CN116410459A - 一种大分子稳定剂的制备方法及应用 - Google Patents
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Abstract
本发明公开了一种大分子稳定剂的制备方法及应用,将基础聚醚与碱进行反应后,加入卤代烃进行封端;然后将封端产物与酸酐、封端剂反应生成大分子稳定剂。该方法合成的稳定剂与传统稳定剂相比,可以降低聚合物多元醇中聚苯乙烯‑丙烯腈颗粒在DCM(二氯甲烷)中的溶解性能,进而改善聚合物多元醇与DCM混合后的过滤性能,不易堵塞设备。
Description
技术领域
本发明属于聚合物多元醇领域,具体涉及一种制备聚合物多元醇用的稳定剂的制备方法及应用。
背景技术
聚合物多元醇与聚醚多元醇相比,制备的聚氨酯泡沫塑料硬度更高,主要用于高回弹,高承载和模塑泡沫,广泛用于汽车座椅,床垫,家具等领域。
聚合物多元醇主要为苯乙烯和丙烯腈的共混物在聚醚多元醇中的分散液,由大分子稳定剂保证有机固体颗粒在聚醚多元醇中的分散稳定性。大分子稳定剂也在一定程度上决定了聚合物多元醇中有机固体颗粒的表面性质。
在聚氨酯泡沫发泡过程中,需要加入少量发泡剂帮助形成泡沫。发泡剂包括化学发泡剂和物理发泡剂,化学发泡剂包括水等可与异氰酸酯反应生成气体的物质;物理发泡剂为二氯甲烷等沸点较低的物质,在异氰酸酯与聚合物多元醇反应放热后气化的物质。’
目前,常见的大分子稳定剂通常为3~6官能度未封端的基础聚醚与酸酐和环氧化合物合成,其中基础聚醚部分与聚醚相溶性较好,酸酐与环氧化合物部分提供芳香环或双键与苯乙烯/丙烯腈结合,用以保证苯乙烯/丙烯腈固体颗粒在聚醚中分散的稳定性。
这种稳定剂用于合成的聚合物多元醇时,由于有机固体颗粒表面羟基的存在,在与发泡剂二氯甲烷(DCM)混合后会析出纤维状固体,堵塞过滤器,影响下游使用。
发明内容
为解决上述问题,本发明提供一种新的大分子稳定剂的制备方法及应用,使其合成的聚合物多元醇在与发泡剂DCM混合时不会析出固体,满足过滤要求,不堵塞设备。
一种大分子稳定剂的制备方法,包括以下步骤:
(1)将基础聚醚与碱进行反应后,加入卤代烃进行封端。
(2)将步骤(1)得到的封端产物与酸酐、封端剂反应生成大分子稳定剂。
优选的,所述步骤(1)中基础聚醚为以小分子多元醇在催化剂的存在下引发环氧化合物开环反应所得的高分子聚醚多元醇。优选的,小分子多元醇为甘油、三羟甲基丙烷、季戊四醇、己六醇、山梨醇,环氧化合物为环氧乙烷和环氧丙烷。
优选的,本发明中基础聚醚的分子量为3000~12000,优选10000~12000,官能度n为3~8,优选5~6。
本发明中采用卤代烃对基础聚醚进行封端前需要先将基础聚醚的醇羟基转变为碱金属或碱土金属的醇盐,优选的,所述步骤(1)中碱可以是碱金属、碱土金属、碱金属或碱土金属的氢氧化物、碱金属或碱土金属的醇盐,优选碱金属的醇盐,其用量与基础聚醚官能度n相关,碱与基础聚醚摩尔比为1:1~1.3n:1,优选为n:1-1.2n:1。加入碱后需对基础聚醚进行脱挥以形成醇盐。
基础聚醚与碱的反应温度为80℃~120℃,优选为100℃~120℃。脱挥真空度优选为80kPa~100kPa。脱挥时间为1h~5h,优选为3h~5h。
对基础聚醚进行封端需要卤代烃与醇盐进行反应,生成烃基封端的聚醚,优选的,所述卤代烃为碳数1~3的脂肪烃单卤代物,优选氯甲烷、氯乙烷,其用量为加入的碱摩尔量的1~2倍,优选1.1-1.5倍。
醇盐与卤代烃反应温度为60℃~180℃,优选为70℃~90℃。反应时间为1~5h,优选1h~1.5h。反应完成后脱挥除去未反应的卤代烃。
所述步骤(1)中,将封端后的基础聚醚调节pH到6~8,吸附脱水后过滤除盐,得到封端产物。
优选的,所述步骤(2)中,酸酐为含芳香环或双键的酸酐,优选为马来酸酐、邻苯二甲酸酐、丁二酸酐和衣康酸酐等,酸酐加入的摩尔量为基础聚醚摩尔量的0.8~1.5倍,优选1-1.5倍。酸酐与封端产物的反应温度为85℃~100℃。
步骤(2)中,先将步骤(1)得到的封端产物与酸酐反应,然后再将反应产物与封端剂进行反应。
所述步骤(2)中,封端剂为含有环氧基团的物质,优选环氧乙烷、环氧丙烷、环氧苯乙烯和甲基丙烯酸缩水甘油酯,封端剂的加入量为基础聚醚摩尔量的0.8~1.5倍,优选1-1.5倍。反应后需要进行脱挥处理。述步骤(2)中,封端反应的温度80℃~160℃,优选为100℃~120℃。
一种聚合物多元醇,采用权利要求1-9任一项所述的制备方法制备的大分子稳定剂。
与现有技术相比,本申请具有以下有益效果:
通过对稳定剂中基础聚醚进行烷基封端,降低POP中固体颗粒表面羟基含量,进而降低固体表面极性。固体颗粒表面极性降低后,混合加入的极性较高的二氯甲烷发泡剂,POP中不会析出纤维状固体,过滤性能良好。封端改性后的稳定剂制备的POP,十分适用于预混二氯甲烷过滤发泡工艺,不会出现堵塞枪头的问题。
附图说明
图1为聚合物多元醇A与DCM混合过滤效果图。
图2为聚合物多元醇B与DCM混合过滤效果图。
图3为聚合物多元醇C与DCM混合过滤效果图。
图4为聚合物多元醇D与DCM混合过滤效果图。
图5为聚合物多元醇E与DCM混合过滤效果图。
具体实施方式
基础聚醚a:通过官能度为6的山梨醇与环氧丙烷和环氧乙烷反应制备的聚醚,环氧乙烷含量为18%,分子量为12000。
基础聚醚b:通过官能度为3的甘油与环氧丙烷和环氧乙烷反应制备的聚醚,环氧乙烷含量10%,分子量为4800。
基础聚醚c:通过官能度为3的甘油和官能度为6的山梨醇混合为平均官能度为5的原料醇与环氧乙烷和环氧丙烷反应制备的聚醚,环氧乙烷含量12%,分子量为9350。
实施例1
将基础聚醚a 502g与质量分数30%的甲醇钾的甲醇溶液44g加入到反应釜中,搅拌抽真空至-0.1MPa,升温至110℃脱甲醇3h。降温至90℃后加入氯甲烷18g,反应1.5h。真空脱除未反应的氯甲烷后中和脱盐精制。测量封端后的基础聚醚羟值为13mgKOH/g,计算的封端率为52%。
取精制后的封端聚醚360g,加入0.022g的50%KOH溶液,真空脱水2h。加入马来酸酐4.38g,反应3h后加入环氧乙烷1.9g,老化脱挥后即得封端大分子稳定剂A。
实施例2
将基础聚醚a 667g与质量分数30%甲醇钾的甲醇溶液75g加入到反应釜中,搅拌抽真空至-0.1MPa,升温至115℃脱甲醇3h。降温至90℃后加入氯甲烷21g,反应1.5h。真空脱除未反应的氯甲烷后中和脱盐精制。测量封端后的基础聚醚羟值为6mgKOH/g,计算的封端率为78%
取精制后的封端聚醚360g,加入0.022g的50%KOH溶液,真空脱水2h。加入马来酸酐3.5g,反应3h后加入环氧乙烷1.7g,老化脱挥后即得封端大分子稳定剂B。
实施例3
将基础聚醚b 667g与质量分数30%甲醇钠的甲醇溶液52g加入到反应釜中,搅拌抽真空至-0.1MPa,升温至115℃脱甲醇3.5h。降温至90℃后加入氯甲烷26g,反应1.5h。真空脱除未反应的氯甲烷后中和脱盐精制。测量封端后的基础聚醚羟值为15.1mgKOH/g,计算的封端率为56.7%
取精制后的封端聚醚360g,加入0.022g的50%KOH溶液,真空脱水2h。加入邻苯二甲酸酐12.5g,反应3h后加入环氧丙烷5.6g,老化脱挥后即得封端大分子稳定剂C。
实施例4
将基础聚醚c 667g与质量分数30%甲醇钠的甲醇溶液68g加入到反应釜中,搅拌抽真空至-0.1MPa,升温至110℃脱甲醇3.5h。降温至90℃后加入氯乙烷36g,反应1.5h。真空脱除未反应的氯甲烷后中和脱盐精制。测量封端后的基础聚醚羟值为7.2mgKOH/g,计算的封端率为76%。
取精制后的封端聚醚360g,加入0.022g的50%KOH溶液,真空脱水2h。加入衣康酸酐4.8g,反应3h后加入甲基丙烯酸缩水甘油酯6.3g,老化脱挥后即得封端大分子稳定剂D。
对比例1
直接取基础聚醚(未封端,羟值为28mgKOH/g)360g,加入0.022g的50%KOH溶液,真空脱水2h。加入马来酸酐4.38g,反应3h后加入环氧乙烷1.9g,老化脱挥后即得封端大分子稳定剂E。
将实施例1-4和对比例1中所制得的大分子稳定剂分别制成固含量为45%的聚合物多元醇。分别取100g聚合物多元醇与10g二氯甲烷混合后静置6h,再通过150目滤网,测量通过率如表1。
表1聚合物多元醇基本指标
如图1-5分别为聚合物多元醇A、B、C、D与对比例E的DCM过滤性能图。对比例E在加入DCM后形成大量纤维状固体,难以过滤;与对比例相比,封端后聚合物多元醇的DCM过滤性能均有所改善,且封端率高的聚合物多元醇B过滤后滤网上残留物的量少于聚合物多元醇A、C和D,DCM过滤性能更好。
Claims (10)
1.一种大分子稳定剂的制备方法,其特征在于,包括以下步骤:
(1)将基础聚醚与碱进行反应后,加入卤代烃进行封端;
(2)将步骤(1)得到的封端产物与酸酐、封端剂反应生成大分子稳定剂。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤(1)中基础聚醚为以小分子多元醇在催化剂的存在下引发环氧化合物开环反应所得的高分子聚醚多元醇;
优选的,小分子多元醇为甘油、三羟甲基丙烷、季戊四醇、己六醇、山梨醇,环氧化合物为环氧乙烷和环氧丙烷。
3.根据权利要求1或2所述的制备方法,其特征在于,所述基础聚醚的分子量为3000~12000,优选10000~12000,官能度n为3~8,优选5~6。
4.根据权利要求1-3任一项所述的制备方法,其特征在于,所述步骤(1)中碱为碱金属、碱土金属、碱金属或碱土金属的氢氧化物、碱金属或碱土金属的醇盐,优选碱金属的醇盐,其用量与基础聚醚官能度n相关,碱与基础聚醚摩尔比为1:1~1.3n:1,优选为n:1-1.2n:1;
优选的,所述基础聚醚与碱的反应温度为80℃~120℃,优选为100℃~120℃。
5.根据权利要求1-4任一项所述的制备方法,其特征在于,所述卤代烃为碳数1~3的脂肪烃单卤代物,优选氯甲烷、氯乙烷,其用量为加入的碱摩尔量的1~2倍,优选1.1-1.5倍。
6.根据权利要求1-5任一项所述的制备方法,其特征在于,卤代烃封端反应温度为60℃~180℃,优选为70℃~90℃;反应时间为1~5h,优选1h~1.5h;
优选的,所述步骤(1)中,将封端后的基础聚醚调节pH到6~8,吸附脱水后过滤除盐,得到封端产物。
7.根据权利要求1-6任一项所述的制备方法,其特征在于,所述步骤(2)中,酸酐为含芳香环或双键的酸酐,优选为马来酸酐、邻苯二甲酸酐、丁二酸酐和衣康酸酐;
优选的,酸酐加入的摩尔量为基础聚醚摩尔量的0.8~1.5倍,优选1-1.5倍;
优选的,酸酐与封端产物的反应温度为85℃~100℃。
8.根据权利要求1-7任一项所述的制备方法,其特征在于,步骤(2)中,先将步骤(1)得到的封端产物与酸酐反应,然后再将反应产物与封端剂进行反应。
9.根据权利要求1-8任一项所述的制备方法,其特征在于,所述步骤(2)中,封端剂为含有环氧基团的物质,优选环氧乙烷、环氧丙烷、环氧苯乙烯和甲基丙烯酸缩水甘油酯;
优选的,封端剂的加入量为基础聚醚摩尔量的0.8~1.5倍,优选1-1.5倍;
优选的,述步骤(2)中,封端反应的温度80℃~160℃,优选为100℃~120℃。
10.一种聚合物多元醇,采用权利要求1-9任一项所述的制备方法制备的大分子稳定剂。
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