CN110234674B - 冷柔聚氨酯制剂 - Google Patents

冷柔聚氨酯制剂 Download PDF

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CN110234674B
CN110234674B CN201880008354.7A CN201880008354A CN110234674B CN 110234674 B CN110234674 B CN 110234674B CN 201880008354 A CN201880008354 A CN 201880008354A CN 110234674 B CN110234674 B CN 110234674B
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CN110234674A (zh
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N·蒙梅耶
O·格拉尔曼
C·格莱瑟-施密茨
A·艾森哈特
J-D·埃斯拉瓦
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BASF SE
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Abstract

本发明涉及制备冷柔聚氨酯绝热体的方法，其中将(a)多异氰酸酯与(b)具有对异氰酸酯呈反应性的基团的化合物、(c)发泡剂、(d)催化剂、(e)增塑剂和任选地(f)其他添加剂混合，得到反应混合物，并将混合物施用至表面并固化以形成绝热体，其中具有对异氰酸酯呈反应性的基团的化合物(b)包括：至少一种聚醚醇(b1)，其标称官能度为4以上，环氧丙烷比例基于聚醚醇(b1)中环氧烷的总重量计大于60重量％，且OH值为至少300mg KOH/g；至少一种聚醚醇(b2)，其标称官能度为3.5以下，伯OH基团比例大于50％，且OH值为小于300mg KOH/g；至少一种聚酯醇(b3)和扩链剂和/或交联剂(b4)。本发明还涉及可通过本发明方法获得的聚氨酯绝热体。

Description

冷柔聚氨酯制剂
技术领域
本发明涉及制备冷柔聚氨酯绝热体的方法，其中将(a)多异氰酸酯与(b)具有对异氰酸酯呈反应性的基团的化合物、(c)发泡剂、(d)催化剂、(e)增塑剂和任选地(f)其他添加剂混合，得到反应混合物，并将混合物施用至表面并固化以形成绝热体，其中异氰酸酯(a)和具有对异氰酸酯呈反应性的基团的化合物(b)、发泡剂(c)、催化剂(d)、增塑剂及任选地其他添加剂(e)以这样的量反应以使得异氰酸酯指数范围为100至200，具有对异氰酸酯呈反应性的基团的化合物(b)包括：至少一种聚醚醇(b1)，其标称官能度为4以上，环氧丙烷比例基于聚醚醇(b1)中环氧烷的总重量计大于60重量％，且OH值为至少300mg KOH/g；至少一种聚醚醇(b2)，其标称官能度为3.5以下，伯OH基团比例大于50％，且OH值为小于300mgKOH/g；至少一种聚酯醇(b3)和扩链剂和/或交联剂(b4)，聚醚醇(b2)包括：至少一种聚醚醇(b2a)，其标称官能度为3.5以下，环氧乙烷的比例基于多元醇(b2a)中环氧烷的总重量计为至少80重量％，伯OH基团的比例大于80重量％，且OH值为大于100mg KOH/g至小于300mgKOH/g；和至少一种聚醚醇(b2b)，其标称官能度为3.5以下，伯OH基团的比例大于60％，且OH值为大于20mg KOH/g至小于80mg KOH/g,且其中发泡剂的水含量基于组分(b)至(e)的总重量计小于0.5重量％。本发明还涉及可通过本发明方法获得的聚氨酯绝热体。
背景技术
除石油外，天然气是我们这个时代最重要的能源之一。天然气作为相对清洁的能源更经常地用于尤其是移动运输工具，例如乘用车、货车、航空器或特别是船上。在该处，尤其是在人口密集的地区如港口城市以及北海和波罗的海等沿海水域，尝试省却目前在航运中用作主要能源的重质燃料油的燃烧并使用天然气作为清洁能源。然而，在正常状态下天然气的大的空间需求在此是一个问题。因此，天然气被液化以减少空间需求。由于天然气仅在约-160℃的非常低的温度下液化，并且必须在这些温度下储存和运输，因此必须尽可能地使罐绝热以保持液化气体通过蒸发造成的损失小。
目前，液化天然气罐使用例如珍珠岩或基于硬质聚氨酯泡沫的绝热板绝热。因此，例如在EP 1698649、WO 2008083996和WO 2008/083996中描述了基于聚氨酯的绝热板及其用于船上液化天然气罐的绝热的用途。这些文件描述了如何将绝热板定尺切割并与胶合板薄板和树脂-浸渍的玻璃纤维垫粘合在一起。还陈述了然后在罐的构造中直接使用这些元件。该方法的缺点是它是一个复杂的程序。此外，由于没有足够的可用空间，因此不能用于液化天然气罐的改装。
发明内容
因此，本发明的一个目的是提供一种聚氨酯材料，其适用于使液化天然气罐绝热，特别是在船上，并且可以简单地安装。特别地，本发明的一个目的是提供一种在非常狭窄的地方使液化天然气罐绝热的方法，例如在船上在这种罐的改装中。获得的聚氨酯在低温下应具有特别优选的性能，特别是根据CINI(Committee Industrial Insulation)具有高CTSR因子(低温热应力抗性)。
本发明的目的已通过一种制备冷柔聚氨酯绝热体的方法实现，其中将(a)多异氰酸酯与(b)具有对异氰酸酯呈反应性的基团的化合物、(c)发泡剂、(d)催化剂、(e)增塑剂和任选地(f)其他添加剂混合，得到反应混合物，并将混合物施用至表面并固化以形成绝热体，其中异氰酸酯(a)和具有对异氰酸酯呈反应性的基团的化合物(b)、发泡剂(c)、催化剂(d)、增塑剂及任选地其他添加剂(e)以这样的量反应以使得异氰酸酯指数范围为100至200，具有对异氰酸酯呈反应性的基团的化合物(b)包括：至少一种聚醚醇(b1)，其标称官能度为4以上，环氧丙烷的比例基于聚醚醇(b1)中环氧烷的总重量计大于60重量％，且OH值为至少300mg KOH/g；至少一种聚醚醇(b2)，其标称官能度为3.5以下，伯OH基团的比例大于50％且OH值小于300mg KOH/g；至少一种聚酯醇(b3)；以及扩链剂和/或交联剂(b4)，聚醚醇(b2)包括：至少一种聚醚醇(b2a)，其标称官能度为3.5以下，环氧乙烷的比例基于多元醇(b2a)中环氧烷的总重量计为至少80重量％，伯OH基团的比例大于80重量％，且OH值为大于100mg KOH/g至小于300mg KOH/g；和至少一种聚醚醇(b2b)，其标称官能度为3.5以下，伯OH基团的比例大于60％，且OH值为大于20mg KOH/g至小于80mg KOH/g,且其中发泡剂的水含量基于组分(b)至(e)的总重量计小于0.5重量％。
具体实施方式
出于本发明目的，多异氰酸酯(a)为每分子包括至少两个反应性异氰酸酯基团(即官能度至少为2)的有机化合物。如果所用的多异氰酸酯或多种多异氰酸酯的混合物不具有一致的官能度，则所用的组分a)的数均官能度至少为2。优选地，多异氰酸酯a)的平均异氰酸酯官能度至少为2.2，特别优选地为2.2至4。
可能的多异氰酸酯a)为本身已知的脂族、脂环族、芳脂族和优选地芳族多官能异氰酸酯。这种多官能异氰酸酯本身是已知的，或可通过本身已知的方法制备。特别地，多官能异氰酸酯其也可作为混合物使用，如此，在这种情况下组分a)包括多种多官能异氰酸酯。考虑作为多异氰酸酯的多官能异氰酸酯每分子具有两个(下文称为二异氰酸酯)或多于两个异氰酸酯基团。
特别地，可具体提及：亚烷基基团中具有4至12个碳原子的亚烷基二异氰酸酯，例如十二烷1,12-二异氰酸酯、2-乙基四亚甲基1,4,2-二异氰酸酯、甲基五亚甲基1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯以及优选地六亚甲基1,6-二异氰酸酯；脂环族二异氰酸酯，例如环己烷1,3-二异氰酸酯和环己烷1,4-二异氰酸酯以及这些异构体的任意混合物，1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(IPDI)，六氢甲苯2,4-二异氰酸酯和六氢甲苯2,6-二异氰酸酯以及相应的异构体混合物，二环己基甲烷4,4'-二异氰酸酯、二环己基甲烷2,2'-二异氰酸酯和二环己基甲烷2,4'-二异氰酸酯以及相应的异构体混合物；以及优选地芳族多异氰酸酯，例如甲苯2,4-二异氰酸酯和甲苯2,6-二异氰酸酯以及相应的异构体混合物，二苯基甲烷4,4'-二异氰酸酯、二苯基甲烷2,4'-二异氰酸酯和二苯基甲烷2,2'-二异氰酸酯以及相应的异构体混合物，二苯基甲烷4,4'-二异氰酸酯和二苯基甲烷2,4'-二异氰酸酯的混合物，多苯基多亚甲基多异氰酸酯，二苯基甲烷4,4'-二异氰酸酯、二苯基甲烷2,4'-二异氰酸酯和二苯基甲烷2,2'-二异氰酸酯和多苯基多亚甲基多异氰酸酯的混合物(粗MDI)，以及粗MDI和甲苯二异氰酸酯的混合物。
特别合适的多异氰酸酯为二苯基甲烷2,2'-二异氰酸酯、二苯基甲烷2,4'-二异氰酸酯和二苯基甲烷4,4'-二异氰酸酯(MDI)，1,5-萘二异氰酸酯(NDI)，甲苯2,4-二异氰酸酯和/或甲苯2,6-二异氰酸酯(TDI)，3,3'-二甲基二苯基二异氰酸酯，1,2-二苯基乙烷二异氰酸酯和/或对苯二异氰酸酯(PPDI)，三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯、六亚甲基二异氰酸酯、七亚甲基二异氰酸酯和/或八亚甲基二异氰酸酯，2-甲基五亚甲基-1,5-二异氰酸酯，2-乙基亚丁基-1,4-二异氰酸酯，五亚甲基-1,5-二异氰酸酯，亚丁基-1,4-二异氰酸酯，1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(异佛尔酮二异氰酸酯，IPDI)，1,4-双(异氰酸酯基甲基)环己烷和/或1,3-双(异氰酸酯基甲基)环己烷(HXDI)，1,4-环己烷二异氰酸酯，1-甲基-2,4-环己烷二异氰酸酯和/或1-甲基-2,6-环己烷二异氰酸酯，以及二环己基甲烷4,4'-二异氰酸酯、二环己基甲烷2,4'-二异氰酸酯和/或二环己基甲烷2,2'-二异氰酸酯。
经常还使用改性多异氰酸酯，即通过有机多异氰酸酯的化学反应获得并且每分子具有至少两个反应性异氰酸酯基团的产物。特别提及的可为包含酯、脲、缩二脲、脲基甲酸酯、碳二亚胺、异氰脲酸酯、脲二酮(uretdione)、氨基甲酸酯和/或氨基甲酸乙酯基团的多异氰酸酯，经常还与未反应的多异氰酸酯一起。
组分a)的多异氰酸酯特别优选地包括：2,2’-MDI或2,4’-MDI或4,4’-MDI(也称为单体二苯甲烷或MMDI)；或低聚MDI，其由具有多于两个环的MDI的更高级同系物组成，其具有至少3个芳族环且官能度至少为3；或上述二苯基甲烷二异氰酸酯中的两种或三种的混合物；或粗MDI，其在MDI的制备中获得；或优选地至少一种MDI的低聚物和上述低分子量MDI衍生物2,2’-MDI、2,4’-MDI或4,4’-MDI中的至少一种的混合物(也称为聚合MDI)。MDI的异构体和同系物通常通过蒸馏粗MDI获得。
除了双环MDI之外，聚合MDI优选包含一种或多种官能度大于2、特别是3或4或5的MDI的多环缩合产物。聚合MDI是已知的并且经常被称为多苯基多亚甲基多异氰酸酯。
包含聚合MDI的多异氰酸酯的(平均)官能度可在约2.2至约4、特别是2.4至3.8且特别是2.6至3.0的范围内变化。特别地，具有不同官能度的这种MDI-基的多官能异氰酸酯的混合物为在MDI制备中作为中间体获得的粗MDI。
基于MDI的多官能异氰酸酯或多种多官能异氰酸酯的混合物是已知的，并且例如由BASF Polyurethanes GmbH以商品名
Figure GDA0003170971330000051
M20或
Figure GDA0003170971330000052
M50销售。
组分(a)优选包含至少70重量％、特别优选至少90重量％且特别是100重量％的一种或多种选自2,2'-MDI、2,4'-MDI、4,4'-MDI和MDI低聚物的异氰酸酯，基于组分(a)的总重量计。此处，低聚MDI的含量优选为至少20重量％，特别优选为大于30重量％至小于80重量％，基于组分(a)的总重量计。
作为具有对异氰酸酯呈反应性的基团的化合物(b)，可以使用具有至少两个对异氰酸酯呈反应性的基团(例如OH-、SH-、NH-和CH-酸基团)的所有化合物。具有对异氰酸酯呈反应性的基团的化合物(b)通常包括具有对异氰酸酯呈反应性的基团的聚合物，并且具有2至8个对异氰酸酯呈反应性的氢原子，例如聚醚多元醇和聚酯多元醇。此处，聚醚醇和聚酯醇的分子量为300g/mol或更高，扩链剂和交联剂的分子量小于300g/mol。
聚醚醇通过已知方法获得，例如通过在催化剂的存在下加入至少一种包含2至8个、优选2至6个结合形式的反应性氢原子的起始剂分子的情况下的环氧烷的阴离子聚合。因此，聚醚醇的标称官能度为2至8、优选为2至6，并且对应于起始剂分子的官能度。如果使用具有不同官能度的起始剂分子的混合物，则可获得分数官能度(fractionalfunctionality)。对官能度的影响，例如由于二次反应造成的影响，不被考虑在标称官能度中。作为催化剂，可以使用碱金属氢氧化物如氢氧化钠或氢氧化钾或碱金属醇盐如甲醇钠、乙醇钠或乙醇钾或异丙醇钾，或在阳离子聚合的情况下，可以使用路易斯酸如五氯化锑、三氟化硼醚合物或漂白土作催化剂。此外，双金属氰化物——称为DMC催化剂——也可用作催化剂。
作为环氧烷，优选使用一种或多种在亚烷基中具有2至4个碳原子的化合物，例如四氢呋喃、1,3-环氧丙烷、1,2-环氧丁烷或2,3-环氧丁烷，在每种情况下单独或以混合物的形式使用，且优选环氧乙烷和/或1,2-环氧丙烷。
可能的起始剂分子为，例如，乙二醇、二乙二醇、丙三醇、三羟甲基丙烷、季戊四醇、糖衍生物如蔗糖、己糖醇衍生物如山梨糖醇、甲胺、乙胺、异丙胺、丁胺、苄胺、苯胺、甲苯胺、甲苯二胺、萘胺、乙二胺、二亚乙基三胺、4,4'-亚甲基二苯胺、1,3-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺和其他二元醇或多元醇或单官能胺或多官能胺。
聚酯醇通常通过使具有2至12个碳原子的多官能醇与具有2至12个碳原子的多官能羧酸缩合来制备，所述多官能醇为例如乙二醇、二乙二醇、丁二醇、三羟甲基丙烷、丙三醇或季戊四醇，所述多官能羧酸例如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸二羧酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸的异构体或所述酸的酸酐。
作为制备聚酯的其他起始原料，也可同时使用疏水性材料。疏水性材料是水不溶性材料，其包括非极性有机基团并且还具有至少一个选自羟基、羧基、羧酸酯及其混合物的反应性基团。疏水性材料的当量重量优选为130至1000g/mol。还可以使用例如脂肪酸如硬脂酸、油酸、棕榈酸、月桂酸或亚油酸，以及脂肪和油如蓖麻油、玉米油、向日葵油、大豆油、椰子油、橄榄油或妥尔油。如果聚酯包括疏水性材料，则疏水性材料的比例基于聚酯醇的总单体含量计优选为1-30摩尔％，特别优选为4至15摩尔％。
此处聚酯醇的官能度优选为1.5至5，特别优选为1.8-3.5，且特别是1.9至2.2。
根据本发明，具有对异氰酸酯呈反应性的基团的化合物(b)包括：至少一种聚醚醇(b1)，其标称官能度为4以上，环氧丙烷的比例基于聚醚醇(b1)中环氧烷的总重量计大于60重量％、优选大于80重量％、特别优选大于90重量％且特别是100重量％，且仲OH基团的比例优选地大于50％、特别优选地大于70％、更优选地大于90％且特别是100％，且OH值至少为300mg KOH/g、优选地至少400mg KOH/g；至少一种聚醚醇(b2)，其标称官能度为3.5以下、优选地为2.0至3.5且特别优选地为2.8至3.2，伯OH基团的比例大于50％、优选地大于70％且特别优选地大于80％，且OH值小于300mg KOH/g；至少一种聚酯醇(b3)；以及扩链剂和/或交联剂(b4)。作为组分(b1)至(b3)，在每种情况下可以使用单独的化合物或混合物，其中所使用的每种化合物都符合(b1)至(b3)的定义。
聚醚醇(b1)的环氧丙烷的比例优选大于80重量％、特别优选大于90重量％且特别是100重量％，基于聚醚醇(b1)中环氧烷的总重量计。仲OH基团的比例优选大于50％、特别优选大于70％、更优选大于90％且特别是100％。聚醚醇(b1)的OH值优选为300至1000，特别优选为400至800。在优选的实施方案中，在聚醚醇(b1)的制备中使用4-官能胺、优选乙二胺作为起始剂。
聚醚醇(b2)包括：至少一种聚醚醇(b2a)，其标称官能度为3.5以下，环氧乙烷的比例基于多元醇(b2a)中环氧烷的总重量计为至少80重量％、优选至少90重量％且特别是至少100重量％，伯OH基团的比例大于80重量％、优选大于90重量％且特别是100重量％，且OH值为大于100mg KOH/g至小于300mg KOH/g；和至少一种聚醚醇(b2b)，其标称官能度为3.5以下，环氧丙烷的比例基于多元醇(b2b)中环氧烷的总重量计优选为至少50重量％、特别优选60至90重量％，伯OH基团的比例大于50％、优选60至90％，且OH值为大于20mg KOH/g至小于80mg KOH/g，优选为大于25mg KOH/g至小于60mg KOH/g且特别优选为大于30mg KOH/g至小于50mg KOH/g。
聚酯多元醇(b3)的官能度优选为2.0至2.5，羟值为100mgKOH/g至400mgKOH/g，特别优选为200mgKOH/g至300mgKOH/g。聚酯多元醇(b3)优选通过二酸与二醇的缩合获得，其中二酸组分优选包含芳族二酸。特别优选不使用除芳族二酸之外的任何其他二酸来制备聚酯多元醇(b3)。特别优选使用邻苯二甲酸、间苯二甲酸和/或对苯二甲酸作为二酸。二醇组分优选包括二乙二醇。
作为扩链剂和/或交联剂(b4)，特别优选使用双官能或三官能的胺和醇，特别是二醇、三醇或两者，在每种情况下具有小于250g/mol、优选60至250g/mol且特别是60至200g/mol的分子量。此处，双官能化合物被称为扩链剂，三官能或更高官能的化合物被称为交联剂。可能的是，例如，具有2至14个、优选2至10个碳原子的脂族、脂环族和/或芳族二醇，例如乙二醇，1,2-丙二醇、1,3-丙二醇，1,2-戊二醇、1,3-戊二醇，1,10-癸二醇，1,2-二羟基环己烷、1,3-二羟基环己烷、1,4-二羟基环己烷，二乙二醇以及三乙二醇、二丙二醇和三丙二醇，1,4-丁二醇、1,6-己二醇和双-(2-羟乙基)氢醌；三醇如1,2,4-三羟基环己烷、1,3,5-三羟基环己烷、丙三醇和三羟甲基丙烷，三乙醇胺，基于环氧乙烷和/或1,2-环氧丙烷的低分子量的含羟基的聚环氧烷；和作为起始剂分子的上述二醇和/或三醇以及胺例如3,6-二氧杂八亚甲基二胺。优选使用三官能醇如丙三醇和三乙醇胺以及二胺如3,6-二氧杂八亚甲基二胺。扩链剂和/或交联剂(b4)优选包括至少一种具有胺端基的化合物。
组分(b1)的比例优选为15至35重量％，组分(b2)的比例优选为15至35重量％，组分(b3)的比例优选为20至35重量％，且组分(b4)的比例优选为10至35重量％，在每种情况下基于组分(b)的总重量计。
在特别优选的实施方案中，除组分(b1)至(b4)外，组分(b)包括小于20重量％、特别优选小于10重量％的且特别是不包括其他具有对异氰酸酯呈反应性的基团的化合物。如果使用异氰酸酯预聚物作为异氰酸酯(a)，则具有对异氰酸酯呈反应性的基团的化合物(b)的含量的计算包括用于制备异氰酸酯预聚物的具有对异氰酸酯呈反应性的基团的化合物(b)。
此外，本发明的冷柔聚氨酯绝热体的生产中存在发泡剂(c)。作为发泡剂(c)，可以使用化学作用的发泡剂和/或物理作用的化合物。出于本发明的目的，化学发泡剂为通过与异氰酸酯反应形成气态产物(例如水或甲酸)的化合物。出于本发明的目的，物理发泡剂为溶解或乳化于用于制备聚氨酯的起始材料中并在聚氨酯形成条件下蒸发的化合物。它们例如是烃类、卤代烃类和其他化合物，例如全氟化烷烃例如全氟己烷、氯氟烃，以及醚、酯、酮和/或缩醛，例如具有4至8个碳原子的(环)脂族烃，氟化烃如
Figure GDA0003170971330000081
365mfc或HFC 245-fa，或气体如二氧化碳。在优选的实施方案中，物理发泡剂、优选不可燃的物理发泡剂用作发泡剂。特别地，氟化烃用作发泡剂。它们可包括少量化学发泡剂，优选水。此处，水的比例基于组分(b)至(e)的总重量计小于0.5重量％、优选小于0.2重量％且特别是小于0.1重量％。在一个优选的实施方案中，物理发泡剂的含量范围为5至30重量％、特别是10至25重量％，基于组分(b)至(e)的总重量计。
发泡剂的用量应使本发明的冷柔聚氨酯绝热体的密度优选为30至80克/升，特别优选为50至70克/升。
作为催化剂(d)，可以使用加速异氰酸酯-水反应或异氰酸酯-多元醇反应的所有化合物。这些化合物是已知的并描述于例如“Kunststoffhandbuch，第7卷，Polyurethane(聚氨酯)”，Carl Hanser Verlag，第3版，1993，第3.4.1章中。它们包括胺-基催化剂和基于有机金属化合物的催化剂。
作为基于有机金属化合物的催化剂，可以使用例如有机锡化合物，例如有机羧酸的锡(II)盐如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II)，以及有机羧酸的二烷基锡(IV)盐例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡；以及羧酸铋如新癸酸铋(III)、2-乙基己酸铋和辛酸铋或羧酸的碱金属盐如乙酸钾或甲酸钾。
通常使用含叔胺的化合物作为胺-基催化剂。它们也可带有对异氰酸酯呈反应性的基团，例如OH、NH或NH2基团。一些最经常使用的催化剂为双(2-二甲基氨基乙基)醚、N,N,N,N,N-五甲基二亚乙基三胺、N,N,N-三乙氨基乙氧基乙醇、二甲基环己胺、二甲基苄胺、三乙胺、三亚乙基二胺、五甲基二亚丙基三胺、二甲基乙醇胺、N-甲基咪唑、N-乙基咪唑、四甲基六亚甲基二胺、三(二甲基氨基丙基)六氢三嗪、二甲基氨基丙胺、N-乙基吗啉、二氮杂双环十一碳烯和二氮杂双环壬烯。
优选使用包含至少一种叔胺和至少一种基于有机金属化合物的催化剂的混合物作为催化剂(d)。
作为增塑剂(e)，可以提及例如多元羧酸、优选二元羧酸与一元醇的酯。这些酯的酸组分可例如衍生自琥珀酸、间苯二甲酸、对苯二甲酸、偏苯三酸、柠檬酸、邻苯二甲酸酐、四氢邻苯二甲酸酐和/或六氢邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、戊二酸酐、马来酸酐、富马酸和/或任选地与单体脂肪酸混合的二聚脂肪酸和/或三聚脂肪酸例如油酸。这些酯的醇组分可例如衍生自具有1至20个碳原子的支链和/或非支链脂族醇，例如，甲醇、乙醇、丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、戊醇的各种异构体、己醇、辛醇(如2-乙基己醇)、壬醇、癸醇、月桂醇、肉豆蔻醇、鲸蜡醇、硬脂醇和/或天然存在的脂肪醇和蜡醇或可通过天然存在的羧酸的氢化获得的脂肪醇和蜡醇。可能的醇组分还有脂环族和/或芳族羟基化合物，例如环己醇及其同系物、苯酚、甲酚、百里香酚、香芹酚、苄醇和/或苯基乙醇。还可用作增塑剂的是一元羧酸与二元醇的酯，例如Texanol酯醇，例如2,2,4-三甲基-1,3-戊二醇二异丁酸酯(TXIB)或2,2,4-三甲基-1,3-戊二醇二苯甲酸酯；低聚亚烷基二醇和烷基羧酸的二酯，例如三乙二醇二己酸酯或四乙二醇二庚酸酯及类似化合物。
此外，上述醇与磷酸的酯可用作增塑剂(e)。也可任选使用衍生自卤代醇的磷酸酯，例如磷酸三氯乙酯。在后一种情况下，可在增塑剂效果的同时实现阻燃效果。当然，也可以使用上述醇和羧酸或磷酸的混合酯。
增塑剂也可为聚合物增塑剂，例如己二酸、癸二酸和/或邻苯二甲酸的聚酯。
此外，苯酚的烷基磺酸酯，例如苯基链烷烃磺酸酯和芳族磺酰胺，例如乙基甲苯磺酰胺也可用作增塑剂。也可以使用聚醚例如三乙二醇二甲醚作为增塑剂。
此外，通常用作阻燃剂的有机磷酸盐(如三氯丙基磷酸酯(TCPP)、乙基膦酸二乙酯(DEEP)、磷酸三乙酯(TEP)、二甲基丙基膦酸酯(DMPP)、二苯基甲酚基磷酸酯(DPC)或磷酸三乙酯)也具有增塑效果且可用作增塑剂(e)。
增塑剂(d)优选包括有机磷酸酯，特别优选磷酸三氯丙酯和/或磷酸三乙酯，优选磷酸三氯丙酯和磷酸三乙酯。此处，磷酸三氯丙酯与磷酸三乙酯的重量比为1:10至10:1，优选为1:5至2:1，特别优选为1:2至1:1。在特别优选的实施方案中，除了磷酸三氯丙酯和磷酸三乙酯之外，不使用其他增塑剂。
增塑剂的用量优选为0.1至30重量％，特别优选为5至25重量％，特别是10至20重量％，基于组分(b)至(e)的总重量计。通过添加增塑剂可以进一步改善硬质聚氨酯泡沫的机械性能，尤其是在低温下。
作为其他添加剂(e)，可以使用阻燃剂、泡沫稳定剂、其他填料和其他添加剂如抗氧化剂。
作为阻燃剂，通常可以使用现有技术中已知的阻燃剂。合适的阻燃剂为，例如，溴化醚(Ixol B 251)，溴化醇如二溴新戊醇、三溴新戊醇和PHT-4-二醇，以及也用作增塑剂的氯化磷酸酯，例如化合物三(2-氯乙基)磷酸酯、三(2-氯异丙基)磷酸酯(TCPP)、三(1,3-二氯异丙基)磷酸酯、三(2,3-二溴丙基)磷酸酯和四(2-氯乙基)亚乙基二磷酸酯，或它们的混合物。
除了上述卤素-取代的磷酸酯以外，还可以使用无机阻燃剂例如红磷、含红磷的制剂、可膨胀石墨、氧化铝水合物、三氧化锑、三氧化二砷、多磷酸铵和硫酸钙，或氰尿酸衍生物例如三聚氰胺，或至少两种阻燃剂的混合物，例如多磷酸铵和三聚氰胺，以及任选地淀粉，用于使根据本发明制备的硬质聚氨酯泡沫具有阻燃性。
作为其他液体无卤阻燃剂，可以使用乙基膦酸二乙酯(DEEP)、磷酸三乙酯(TEP)、二甲基丙基膦酸酯(DMPP)、二苯基甲酚基磷酸酯(DPC)等，它们同样具有增塑效果，因此也可用作增塑剂。
出于本发明的目的，阻燃剂优选以基于组分(b)至(e)的总重量计0至25％的量使用。如果使用有机磷化合物作为增塑剂，则优选不使用其他阻燃剂。
出于本发明的目的，泡沫稳定剂为在发泡期间促进形成规则泡孔结构的材料。可提及以下实例：含聚硅氧烷的泡沫稳定剂，例如硅氧烷-氧化烯共聚物和其他有机聚硅氧烷。另外，脂肪醇、羰基合成醇、脂肪胺、烷基酚、二烷基酚、烷基甲酚、烷基间苯二酚、萘酚、烷基萘酚、萘胺、苯胺、烷基苯胺、甲苯胺、双酚A、烷基化双酚A、聚乙烯醇的烷氧基化产物，以及此外甲醛和烷基酚、甲醛和二烷基酚、甲醛和烷基甲酚、甲醛和烷基间苯二酚、甲醛和苯胺、甲醛和甲苯胺、甲醛和萘酚、甲醛和烷基萘酚以及甲醛和双酚A的缩合产物的烷氧基化产物，或两种或更多种这些泡沫稳定剂的混合物。
如果存在，则泡沫稳定剂的用量优选为0.5至4重量％，特别优选为1至3重量％，基于组分(b)至(e)的总重量计。
出于本发明的目的，其他填料、特别是增强填料，是本身已知的常规有机和无机填料、增强材料等。具体实例为：无机填料，如含硅矿物，例如片状硅酸盐，如叶蛇纹石、蛇纹石、角闪石岩(hornblends)、闪石、温石棉、滑石；金属氧化物如高岭土、氧化铝、氧化钛和氧化铁，金属盐如白垩、重晶石和无机颜料如硫化镉、硫化锌以及玻璃等。优选使用高岭土(瓷土)、硅酸铝以及硫酸钡和硅酸铝的共沉淀物以及可任选被胶料涂覆的天然的和合成的纤维矿物质例如硅灰石、金属纤维以及特别是各种长度的玻璃纤维。也可使用中空玻璃微球。可能的有机填料为，例如：碳、三聚氰胺、松香、环戊二烯基树脂和接枝聚合物以及纤维素纤维、聚酰胺纤维、聚丙烯腈纤维、聚氨酯纤维、基于芳族和/或脂族二羧酸酯的聚酯纤维以及特别是碳纤维。
无机填料和有机填料可单独使用或作为混合物使用，且如果存在，以基于组分(b)至(e)的重量计0.5至30重量％、优选1至15重量％的量掺入反应混合物中。
优选通过喷雾将反应混合物施加至待绝热的表面上。待绝热的表面优选是罐，特别优选是用于液化天然气的罐。其也可由金属或塑料组成。为此目的，优选将组分(b)至(d)和任选地(e)混合，得到多元醇组分。然后优选将它们与异氰酸酯组分(a)在低压混合设备中、在高压混合设备中在小于100bar的减压下或在高压机器中混合，并通过喷嘴直接施用至待绝热表面。表面可任选地以已知方式预先预处理，以改善粘附性，例如通过施加已知的粘合剂。
异氰酸酯(a)和具有对异氰酸酯呈反应性的基团的化合物(b)、发泡剂(c)、催化剂(d)、增塑剂及任选地其他添加剂(e)优选以这样的量反应以使得异氰酸酯指数范围为100至200，优选为100-150。
出于本发明的目的，异氰酸酯指数为异氰酸酯基团与对异氰酸酯呈反应性的基团的化学计量比，乘以100。对于本发明目的，对异氰酸酯呈反应性的基团为对异氰酸酯呈反应性并包含在反应混合物中的所有基团，包括化学发泡剂，但不包括异氰酸酯基团本身。
本发明还提供可通过本发明方法获得的聚氨酯绝热体。本发明的聚氨酯绝热体优选用于使船上的液化天然气罐绝热，尤其是包括用于在船上产生能量的液化天然气并包括绝热罐、优选液化天然气罐的船上的液化天然气罐。本发明的聚氨酯绝热体显示出优异的冷柔性；此处垂直于发泡方向和平行于发泡方向上的CTSR因子(低温热应力抗性)优选为至少1.2，特别优选为至少1.5。此处，出于本发明的目的，CTSR因子确定如下：(温度范围＝-163℃至30℃)
Figure GDA0003170971330000121
σZT＝根据EN ISO 527在-165℃下的拉伸强度，以kPa计
υ＝泊松比；沿垂直于拉伸方向的两个轴之一的应力增加Δεn与拉伸方向上的相应应力增加Δεl的负比，横向应力/纵向应力曲线的初始线性部分内测量
E＝根据EN ISO 527在-165℃下的弹性模量，以kPa计
α＝根据DIN 53752的长度变化系数，以mm/(mm·k)计
ΔT＝温差(193K)
此外，本发明的聚氨酯绝热体根据EN 14320-1-C.3在垂直于发泡方向和平行于发泡方向上显示出优选小于0.0220W/(m·k)、特别优选0.0210W/(m·k)且特别是0.0200W/(m·k)的优异的导热性，制备泡沫后在10℃(平均温度)下测量。老化后，根据EN 14320-1-C.4或EN 14320-1-C5垂直于发泡方向和平行于发泡方向上的导热率小于0.0280W/(m·k)，优选小于0.024W/(m·k)，特别是小于0.0220W/(m·k)。闭孔的比例根据EN ISO 4590优选为至少90％，特别优选至少94％。此外，本发明的聚氨酯绝热体根据EN ISO 826在室温下具有至少0.3N/mm2、特别优选至少0.4N/mm2且特别是至少0.5N/mm2的优异的压缩强度和根据EN 527-2在室温下至少0.3N/mm2、特别优选至少0.4N/mm2且特别是至少0.5N/mm2的拉伸强度。在-165℃下，根据EN ISO 826的拉伸强度至少为0.5N/mm2、特别优选至少为0.5N/mm2且特别是至少为0.7N/mm2。因此本发明聚氨酯绝热体非常适合用于使液化天然气罐绝热，例如在交通工具上，特别是用于使在包括用于在船上产生能量的液化天然气的船上的液化天然气罐绝热。
下面将借助实施例说明本发明。
实施例
在泡沫生长的平行方向以及垂直方向上确定CTSR因子和产物的导热率。为此目的制备尺寸为至少800mm(宽度)×800mm(长度)×300mm(厚度)的大型多层泡沫块。以下泡沫试样应从泡沫芯上切下：
·12片，各自的尺寸为80mm×80mm×200mm(在泡沫生长的平行方向上200mm厚)，用于确定在低温下在泡沫生长的平行方向上拉伸强度和弹性模量。
·12片，其尺寸为80mm×80mm×200mm(在泡沫生长的垂直方向上200mm厚)，用于确定在低温下在泡沫生长的垂直方向上的拉伸强度和弹性模量。
·2片，其尺寸为50mm×50mm×150mm(在泡沫生长的平行方向上150mm厚)，用于确定在泡沫生长的平行方向上的长度变化。
·2片，其尺寸为50mm×50mm×150mm(在泡沫生长的垂直方向上150mm厚)，用于确定在泡沫生长的垂直方向上的长度变化。
·2片，其尺寸为200mm×200mm×35mm(在泡沫生长的平行方向上35mm厚)，用于确定在泡沫生长的平行方向上的导热率变化。
·2片，其尺寸为200mm×200mm×35mm(在泡沫生长的垂直方向上35mm厚)，用于确定在泡沫生长的垂直方向上的导热率变化。
为根据实施例1和比较实施例C1制备本发明的硬质聚氨酯泡沫，根据表1将异氰酸酯-反应性化合物与催化剂、稳定剂、增塑剂和发泡剂通过搅拌混合，随后与异氰酸酯混合并发泡以形成硬质聚氨酯泡沫。在每种情况下，异氰酸酯指数为125。然后将反应混合物以多层喷雾到基底上并允许固化，如此获得尺寸为至少800mm宽×800mm长×300mm厚的多层泡沫块。
用于根据实施例1和比较实施例C1制备硬质聚氨酯泡沫的反应混合物组成及其机械性能报告于表1中(数字以重量份计)。
遵循上述程序确定机械性能。
表1：
Figure GDA0003170971330000141
Figure GDA0003170971330000151
Figure GDA0003170971330000161
此处使用以下起始材料：
Figure GDA0003170971330000162

Claims (15)

1.一种制备冷柔聚氨酯绝热体的方法，其中将
a)多异氰酸酯与
b)具有对异氰酸酯呈反应性的基团的化合物，
c)发泡剂，
d)催化剂，
e)增塑剂和任选地
f)其他添加剂
混合，得到反应混合物，并将混合物施用至表面并固化以形成绝热体，其中
异氰酸酯(a)和具有对异氰酸酯呈反应性的基团的化合物(b)、发泡剂(c)、催化剂(d)、增塑剂(e)及任选地其他添加剂(f)反应以使得异氰酸酯指数范围为100至200，
具有对异氰酸酯呈反应性的基团的化合物(b)包括：至少一种聚醚醇(b1)，其标称官能度为4以上，环氧丙烷比例基于聚醚醇(b1)中环氧烷的总重量计大于60重量％，且OH值为至少300mg KOH/g；至少一种聚醚醇(b2)，其标称官能度为3.5以下，伯OH基团比例大于50％，且OH值为小于300mg KOH/g；至少一种聚酯醇(b3)和扩链剂和/或交联剂(b4)，聚醚醇(b2)包含：至少一种聚醚醇(b2a)，其标称官能度为3.5以下，环氧乙烷的比例基于多元醇(b2a)中环氧烷的总重量计为至少80重量％，伯OH基团的比例大于80重量％，且OH值为大于100mgKOH/g至小于300mg KOH/g；和至少一种聚醚醇(b2b)，其标称官能度为3.5以下，伯OH基团的比例大于60％且OH值为大于20mg KOH/g至小于80mg KOH/g，
且其中发泡剂的水含量基于组分(b)至(e)的总重量计小于0.5重量％。
2.根据权利要求1所述的方法，其中在聚醚醇(b1)的制备中使用乙二胺作为起始剂分子。
3.根据权利要求1或2所述的方法，其中至少一种聚酯醇(b3)具有2至2.5的官能度和100至400mg KOH/g的羟值。
4.根据权利要求1或2所述的方法，其中至少一种聚酯醇(b3)通过二酸与二醇缩合获得，其中二酸组分包含芳族二酸，二醇组分包括二乙二醇。
5.根据权利要求1或2所述的方法，其中至少一种扩链剂和/或交联剂(b4)的化合物具有胺端基。
6.根据权利要求1或2所述的方法，其中组分(b1)的比例为15至35重量％，组分(b2)的比例为15至35重量％，组分(b3)的比例为20至35重量％，组分(b4)的比例为10至35重量％，各自基于组分(b)的总重量计。
7.根据权利要求1或2所述的方法，其中除了组分(b1)-(b4)之外，组分(b)还包含小于20重量％的其他具有对异氰酸酯呈反应性的基团的化合物。
8.根据权利要求1或2所述的方法，其中使用单体二苯基甲烷二异氰酸酯和具有多于两个环的二苯基甲烷二异氰酸酯的高级同系物的混合物作为多异氰酸酯。
9.根据权利要求1或2所述的方法，其中其他添加剂包含5至25重量％的阻燃剂。
10.根据权利要求9所述的方法，其中阻燃剂包括磷酸三乙酯。
11.根据权利要求1或2所述的方法，其中通过喷雾将反应混合物施用至表面。
12.根据权利要求1或2所述的方法，其中聚氨酯绝热体的密度为30至80g/l，且使用物理发泡剂作为发泡剂。
13.通过根据权利要求1-12中任一项所述的方法可获得的聚氨酯绝热体。
14.根据权利要求13所述的聚氨酯绝热体，其中CTSR因子大于1.5。
15.根据权利要求13或14所述的聚氨酯绝热体用于使船上的液化天然气罐绝热的用途。
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