,搅拌缓慢升温至110℃,连续加入顶料(10.47g异丙醇、85.71g基础聚醚多元醇3156,46.55g丙烯腈、69.83g苯乙烯、1.21g偶氮二异丁腈的混合液),控制温度115℃~120℃。100min内滴加完毕,投料完毕,老化反应1小时,升温至160℃,真空脱除未反应单体2h,得到产品,测定产品指标。残留苯乙烯/丙烯腈/异丙醇依次分别为2/2/4ppm,羟值29.8mgKOH/g,固含44.9%,粘度5329cp(25℃)。
实施例4
共聚物多元醇2制备:
500ml四口瓶装有搅拌器、加热装置、温控装置以及加料器作为反应器。在反应器中加入基础聚醚多元醇55.4g(万华3156)、3.4g稳定分散剂2,氮气置换后,搅拌缓慢升温至110℃,连续加入顶料(10.47g异丙醇、85.71g基础聚醚多元醇3156,46.55g丙烯腈、69.83g苯乙烯、1.21g偶氮二异丁腈的混合液),控制温度115℃~120℃。100min内滴加完毕,投料完毕,老化反应1小时,继续真空脱除未反应单体2h,得到产品,测定产品指标。残留苯乙烯/丙烯腈/异丙醇依次分别为2/1/3ppm,羟值30.4mgKOH/g,固含44.8%,粘度5698cp(25℃)。
对比例
500ml四口瓶装有搅拌器、加热装置、温控装置以及加料器作为反应器。在反应器中加入基础聚醚多元醇55.4g(万华3156)、5.6g对比稳定剂,氮气置换后,搅拌缓慢升温至110℃,连续加入顶料(10.47g异丙醇、85.71g基础聚醚多元醇3156,46.55g丙烯腈、69.83g苯乙烯、1.21g偶氮二异丁腈的混合液),控制温度115℃~120℃。100min内滴加完毕,投料完毕,老化反应1小时,继续真空脱除未反应单体2h,得到产品,测定产品指标。残留苯乙烯/丙烯腈/异丙醇依次分别为2/3/6ppm,羟值29.2mgKOH/g,固含45.0%,粘度5783cp(25℃)。与实施例3-4相比,该对比例得到的共聚物多元醇在稳定剂使用量较高的情况下,其粘度却高出许多。
实施例5
对上述实施例3-4和对比例制备的共聚物多元醇分别经过乙醇洗涤、离心分离后,收集固体,经过SEM测试。实施例3-4的依次分别如图3-4,对比例的结果如图5,可见本发明制备的共聚物多元醇的粒径均一,外观细腻,无团聚现象。
实施例6
聚氨酯泡沫的制备方法:
按照表1中所示原料及重量份制备组合料,开展1#、2#、3#实验。将组合料以及异氰酸酯原料分别放置在22℃环境中恒温3小时。然后各取100g组合料,将其与60g8001组分在搅拌器(旋转数3000rpm)中搅拌混合6秒钟。然后迅速将搅拌后的混合物倒入预先加热到60℃的铝质敞口模具中(尺寸:长300mm,宽300mm,厚50mm),使混合物发泡。7分钟后,将泡沫取出,即得到聚氨酯泡沫。
表1组合料配方
其中,1#实验所用的聚合物分散体为对比例所制得的共聚物多元醇,2#、3#实验所用的聚合物分散体依次分别为实施例3-4制得的共聚物多元醇。
测试所制备的聚氨酯泡沫的性能指标及相应的测试标准见下表2:
表2聚氨酯泡沫性能
项目 | 测试标准 | 1# | 2# | 3# |
VOC | VDA 278 90℃/0.5h | 65 | 50 | 50 |
气味,μgC/g | VDA 270B3 80℃/2h | 5 | 3 | 2 |
拉伸强度,Kpa | ISO1798 | 90 | 100 | 105 |
断裂伸长率,Kpa | ISO1798 | 75 | 80 | 85 |
从表2的实验结果可知:使用新型稳定剂制备的共聚物多元醇在拉伸强度和断裂伸长率有较优的表现。
本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (11)
1.一种稳定分散剂的制备方法,其特征在于,所述制备方法包括如下步骤:
1)将多元醇与二酐化合物接触反应,制得加合物;
2)将步骤1)所得加合物与环氧化合物进行开环加成反应,制得所述稳定分散剂;
其中,所述二酐化合物中不含有能与烯属不饱和单体共聚的双键,所述环氧化合物中含有能与烯属不饱和单体共聚的双键;所述多元醇为聚酯多元醇和/或聚醚多元醇,优选为聚醚多元醇。
2.根据权利要求1所述的制备方法,其特征在于,所述二酐化合物选自均苯四甲酸二酐、二苯酮四甲酸二酐、联苯四甲酸二酐、二苯醚四甲酸二酐、六氟四甲酸二酐、三苯双醚四甲酸二酐、1,2,4,5-环己烷四甲酸二酐、环丁烷四甲酸二酐、双酚A二醚四甲酸二酐、萘-1,4,5,8-四甲酸二酐、3,4,9,10-苝四甲酸二酐、3,3',4,4'-三苯双醚四甲酸二酐、1,2,3,4-环戊烷四甲酸二酐化合物中的一种或两种以上的组合,进一步优选均苯四甲酸二酐和环丁烷四甲酸二酐中的一种或两种。
3.根据权利要求2所述的方法,其特征在于,所述环氧化合物选自缩水甘油醚、丙烯酸缩水甘油酯及其衍生物中的一种或两种以上的组合,优选烯丙基缩水甘油醚、甲基丙烯酸缩水甘油酯、丙烯酸缩水甘油酯中的一种或两种以上的组合,更优选甲基丙烯酸缩水甘油酯。
4.根据权利要求1-3任一项所述的方法,其特征在于,所述多元醇与所述二酐化合物的摩尔比为0.2-4∶1,优选1.5-2.5∶1;
所述二酐化合物与所述环氧化合物的摩尔比为0.1-2∶1,优选0.3-8∶1。
5.根据权利要求1-4任一项所述的制备方法,其特征在于,步骤2)中,在催化剂存在下进行反应;催化剂的用量优选为所述多元醇质量的0.01-0.5%(w/w);
优选的,所述催化剂为有机膦化合物、有机胺化合物和三级胺中的一种或两种以上的组合;
进一步优选的,所述催化剂选自有机磷卤化物、四甲基氢氧化膦中的一种或两种以上的组合;所述有机胺化合物选自咪唑或咪唑衍生物中的至少一种;所述三级胺选自三乙胺、二乙烯三胺、三丙胺和三丁胺中的一种或两种以上的组合;
更进一步优选的,所述有机磷卤化物选自四甲基碘化膦、四甲基溴化膦、三甲基苄基溴化膦、三甲基苄基氯化膦、乙基三苯基碘化膦、乙基三(对甲苯基)溴化膦、乙基三(对甲苯基)氯化膦中的一种或两种以上的组合。
6.根据权利要求1所述的制备方法,其特征在于,步骤1)中,所述多元醇数均分子量为2500-15000,优选5000-14000;平均官能度为2.0以上,优选2.5-6.0。
7.根据权利要求1所述的制备方法,其特征在于,步骤1)和步骤2)的反应在有溶剂或无溶剂存在下进行;优选所述溶剂为不含质子的极性溶剂,且能够溶解所述二酐化合物和所述环氧化合物;
优选的,步骤1)和步骤2)的反应温度分别为60-150℃,更优选80-130℃;步骤1)和步骤2)的反应优选在常压下进行;
任选的,步骤2)中还添加有阻聚剂,所述阻聚剂的用量为所述多元醇总质量的0~1.5%,优选30~2000ppm。
8.一种稳定分散剂,其特征在于,采用权利要求1-7任一项所述的制备方法制得。
9.一种共聚物多元醇的制备方法,其特征在于,所述制备方法包括:在引发剂和稳定分散剂存在下,基础聚醚多元醇与至少一种烯属不饱和单体聚合得到所述共聚物多元醇;所述稳定分散剂为权利要求8所述的稳定分散剂;
优选制备所述共聚物多元醇的反应温度为80-150℃,优选90-120℃;反应压力优选为0-1Mpa,更优选常压至0.5Mpa;
优选的,所述烯属不饱和单体的用量为所述基础聚醚多元醇、所述烯属不饱和单体和所述稳定分散剂的总质量的20-55wt%;
优选的,所述稳定分散剂的用量为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.3%~10%,进一步优选2%~5%;
优选的,所述引发剂的用量为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.01-5wt%;优选所述引发剂选自过氧化物和偶氮化合物中的一种或两种以上的组合;
优选的,制备所述共聚物多元醇的反应体系中,还添加有链转移剂,其用量优选为所述基础聚醚多元醇和所述烯属不饱和单体总质量的0.1-6wt%,优选0.2-5wt%。
10.根据权利要求9所述的制备方法,其特征在于,所述烯属不饱和单体为乙烯基芳香化合物和烯属不饱和腈中的一种或两种以上的组合;优选选自苯乙烯和丙烯腈中的一种或两种,优选所述苯乙烯和丙烯腈的摩尔比为50∶50-100∶0。
11.一种应用,其特征在于,权利要求9-10任一项所述的制备方法得到的共聚物多元醇在制备聚氨酯泡沫材料中应用。
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