CN1278278A - 部分结晶的聚醚多元醇的制备方法 - Google Patents

部分结晶的聚醚多元醇的制备方法 Download PDF

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CN1278278A
CN1278278A CN98810796A CN98810796A CN1278278A CN 1278278 A CN1278278 A CN 1278278A CN 98810796 A CN98810796 A CN 98810796A CN 98810796 A CN98810796 A CN 98810796A CN 1278278 A CN1278278 A CN 1278278A
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W·谢菲尔
J·霍夫曼
P·古普塔
H·P·米勒
H·皮拉特兹克
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Carcoustics Techconsult GmbH
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Abstract

本发明涉及一种制备新的部分结晶的聚醚多元醇的方法,该聚醚多元醇的官能度≥2、平均分子量Mn为500—100000、并且确定结晶度的全同立构三单元组的摩尔比例>28%。该新的聚醚多元醇是在有以羟基化合物改性的双金属μ－氧代醇盐存在下聚合烯化氧而制得的。

Description

部分结晶的聚醚多元醇的制备方法
本发明涉及一种制备羟基-官能度≥2的新的部分结晶的聚醚多元醇的方法，以及新的聚醚多元醇及其应用。
由文献已知，按照异氰酸酯-聚加成方法，用基于官能度为2的环氧丙烷的结晶聚醚多元醇可合成具有改进机械性能的产品(聚合物科学杂志(聚合物化学版)，15卷，1655ff(1977))。由全同立构的聚丙二醇通过臭氧解，接着用对水份敏感的和对氧敏感的试剂氢化以及分馏来制备结晶的羟基官能化的二羟基聚醚是很费力的，并且几乎没有可变性。因此本发明的目的要提供例如适用于PUR-合成的各式各样的官能度≥2的结晶羟基聚醚，而其方法费力少而且有较大的可变性。
还已知，双金属的μ-氧代醇盐适用于从环氧丙烷聚合成结晶的聚环氧丙烷(US-P 3432445，聚合物预印本218(1984))。公开文献未涉及适于在异氰酸酯-聚加成中作为增链剂和交联剂的有合适羟基-官能度的聚醚多元醇的制备的提示。
这些用于环氧丙烷-聚合的双金属催化剂含有单醇取代物，该取代物在聚合过程中结合进聚环氧丙烷中，导致形成羟基-官能度远低于2的聚环氧丙烷，它不适于作为制备聚氨酯的增链剂。
曾意外地发现，通过双金属催化剂与官能度≥2的羟基化合物反应生成一些催化剂，这些催化剂能使烯化氧聚合成其官能度≥2的聚醚多元醇。惊奇地是，这种根据文献(聚合物科学杂志：部分A：聚合物化学，24卷，1423(1986))对杂质是敏感的有催化活性的双金属原始化合物在与羟基化合物反应后，甚至在100-160℃下对烯化氧-聚合仍具有活性。
此外，未预计到的是，对于羟基化合物来说被看作是多官能的双金属催化剂在有官能度≥2的羟基化合物存在下未发生交联及互连，并仍保留催化活性。
因此，本发明涉及一种制备羟基-官能度≥2的新的部分结晶的聚醚多元醇的方法，其特征在于，在有下式(I)的双金属μ-氧代醇盐存在下聚合烯化氧
      (RO)x-1-M2-O-M1-O-M2-(OR)x-1          (I)其中：
R代表C1-C10-烷基
M1代表锌、钴、钼、铁、铬或锰
M2为铝或钛
x代表3-4
其中，μ-氧代醇盐(I)首先与下式(II)的羟基化合物反应
Figure A9881079600051
其中：
Q代表C2-C20-烷基
R1和R2互为独立地为氢或C1-C20-烃基
l和n互为独立地为0-40中的数
y为2-6中的整数
适用的双金属μ-氧代醇盐优选为：M1为锌，M2为铝，x为3，R为正-丙基和异-丙基以及正-丁基。
适用于本发明方法的双金属μ-氧代醇盐是已知的，如在上述美国专利3432445中有详述。
特别适用于与所用的双金属μ-氧代醇盐反应的式(II)的羟基化合物是具有官能度≥2，优选为2-6的平均分子量为90-6000，优选为90-2000的这些羟基化合物。平均分子量通常由测定OH-数或以相对于聚苯乙烯的GPC作比较来确定的。
除已知的低分子量的多羟基化合物外，式(II)的羟基化合物包括特别是聚丙二醇、聚乙二醇、聚环氧乙烷、聚环氧丙烷-嵌段共聚物和无规C-O-PO-共聚物。这些化合物描述于Kirk-Othmer(3)1，754-789中。
特别优选的羟基化合物包括：
1，4-丁二醇、二甘醇、二丙二醇、三丙二醇、以及始于丙二醇、1，4-丁二醇、甘油、三羟甲基丙烷或山梨醇的 Mn为200-2000的聚丙二醇或始于乙二醇、丙二醇、1，4-丁二醇、甘油或三羟甲基丙烷的 Mn为200-2000的环氧丙烷和环氧乙烷混合聚合物。
所用的式(I)的双金属μ-氧代醇盐与式(II)的羟基化合物的反应按如下进行：1mol的多元醇(II)与5×10-4-0.6mol，优选为1×10-3-0.3mol的μ-氧代醇盐混合，该混合物在100-150℃，优选110-130℃下加热0.5-10小时，优选2-5小时。
接着，该反应混合物(需要时还可在真空下)在加热下(约100-150℃)搅拌一段时间(约0.5-5小时)。
然后，反应混合物用有机溶剂和/或稀释剂，例如合适的烃如二甲苯和/或石油醚稀释，优选稀释到80-50％(重量)，然后该溶剂和/或稀释剂在减压(约0.01-1013mbar)下蒸馏掉。
经多元醇改性的双金属μ-氧代醇盐再与合适的烯化氧反应以制备部分结晶的聚醚多元醇。该反应优选在20-200℃，特别是80-150℃下，于常压或高达20bar的压力下进行。
适用于该反应的烯化氧是已知的烯化氧，特别是环氧丙烷、1，2-环氧丁烷、表氯醇、烷基缩水甘油醚以及其混合物。优选使用环氧丙烷和/或环氧乙烷。与烯化氧反应前，改性的μ-氧代醇盐还可用官能度≥2的羟基化合物稀释，优选用式(II)的羟基化合物稀释。
改性的催化剂与烯化氧的反应可在本体中进行或在合适的有机溶剂如甲苯、二甲苯和/或四氢呋喃中进行。溶剂的浓度和用量的选定要使在给定的反应条件能控制该转化反应。
改性的双金属μ-氧代醇盐的使用量按待制备的聚醚多元醇的量计为5×10-2-60％(摩尔)，优选0.1-20％(摩尔)。
按本发明方法制备的官能度≥2，优选2-6的新的部分结晶的聚醚多元醇具有平均分子量 Mn为500-100000，优选1000-10000(按对聚苯乙烯的GPC或通过羟基含量测定的)，并且其确定结晶度的全同立构三单元组的摩尔-比例为＞28％，优选＞33％(通过13C-NMR光谱学测定)。
本发明还涉及上述类的新的部分结晶的聚醚多元醇。
本发明方法不仅能连续进行，也可间歇进行，例如以批量方法或半批量方法进行。
按照本发明方法，其粗产品的加工最好是将所制备的聚醚多元醇溶于溶剂如甲苯、二甲苯、四氢呋喃、乙酸乙酯和/或二氯甲烷中来进行。
然后，催化剂用酸化水破坏，反应产物用含水酸(＜25％(重量))，优选用水萃取。为了破坏催化剂，优选使用1-2酸当量。适用的酸包括盐酸、磷酸、硫酸、苯甲酸、醋酸和/或乳酸。当然其它的酸也可使用。
在与含水酸一起强烈搅动后，多余的酸通过水洗，还可通过在有碱性反应的化合物如碳酸氢钠的存在下的水洗被去除，将所得的多元醇溶液与水分离、干燥和并去除溶剂。
通过在冷态下从合适的溶剂如酮中的分段沉淀可进一步纯化该产品。
由本发明方法制备的部分结晶的聚醚多元醇特别适用于聚氨酯材料如PUR-弹性体、PUR-泡沫体和PUR-涂料的制备。上述PUR-材料的制备是公知的，并描述于“材料手册”卷7，第三版，Carl-VerlagVerlag，1993中。
实施例
制备基于锌和铝的双金属μ-氧代醇盐A
9g醋酸锌和20.4g异丙醇铝在500ml的萘烷中回流加热，所形成的醋酸异丙酯经柱蒸馏掉。
在不再有醋酸异丙酯生成后，从反应溶液中去除溶剂，残余物溶于200ml的正-庚烷中。由此得到0.35摩尔的二-μ-氧代〔2(1-甲基乙氧基)-铝〕锌。
实施例1
a.将溶于10ml庚烷中的1.3g双金属μ-氧代醇盐A加到100g的OH-数为112mg KOH/g的聚丙二醇中，并在0.2mbar的压力和130℃下搅拌3小时。
接着，将10ml甲苯加到溶液中，反应混合物在120-130℃下继续搅拌2小时。然后，在高真空下蒸馏掉甲苯，反应混合物在130℃下再加热1小时。
b.将经预活化的聚丙二醇转入高压釜中，并在3bar的压力和130-140℃下与500g环氧丙烷反应。粗产物溶于甲苯中，并加入2N盐酸直到pH＜5，然后与水一起摇动。该产物还用碳酸氢盐水溶液洗涤以中和。有机相经分离并干燥。
该部分结晶的蜡状产物的OH-数为20mg KOH/g，按GPC的Mn为5900。在聚醚多元醇中的结晶相在55℃熔化。该产物含全同立构三单元组的摩尔比例为64％。
实施例2
a.将溶于20ml庚烷中的2.7g双金属μ-氧代醇盐A加到10g的OH-数为515mg KOH/g的聚丙二醇中，并在0.2mbar的压力和130℃下搅拌5小时。
接着再加入40g的OH-数为515的聚醚，并且该反应混合物在真空下于130℃再搅拌3小时。
b.将该催化剂溶液转入高压釜中，并在3bar的压力和130-140℃下与400g环氧丙烷反应。粗产物溶于二氯甲烷中，加入20％磷酸直到pH＜5，并与水一起摇动。该产物还用碳酸氢盐水溶液洗涤以中和。有机相经分离并干燥。
该部分结晶的蜡状产物的OH-数为65mg KOH/g，按GPC的Mn为1900。
实施例3
a.将溶于40ml庚烷中的5.5g双金属μ-氧代醇盐A加入到100g始于三羟甲基丙烷的基于OH-数为380mg KOH/g的环氧丙烷的羟基聚醚中，并在0.2mbar的压力和130℃下搅拌5小时。
接着，将10ml甲苯加到溶液中，反应混合物在120-130℃下再搅拌2小时。然后在高真空下蒸馏掉甲苯，反应混合物再在130℃下加热1小时。
b.然后将该催化剂溶液转入高压釜中，并在3bar的压力和150℃下与1kg环氧丙烷反应。
将粗产物溶于二氯甲烷中，并加入2N盐酸直到pH＜5，然后与水一起摇动。该产物还用碳酸氢盐水溶液洗涤以中和。有机相经分离并干燥。
该部分结晶的蜡状产物的OH-数为42mg KOH/g，按GPC的Mn为4290。
实施例4
将溶于50g正-庚烷的6.5g双金属μ-氧代醇盐化合物A加到500g的OH-数为56的带有70-80％原OH-基的环氧乙烷-环氧丙烷-聚醚(50％环氧乙烷)中，并在0.2mbar的压力和130℃加热3小时。
接着，将50ml甲苯加到溶液中，反应混合物在120-130℃下再搅拌2小时。然后在高真空下蒸馏掉甲苯，反应混合物再在130℃下加热1小时。
然后，将该催化剂溶液转入高压釜中，并在3bar的压力和130-140℃下与1500g环氧丙烷反应。粗产物溶于甲苯中，并加入2N盐酸直到pH＜5，然后与水一起摇动。该产物还用碳酸氢盐水溶液洗涤以中和。有机相经分离并干燥。
该部分结晶的蜡状产物的OH-数为14，按GPC的Mn为7800。
实施例5
将溶于10ml庚烷中的1.3g双金属μ-氧代醇盐加到100g的OH-数为450mg HOK/g的始于山梨醇的聚丙二醇中，并在0.2mbar的压力和130℃下搅拌3小时。
接着，将10ml甲苯加到溶液中，反应混合物在120-130℃下搅拌2小时。然后在高真空下蒸馏掉甲苯，反应混合物再在130℃下加热1小时。
然后，将该预活化的多元醇在高压釜中在3bar的压力和150℃下与250g环氧丙烷反应。经类似于实施例1b的纯化步骤后，该部分结晶的产物的OH-值为135mg KOH/g，按GPC的Mn为2600。
实施例6
1000g的OH-数为112mg KOH/g的类似实施例1a的预活化的聚丙二醇在常压和120-130℃下与1000g环氧丙烷反应。粗产物溶于甲苯中，并加入150ml的2N盐酸，再与水一起摇动。该产物还用碳酸氢盐溶液洗涤以中和。
有机相经分离和干燥。该部分结晶的产物的OH-数为57mgKOH/g，按GPC的Mn为2000。
实施例7
在50g的OH-数为112mg KOH/g的类似于实施例1a的预活化的聚丙二醇中加入50ml甲苯，接着在120℃下与50g环氧丙烷反应。经类似于实施例1b的纯化步骤后，该粘性产物的OH-值为57.5mgKOH/g，按GPC的Mn为2000。
实施例8
在250g的OH-数为112mg KOH/g的类似于1a的预活化的聚丙二醇中加入500g二甲苯，接着在高压釜中于3bar的压力和150℃下与750g环氧丙烷反应。经类似于实施例1b的纯化步骤后，该在室温下凝固的产物的OH-值为32mg KOH/g，按GPC的Mn为3700。

Claims (7)

1.一种制备羟官能度≥2的新的部分结晶的聚醚多元醇的方法，其特征在于，在有下式(I)的双金属μ-氧代醇盐存在下，聚合烯化氧
       (RO)x-1-M2-O-M1-O-M2-(OR)x-1       (I)其中：
R代表C1-C10-烷基
M1代表锌、钴、钼、铁、铬或锰
M2为铝或钛
x代表3-4
其中，μ-氧代醇盐(I)首先与下式(II)的羟基化合物反应
Figure A9881079600021
其中：
Q代表C2-C20-烷基
R1和R2互为独立地为氢或C1-C20-烃基
l和n互为独立地为0-40中的数
y为2-6中的整数
2.权利要求1的方法，其特征在于，所用的双金属μ-氧代醇盐为其中M1为锌和M2为铝，x为3和R为正-丙基和异-丙基以及正-丁基的这些双金属μ-氧代醇盐。
3.权利要求1的方法，其特征在于，所用的式(II)的羟基化合物是具有官能度≥2和平均分子量为90-6000的这些羟基化合物。
4.权利要求1的方法，其特征在于，将每摩尔式(II)的羟基化合物与5×10-4-0.6摩尔的双金属μ-氧代醇盐混合。
5.权利要求1的方法，其特征在于，在μ-氧代醇盐与羟基化合物混合后，该混合物在100-150℃下加热0.5-10小时。
6.一种部分结晶的聚醚多元醇，其官能度≥2，平均分子量 Mn为500-100000和通过13C-NMR光谱学测定的确定结晶度的全同立构三单元组的摩尔比例为＞28％。
7.权利要求6的聚醚多元醇在制备所有种类的聚氨酯材料中的应用。
CN98810796A 1997-11-03 1998-10-21 部分结晶的聚醚多元醇的制备方法 Expired - Fee Related CN1116335C (zh)

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