CN107406633A - 用于生产pur泡沫的多元醇组分 - Google Patents

用于生产pur泡沫的多元醇组分 Download PDF

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CN107406633A
CN107406633A CN201680014860.8A CN201680014860A CN107406633A CN 107406633 A CN107406633 A CN 107406633A CN 201680014860 A CN201680014860 A CN 201680014860A CN 107406633 A CN107406633 A CN 107406633A
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composition
component
pur foam
weight
foam
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CN107406633B (zh
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C.贝塞勒
D.巴尔
C.查塔德
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Huntsman Advanced Materials Switzerland GmbH
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Abstract

包含（a1）聚醚多元醇、（a2）聚烯烃多元醇和（a3）可以通过不饱和脂肪酸酯的环氧化反应以及随后与含有活性氢的化合物的开环反应获得的聚酯多元醇的组合物可用于制备PUR泡沫，该PUR泡沫的区别之处在于低温柔韧性和低介电损耗，并且适于在树脂浸渍纸（RIP）套管的制造中用于填充电容器芯与外部复合材料或陶瓷绝缘体之间的间隙。

Description

用于生产PUR泡沫的多元醇组分
本发明涉及与合适的多异氰酸酯结合提供聚氨酯（PUR）泡沫的多元醇组合物，所述聚氨酯（PUR）泡沫可以有利地在制造高电压（HV）树脂浸渍纸（RIP）套管的过程中施加以填充电容器芯与外部中空绝缘体（复合材料类型或陶瓷）之间的间隙。
通过使用连续卷绕的绉纸同时插入铝箔以建立电场强度的电容分级来制造RIP电容器芯。在卷绕过程后，该芯用环氧树脂在真空和加热下浸渍。该固体芯随后机器加工以完成最终尺寸。通常，RIP套管具有外部复合材料或陶瓷绝缘体，并且电容器芯与外部复合材料或陶瓷绝缘体之间的间隙填充有泡沫，通常为PUR泡沫。
可以方便地用作RIP套管的填充材料的PUR泡沫要满足的要求是通用性。
可发泡组合物通常由两种成分组成——多元醇组分和多异氰酸酯组分，其在临应用前，即在临生成PUR泡沫前混合。由于该多元醇组分常常含有多种多元醇以及各种（分散的）添加剂，这些混合物通常倾向于沉淀固体组分或分离。因此，该多元醇组分的储存稳定性是一个重要的因素。
此外，可发泡组合物应确保足够长的适用期以允许填充大的超高电压（UV）套管，即在组分混合后，该组合物的粘度应当仅适度提高。该适用期通常规定为将多元醇与异氰酸酯组分（包括添加剂）合并直到粘度增加至15 Pa·s的时间段，并且对预期用途应为>90分钟。
为了承受大的温度差异，固化的PUR泡沫必须表现出显著的低温柔韧性。由此，玻璃化转变温度Tg应相当低：Tg < -50℃。
对用于HV套管的绝缘材料来说最重要的是介电性质。因此，介电损耗的目标分别为tan δ < 5%（RT）和tan δ < 15%（100℃）。
US 4,752,626描述了在宽范围的异氰酸酯指数下具有低压缩永久变形的高回弹性聚氨酯泡沫，其用于在集成泡沫部件中填充小的空隙。
可以在发泡液体不渗透到现有泡孔中的情况下填充在集成泡沫部件的模塑过程中形成的小空隙。此外，所得泡沫在宽范围的异氰酸酯指数下具有极低的压缩永久变形值。
根据US 4,752,626的发泡体系由触变性多异氰酸酯组分和触变性多元醇组分组成，所述触变性多元醇组分是重量比为95/5至50/50的聚烯烃多元醇和聚氧化烯多元醇的共混物。通过向各组分中加入苯亚甲基山梨糖醇来获得触变性。尽管这种PUR泡沫非常适于填充汽车泡沫部件的模塑过程中形成的小空隙，在HV电容器中的应用在适用期、低温柔韧性和电气性能方面需要更严格的要求。
本发明的一个目的是提供一种由储存稳定的多元醇组分和多异氰酸酯组分组成的可发泡组合物，其确保足够长的适用期、低温柔韧性、低介电损耗和固化过程中组分的令人满意的相容性。
现在已经发现，通过使用特定组合物（A）作为多元醇组分可以实现这些性质，所述组合物（A）包含：
（a1）聚醚多元醇，
（a2）羟基封端的聚丁二烯或聚异戊二烯，和
（a3）可以通过不饱和脂肪酸酯的环氧化反应以及随后与含有活性氢的化合物的开环反应获得的聚酯多元醇。
作为组分（a1）的聚醚多元醇可以例如通过起始剂（starter）与环氧烷，例如与环氧乙烷、环氧丙烷或环氧丁烷或四氢呋喃的反应来获得。起始剂在这里为所有通常适于制备具有2或3的官能度的聚醚多元醇的那些，例如水，具有2或3个羟基基团的脂族、脂环族或芳族多羟基化合物，如乙二醇、丙二醇、丁二醇、己二醇、辛二醇、二羟基苯或双酚（例如双酚A），三羟甲基丙烷或胺类（参见Ullmanns Encyclopädie der Technischen Chemie(Ullmann's Encyclopedia of Industrial Chemistry)，第4版，第19卷，Verlag ChemieGmbH, Weinheim 1980，第31-38、304和305页）。
特别适于作为本发明的组合物的成分（a1）的物质是基于环氧乙烷的聚醚多元醇和基于环氧丙烷的聚醚多元醇，以及相应的环氧乙烷/环氧丙烷共聚物（其可以是无规或嵌段共聚物）。这些共聚物中环氧乙烷对环氧丙烷的比率可以在宽范围内改变。由此，例如可以仅使聚醚多元醇的末端羟基与环氧乙烷反应（末端掩蔽）。
基于聚乙烯和/或聚丙烯的聚醚多元醇的分子量Mw优选为100-2000克/摩尔、更优选200-1000克/摩尔、特别是300-600克/摩尔。
类似于上文已经限定的聚亚烷基二醇，同样可商购的聚四氢呋喃（例如由LyondellBasell供应的POLYMEG®）也是要注意的。
优选地，线性或支化聚环氧乙烷或聚环氧丙烷用作本发明的组合物中的组分（a1）。
羟基封端的环氧乙烷/环氧丙烷嵌段共聚物特别优选作为组分（a1）。
根据组分（a2）的聚烯烃多元醇是已知的，并在一定程度上是可商购的。聚烯烃多元醇的聚合物骨架通常是烯属单体或烯属单体与乙烯基芳族单体的聚合产物。该烯属单体方便地含有2至12个碳原子。优选地，该烯属单体是具有4至10个碳原子、更优选4至6个碳原子的二烯。
最优选的烯属单体是丁二烯和异戊二烯，特别是1,3-丁二烯。
可以与该烯属单体共聚合的乙烯基芳族单体优选是单乙烯基芳族单体，如苯乙烯或烷基取代的苯乙烯。
根据组分（a2）的聚烯烃多元醇可以含有至多50重量%的聚合的乙烯基芳族单体，例如0.01至20.0重量%，尤其为0至5重量%。
在一个优选实施方案中，根据组分（a2）的聚烯烃多元醇不含有任何聚合的乙烯基芳族单体。
根据本发明合适的聚烯烃多元醇还可以是完全或部分氢化的烯属单体或烯属单体与乙烯基芳族单体的聚合产物。该聚合物的氢化可以根据已知方法来处理，例如通过如美国专利5,039,755中所述在催化剂如兰尼镍、铂、钯或可溶性过渡金属催化剂和钛催化剂的存在下氢化。
如果该聚烯烃多元醇衍生自1,3-丁二烯，该聚丁二烯优选由至少15%的1,2-加成产物组成。
如果该聚烯烃多元醇衍生自异戊二烯，该聚异戊二烯优选由至少80%的1,4-加成产物组成。
该聚烯烃多元醇优选具有500-20000、更优选1000-15000和尤其优选2000-5000的分子量Mn（数均，通过凝胶渗透色谱法GPC测得）。
该聚烯烃多元醇优选表现出每分子1.5至3.0个羟基基团、更优选每分子1.8至2.6个、特别是1.9至2.5个羟基基团的官能度。
该聚烯烃多元醇优选是聚二烯二醇，尤其是聚-1,3-丁二烯二醇。
合适的聚-1,3-丁二烯二醇是下式的化合物：
其中x、y、z、v和w代表结构单元的百分比，并表示以下范围：
x = 10-70%，
y = 15-70%，
z = 10-30%，
v = 10-75%，
w = 25-90%，
条件是x + y + z = 100%且v + w = 100%。
式（1）和（2）的聚烯烃多元醇是可商购的，例如Poly bd® R45 HTLO（由CRAYVALLEY供应）。
根据要求保护的组合物的组分（a3）的聚酯多元醇同样是已知的，并例如描述在Polymer Reviews 52 (1 ), 38 - 79 (2012)中。
用于制备所述聚酯多元醇的起始产品是主要由甘油三酯组成的植物油，其中甘油的三个羟基基团已经用脂肪酸酯化。这些脂肪酸可以是饱和的，即含有非反应性脂族链（如硬脂酸或棕榈酸），或不饱和的，即含有带双键的脂族链（如油酸、亚油酸、亚麻酸或蓖麻油酸）。然而，该甘油三酯必须含有至少两个双键。
植物油可以根据本身已知的方法来环氧化，例如通过与过乙酸的反应，所述过乙酸由乙酸和过氧化氢的反应原位形成。其它合适的方法是植物油的酶促环氧化或通过微波进行的环氧化。
环氧化物的开环反应可以用各种氢活性化合物Nu-H在酸性催化剂（如硫酸、对甲苯磺酸、氟硼酸、高氯酸或氟锑酸）的存在下来进行，其中Nu表示羟基、氨基、烷基氨基、羟基烷基氨基、二烷基氨基、二(羟基烷基)氨基、烷氧基、羟基烷氧基、烷基硫基或烷酰基氧基。
以这种方式，可以制备在分子量、粘度和官能度方面有区别的多种聚酯多元醇。
优选的聚酯多元醇表现出2-4、特别是2.5-3.5的官能度（每分子的羟基基团数），100-300、特别是150-250的中等羟基值，200-500、特别是300-400的中等羟基当量，以及100-2500 mPa·s、特别是200-500 mPa·s的中等粘度（25℃）。
这种类型的聚酯多元醇例如可以以商品名SOVERMOL®商购得（由BASF供应）。
特别优选作为组分（a3）的是SOVERMOL®1111，具有3.0的官能度、160的中等羟基值、350的中等羟基当量和500 mPa·s的中等粘度（25℃）的支化聚酯多元醇。
本发明的多元醇组分（A）可以包含适于PUR技术的其它常规添加剂，例如催化剂、表面活性物质、干燥剂、填料、染料、颜料、阻燃剂、软化剂、热老化稳定剂、触变剂、发泡剂和泡沫稳定剂，例如硅酮和二羧酸。
合适的催化剂是例如叔胺，如N-甲基二乙醇胺、三乙醇胺、二苄基甲基胺或二氮杂双环辛烷或有机锡化合物，如月桂酸二丁基锡。
作为用于PUR泡沫的阻燃剂，通常使用含磷化合物如三鲸蜡醇磷酸酯（tricesylphosphate）或二甲基甲烷膦酸酯（dimezhylmethane phosphonate）或含卤素的多元醇。也可以使用无机阻燃剂如水合氧化铝、三氧化锑和聚磷酸铵。
可以加入矿物油作为软化剂。合适的产品是例如以商品名NYFLEX®出售的油（由Nynas供应）。
适于本发明的多元醇组分的热老化稳定剂是例如脂族缩水甘油醚，如聚丙二醇二缩水甘油醚。
优选的触变剂是熔融二氧化硅，例如以商品名AEROSIL®出售的产品（由Evonik供应）。
本发明的多元醇组分中添加剂的总含量有利地为总组合物的0-30重量%、优选0-15重量%。
在极低反应性（凝胶时间>2小时）的情况下，强烈建议加入特定的泡沫稳定剂。
因此，本发明的另一实施方案是含有如上限定的组分（a1）、（a2）和（a3）以及附加的（a4）聚硅氧烷-聚氧化烯嵌段共聚物的多元醇组分（A）。
作为用于PUR泡沫的稳定剂的聚硅氧烷-聚氧化烯嵌段共聚物例如描述在US-A 6,166,098和EP-A 936 240中，并且可以例如以商品名TEGOSTAB®（由Evonik供应）和DABCO®（由Air Products供应）商购得。
稳定剂TEGOSTAB® B 8863 Z是特别优选的。
组分（a1）、（a2）和（a3）以及任选的（a4）在多元醇组分（A）中所使用的量可以在宽范围内改变。
基于总组合物（包含添加剂）的重量计，包含以下成分的组合物已经证实是有利的：（a1）5-30重量%、优选7-20重量%、尤其是8-15重量%的聚醚多元醇，（a2）30-70重量%、优选35-65重量%、尤其是40-60重量%的羟基封端的聚丁二烯或聚异戊二烯，和（a3）10-50重量%、优选12-40重量%、尤其是15-30重量%的可以通过不饱和脂肪酸酯的环氧化反应以及随后与含有活性氢的化合物的开环反应获得的聚酯多元醇。
在制造PUR泡沫时，含有包含组分（a1）、（a2）和（a3）的组合物的多元醇组分（A）与多异氰酸酯反应。根据本发明可用于制造PUR泡沫的多异氰酸酯在本领域中也是公知的，并且是含有每分子至少两个异氰酸酯基团的有机化合物。可以使用任何这样的化合物或其混合物。异氰酸酯可以是芳族的、脂环族的或脂族的，并可以是单体化合物或低聚化合物。
本发明因此进一步涉及一种组合物，其含有：
（A）如权利要求1所述的包含组分（a1）、（a2）和（a3）的组合物，和
（B）多异氰酸酯。
合适的多异氰酸酯的具体实例是十二烷-1,12-二异氰酸酯、2-乙基四亚甲基-1,4-二异氰酸酯、2-甲基五亚甲基-1,5-二异氰酸酯、四亚甲基-1,4-二异氰酸酯、六亚甲基-1,6-二异氰酸酯、环己烷-1,3-二异氰酸酯、环己烷-1,4-二异氰酸酯、异佛尔酮二异氰酸酯、六氢甲苯-2,4-二异氰酸酯、六氢甲苯-2,5-二异氰酸酯、二环己基甲烷-2,2'-二异氰酸酯、二环己基甲烷-4,4'-二异氰酸酯、二环己基甲烷-2,4'-二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、二苯基甲烷-2,2'-二异氰酸酯（2,2'-MDI）、二苯基甲烷-4,4'-二异氰酸酯（4,4'-MDI）、二苯基甲烷-2,4'-二异氰酸酯（2,4'-MDI）和多苯基多亚甲基多异氰酸酯（粗MDI）。
该有机二异氰酸酯和多异氰酸酯可以单独使用，或以它们的混合物的形式使用。
可商购的二异氰酸酯通常含有二聚（脲二酮）、三聚（三嗪）和低聚化合物。在本发明的组合物中，可以在不分离副产物或纯化的情况下使用这些单体与低聚物的混合物。
优选地，二苯基甲烷二异氰酸酯、更优选二苯基甲烷-4,4'-二异氰酸酯或二苯基甲烷-2,4'-二异氰酸酯用于本发明的PUR泡沫。
在本发明的特别优选的实施方案中，大约60%的4,4'-二苯甲烷二异氰酸酯、大约20%的2,4'-二苯甲烷二异氰酸酯和大约20%的聚合的二苯甲烷二异氰酸酯的混合物用作异氰酸酯组分（B）。
根据本发明由组分（A）和（B）制备的PUR（发泡或不发泡）表现出突出的性能，并可用于各种应用，优选在电工中用作绝缘材料。
本发明因此涉及含有如上定义的组分（A）和（B）的组合物作为用于电气组件的封装材料的用途。
为了制造本发明的PUR泡沫，组分（A）和（B）以使得组分（B）的NCO基团对组分（a1）、（a2）和（a3）的反应性氢原子的总和的当量比为(0.85-1.75):1、优选(1.0-1.3):1的量反应。如果基于异氰酸酯的泡沫含有至少一部分键合的异氰脲酸酯基团，通常采用(1.5-60):1、优选(3-8):1的所述组分的比率。
通常，在PUR形成反应的过程中提供发泡剂。该发泡剂可以是空气、氮气、二氧化碳或任何其它惰性气体。该发泡剂还可以是水，其与异氰酸酯反应以原位生成二氧化碳，或氟化烃如二氯二氟甲烷、1,1-二氯-1-氟乙烷、1-氯-1,1-二氟乙烷、2,2-二氯乙烷等等。非氟化的有机化合物如戊烷和丙酮也可以用作发泡剂。所需发泡剂的量根据所需泡沫密度而改变。发泡剂的合适水平是本领域技术人员已知的。
本发明进一步涉及通过上述方法制备的PUR泡沫在树脂浸渍纸（RIP）套管的制造中用于填充电容器芯与外部复合材料或陶瓷绝缘体之间的间隙的用途。
本发明的PUR泡沫的另一潜在应用领域是暴露于极端温度与压力下的管道的热隔绝，例如用于深海中油气沉积物开采的管道。
因此，本发明进一步涉及通过上述方法制备的PUR泡沫作为用于管道的隔绝材料的用途。
此外，通过本发明的方法制备的PUR泡沫可以有利地用作中空芯复合绝缘体中的填充材料。
因此，通过上述方法制备的PUR泡沫在中空芯复合绝缘体的制造中用于填充中空芯管中的空间的用途是本发明的另一目的。
通过下列非限制性实施例来举例描述本发明。
实施例
所用原材料列表
BAYGAL® K 55（由Bayer供应）：
无色至黄色的三官能聚环氧丙烷/聚环氧乙烷嵌段共聚物；粘度：≈600 mPa·s；羟基值：370 - 400 mgKOH/g；
TEGOSTAB® B 8863 Z（由Evonik供应）：
聚醚改性聚硅氧烷，推荐用作PUR泡沫的泡沫稳定剂；
LUPRANOL® 2095（由BASF供应）：
具有伯羟基端基的三官能聚醚多元醇；推荐用于生产弹性泡沫材料；粘度：≈850mPa·s；羟基值：35 mgKOH/g（DIN 53 240）；
ARALDITE® DY 3601（由Huntsman供应）：
聚丙二醇二缩水甘油醚，环氧值：2.47 - 2.60 eq/kg（ISO 3001）；
NYFLEX 820（由Nynas GmbH供应）：
来自石油的液体环烷烃，粘度：在40℃下为90-110 cSt（ASTM 445）；
Poly bd® R45 HTLO（由CRAY VALLEY供应）：
液体羟基封端的聚丁二烯，粘度：在30℃下为5 Pa·s，羟基官能度：2.5，分子量Mn：2800克/摩尔，1,2-乙烯基含量：20%；
SOVERMOL® 1111（由BASF供应）：
支化聚醚酯，粘度：在25℃下为300-700 mPa·s（DIN 53015）；
UOP L糊剂（由UOP供应）：
在蓖麻油中的具有3Å的近似孔径的沸石A类型的硅酸铝钾钙钠的50%糊剂；
AEROSIL® 200（由Evonik供应）：
亲水性热解二氧化硅，比表面积为200 m2/g；
SUPRASEC® 2447（由Huntsman供应）：
含有大约60%的4,4'-二苯甲烷-二异氰酸酯、大约20%的2,4'-二苯甲烷-二异氰酸酯和大约20%的聚合的二苯甲烷二异氰酸酯的异氰酸酯共混物。
制备组分A：
制备用于本发明的实施例1-3（实施例1-实施例3）和参比例1-3（C1-C3）的组分A：
除SUPRASEC® 2447之外，将根据表1的各配制品的所有组分以所给比例放入足够尺寸的金属罐中，获得200克多元醇混合物。随后通过在23℃下用螺旋桨搅拌器搅拌组分大约2分钟来制备该混合物，得到组分A。
制备组分B：
作为用于本发明的实施例1-3（实施例1-实施例3）和参比例1-3（C1-C3）的组分B，使用100%的Huntsman的SUPRASEC® 2447。
制备组分A和B的反应性混合物：
将大约150克的组分A和根据表1的相应量的组分B放入金属罐中并在环境温度下用螺旋桨搅拌器混合2分钟。随后将80克该反应性混合物用于制造泡沫并重新设定以制造用于下文中描述的tan δ测试的板。结果概括在表1中。
制造泡沫和泡沫稳定性评价：
将80克多元醇/异氰酸酯混合物放入200毫升杯中并随后用小型高剪切分散混合机以2000 rpm搅拌30秒。采用该设备的剪切足以引入因泡沫形成而使体积增加大约30%的空气量。生成的泡沫随后在23℃下固化72小时。随后在均匀性方面检查固化的泡沫样品的外观。通过泡沫稳定性测试的要求是不显示塌陷的迹象。
评价多元醇混合物的储存稳定性：
要求该多元醇混合物（组分A）在室温下经1个月保持澄清，没有分离的迹象。显示出组分的不相容性的配制品通常在一段时间后表现出超过1个的相。
粘度测量：
对组分A和B的混合物施以Rheomat粘度计，并记录粘度的发展，直到达到15 Pa·s。记录达到15 Pa·s所需的时间。根据DIN 53019测量粘度。
Tan δ和Tg测量：
将组分A和B的混合物浇铸（不发泡）到模具中，并通过在90℃下固化该混合物4小时来制造1毫米和2毫米厚的板。 随后根据IEC 60250在2毫米厚的板上测量该tan δ。
根据IEC 6721-2通过DMA在1毫米厚的板上测量Tg。
实施例1-3的组合物提供了长适用期、低Tg（良好的低温柔韧性）、低tan δ（良好的电气性能）和高储存稳定性的组合，而参比例1-3（C1-C3）的组合物不能实现目标的< -50℃的低Tg和所需的<5%（RT）与<15%（100℃）的低tan δ。
表1
*）pbw：重量份
**）n.d.：未测定。

Claims (14)

1.组合物，包含：
（a1）聚醚多元醇，
（a2）聚烯烃多元醇，和
（a3）可以通过不饱和脂肪酸酯的环氧化反应以及随后与含有活性氢的化合物的开环反应获得的聚酯多元醇。
2.如权利要求1所述的组合物，包含线性或支化聚环氧乙烷或聚环氧丙烷作为组分（a1）。
3.如权利要求1所述的组合物，包含羟基封端的环氧乙烷/环氧丙烷嵌段共聚物作为组分（a1）。
4.如前述权利要求任一项所述的组合物，包含聚-1,3-丁二烯多元醇或聚异戊二烯多元醇作为组分（a2）。
5.如前述权利要求任一项所述的组合物，包含可以由作为不饱和脂肪酸酯的植物油获得的聚酯多元醇作为组分（a3）。
6.如前述权利要求任一项所述的组合物，附加地含有：
（a4）聚硅氧烷-聚氧化烯嵌段共聚物。
7.如权利要求1所述的组合物，基于总组合物的重量计，包含：
（a1）5-30重量%的聚醚多元醇，
（a2）30-70重量%的羟基封端的聚丁二烯或聚异戊二烯，和
（a3）10-50重量%的可以通过不饱和脂肪酸酯的环氧化反应以及随后与含有活性氢的化合物的开环反应获得的聚酯多元醇。
8.组合物，含有：
（A）如权利要求1所述的包含组分（a1）、（a2）和（a3）的组合物，和
（B）多异氰酸酯。
9.如权利要求8所述的组合物，含有二苯基甲烷二异氰酸酯作为组分B。
10.如权利要求8所述的组合物作为用于电气组件的封装材料的用途。
11.用于制造PUR泡沫的方法，通过使以下物质在发泡剂的存在下反应：
（A）含有如权利要求1所述的组合物的多元醇组分，与
（B）多异氰酸酯。
12.通过如权利要求11所述的方法制备的PUR泡沫在树脂浸渍纸（RIP）套管的制造中用于填充电容器芯与外部复合材料绝缘体之间的间隙的用途。
13.通过如权利要求11所述的方法制备的PUR泡沫作为用于管道的隔绝材料的用途。
14.通过如权利要求11所述的方法制备的PUR泡沫在中空芯复合绝缘体的制造中用于填充中空芯管中的空间的用途。
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