CN114341238B - 用烃类发泡剂和1,1,1,4,4,4-六氟丁-2-烯制备的硬质聚氨酯泡沫 - Google Patents

用烃类发泡剂和1,1,1,4,4,4-六氟丁-2-烯制备的硬质聚氨酯泡沫 Download PDF

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CN114341238B
CN114341238B CN202080061364.4A CN202080061364A CN114341238B CN 114341238 B CN114341238 B CN 114341238B CN 202080061364 A CN202080061364 A CN 202080061364A CN 114341238 B CN114341238 B CN 114341238B
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H·克雷默
T·莫夏蒂
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Abstract

在少量顺式和/或反式1,1,1,4,4,4‑六氟丁‑2‑烯和烃类发泡剂的存在下制备聚氨酯绝热泡沫。获得非常低的λ值。

Description

用烃类发泡剂和1,1,1,4,4,4-六氟丁-2-烯制备的硬质聚氨 酯泡沫
本发明涉及制备硬质聚氨酯泡沫的方法。
硬质聚氨酯泡沫广泛用作诸如冰箱和冰柜的电器以及其他用途的绝缘泡沫。泡沫绝缘的绝热特性对于电器的整体性能非常重要。较好的绝热性能可降低能耗并降低运行成本。出于这个原因,对具有较低λ(λ)值的聚氨酯泡沫(即表现出绝热性甚至更好)存在持续需要。
在过去几十年中,为了实现这一结果已做了大量工作,现在人们认为聚氨酯泡沫的绝缘能力正在接近技术极限。因此,即使是很小的改进也变得难以实现。然而,由于需求强劲,市场欢迎绝缘能力的进一步改进,即使那些改进很小。
目前,具有最佳绝缘能力的商业用途的硬质聚氨酯泡沫是由含有大比例的邻甲苯二胺引发的聚醚多元醇的泡沫配制物制备的。这种多元醇的使用,尤其是与真空辅助工艺结合使用,例如在WO 2010/046361中描述的,已在商业电器生产环境中成功地生产出具有非常低的λ值的聚氨酯泡沫。然而,邻甲苯二胺引发的多元醇价格昂贵,因此期望限制在泡沫配制物中使用的量。执行真空辅助方法所需的设备可能并非在所有制造地点都可用。
当在制备硬质聚氨酯泡沫塑料中用作发泡剂时,某些氢氟烯烃(HFO)和氢氯氟烯烃(HCFO)化合物与低λ值相关。然而,这些化合物,如邻甲苯二胺引发的多元醇,相对昂贵,并且将它们用作发泡剂会显着增加成本。一种特殊的HFO,即1,1,1,4,4,4-六氟丁-2-烯(HFO-1336mzz),已与环戊烷和其他发泡剂一起用于制备硬质聚氨酯泡沫塑料。参见例如AU2016-200022A和WO 2019/096763。WO 2019/096763描述了含有4至20份HFO-1336mzz和2至10份环戊烷(按多元醇重量计)的聚氨酯泡沫系统。这些泡沫系统用于制备复合板,例如用于冷藏柜/拖车的复合板。据报道,由该工艺制备的泡沫的芯密度为约45-50kg/m3,并且在25℃平均板温下λ值为20mW/m-K或更高。据说HFO-1336mzz本身会导致泡沫过脆。
本发明在一方面是一种聚氨酯泡沫,其为包含以下的反应系统的反应产物:
a)至少一种聚异氰酸酯;
b)至少一种多元醇;
c)至少一种氨基甲酸酯催化剂;
d)至少一种泡沫稳定表面活性剂;
e)按组分b)、c)、d)和e)的组合重量计0至3重量百分比的水;
f)每100重量份的组分b)、c)、d)和e)中的1至6重量份的顺式-和/或反式-1,1,1,4,4,4-四氟丁-2-烯;以及
g)每100重量份的组分b)、c)、d)和e)中的8到30重量份的一种或多种具有4个到6个碳原子的烃类。
本发明还是一种制备聚氨酯泡沫的方法,其包括形成如关于第一方面所述的反应系统和固化所述反应系统以产生聚氨酯泡沫。
本发明还是一种制造绝热柜的方法,其包括
A)定位外壳构件和内衬构件以便限定在它们之间的空腔;
B)将第一方面的反应系统引入到空腔中;和
C)固化反应系统,使其膨胀并反应以产生填充空腔并粘附到外壳构件和内衬构件的聚氨酯泡沫。
根据本发明制备的泡沫的特征在于具有令人惊讶的良好绝缘性能,即低λ值。与仅使用烃类发泡剂制备的其他类似泡沫相比,λ值通常降低2%至5%或更多。用本发明获得的λ值几乎与大量使用1,1,1,4,4,4-四氟丁-2-烯作为唯一物理发泡剂时获得的值一样好。后一种结果特别令人惊讶和有益,因为本发明允许用廉价的烃类发泡剂代替大部分昂贵的1,1,1,4,4,4-四氟丁-2-烯,这降低了材料成本。
本发明的另一个优点是即使在多元醇组分仅含有少量邻甲苯二胺引发的多元醇时也能获得优异的λ值。该益处使得大部分邻甲苯二胺引发的多元醇可以被更便宜的多元醇代替,从而再次降低原材料成本,同时提供出色的绝热特性。
组分a)为至少一种有机聚异氰酸酯,其实例包括脂肪族、环脂肪族、芳脂族或芳香族聚异氰酸酯或其任何两种或更多种的组合。有机聚异氰酸酯可具有例如至多250的异氰酸酯当量。特定有机聚异氰酸酯包括例如亚烷基二异氰酸酯,具体地在亚烷基部分中具有4至12个碳原子的那些,如1,12-十二烷二异氰酸酯、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、2-乙基-2-丁基五亚甲基1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯,并且优选六亚甲基1,6-二异氰酸酯;环脂肪族二异氰酸酯,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何混合物、1-异氰酸基-3,3,5-三甲基-5-异氰酸基-甲基环己烷(异佛尔酮二异氰酸酯)、2,4-六氢甲苯二异氰酸酯和2,6-六氢甲苯二异氰酸酯以及这些异构体的混合物、4,4'-二环己基甲烷二异氰酸酯、2,2'-二环己基甲烷二异氰酸酯和2,4'-二环己基甲烷二异氰酸酯以及这些异构体的混合物,芳脂族二异氰酸酯,如1,4-苯二甲基二异氰酸酯和苯二甲基异氰酸酯异构体的混合物,并且优选芳香族二异氰酸酯和聚异氰酸酯,如2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯以及对应的异构体混合物、4,4'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯和2,2'二苯基甲烷二异氰酸酯以及对应的异构体混合物、4,4'-二苯基甲烷二异氰酸酯和2,4'-二苯基甲烷二异氰酸酯、聚苯基-聚亚甲基聚异氰酸酯的混合物、4,4'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯和2,2'二苯基甲烷二异氰酸酯的混合物以及聚苯基聚亚甲基聚异氰酸酯(粗制MDI)以及粗制MDI和甲苯二异氰酸酯的混合物。
还可使用改性的聚异氰酸酯,即,通过有机二异氰酸酯和/或聚异氰酸酯的化学反应得到的产物。具体实例是含酯、脲、缩二脲、脲基甲酸酯、脲酮亚胺、碳二亚胺、异氰脲酸酯、脲二酮和/或氨基甲酸酯的二异氰酸酯和/或聚异氰酸酯,按改性聚异氰酸酯的总重量计,其含有33.6至15重量%,优选31至21重量%的异氰酸酯基团。
组分b)是至少一种多元醇。可以使用多种多元醇,部分取决于聚合物泡沫的所需特性。因此,可用的多元醇包括聚醚多元醇、聚酯多元醇、羟基封端的聚丁二烯橡胶和聚丙烯酸酯多元醇以及其他类型。可用的多元醇具有约30至3000的羟基当量;然而,优选的是,至少一种多元醇的羟基当量为30至1000,尤其是75至560或100至350。多元醇的羟基官能度可以为每分子2至8个或更多个羟基。
组分b)优选地包括至少一种聚醚多元醇,其羟基当量为75至560,尤其是100至350,并且标称羟基官能度至少为3,例如3至8。此类聚醚多元醇的实例包括当量为30至59的一种或多种含羟基和/或胺基的起始剂的乙氧基化物和/或丙氧基化物,包括例如乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、二丙二醇、三丙二醇、甘油、三羟甲基丙烷、三羟甲基乙烷、新戊二醇、1,6-己二醇、1,4-环己烷二甲醇、1,2,6-己三醇、单乙醇胺、二乙醇胺、三乙醇胺、季戊四醇、赤藓糖醇、山梨糖醇、蔗糖、甘露醇、邻甲苯二胺(甲苯2,3-二胺和/或甲苯3,4-二胺)、2,4-甲苯二胺、2,5-甲苯二胺和/或2,6-甲苯二胺、N,N,N',N'-四(2-羟基丙基)-乙二胺、二乙基甲苯二胺、二甲基硫代甲苯二胺及其组合中的一种或多种。
在本发明的一些实施例中,组分b)含有组分b)、c)、d)和e)的组合重量的不大于65%、不大于50%、不大于40%、不大于35%、不大于30%或不大于25%的量的烷氧基化邻甲苯二胺多元醇。此种烷氧基化邻甲苯二胺多元醇的羟基当量可以为75至560或100至350。烷氧基化邻甲苯二胺多元醇可以不存在,或者当存在时可以构成组分b)、c)、d)和e)的组合重量的至少5%、至少10%或至少15%。本发明的一个显着优点为,即使在烷氧基化邻甲苯二胺多元醇不存在或仅少量存在时也可以获得非常低的λ值。
另一种可用的多元醇是羟基当量为75至560,尤其是100至350并且标称羟基官能度为6至8的聚醚多元醇。此种多元醇的实例是烷氧基化山梨糖醇或烷氧基化蔗糖多元醇。此种多元醇当存在时可以例如构成组分b)、c)、d)和e)的组合重量的至少5%、至少10%或至少25%并且多至80%或多至60%。
另一种可用的多元醇是标称羟基官能度为2-4且羟基当量为75至560的聚醚,它不是邻甲苯二胺的烷氧基化物。此种聚醚多元醇的实例包括一种或多种低分子量含羟基化合物如乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、甘油、三羟甲基丙烷、三羟甲基乙烷、赤藓糖醇、季戊四醇、三乙醇胺、三异丙醇胺等的烷氧基化物,一种或多种胺如2,4-甲苯二胺、2,5-甲苯二胺、双(氨基乙基)胺、乙二胺等的烷氧基化物,以及烷醇胺如单乙醇胺、二乙醇胺、单异丙醇胺、二异丙醇胺、氨基乙基乙醇胺等的烷氧基化物。
在任何前述的烷氧基化物多元醇中,烷氧化物可以是例如1,2-环氧丙烷、1,3-环氧丙烷、环氧乙烷、1,2-环氧丁烷或2,3-环氧丁烷、四氢呋喃、氧化苯乙烯或氧化环己烷中的一种或多种。特别优选丙氧基化物和/或乙氧基化物。这种烷氧基化物优选地未被卤化。
还有另一种可用的多元醇具有2至8,尤其是2至6或3至4的标称羟基官能度,具有30至74的羟基当量,例如乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、甘油、三羟甲基丙烷、三羟甲基乙烷、赤藓糖醇、季戊四醇、山梨糖醇和蔗糖。
还有其他可用的多元醇是聚酯多元醇。可用的聚酯多元醇可以是例如具有约2至约12个碳原子的有机二羧酸(或相应的酸酐或酯),优选具有8至12个碳原子的芳香族二羧酸与多元醇,优选具有2至12个碳原子,优选2至6个碳原子的二醇和/或三醇的反应产物。合适的二羧酸的实例是丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、顺丁烯二酸、反丁烯二酸,并且优选邻苯二甲酸、间苯二甲酸、对苯二甲酸和异构萘二羧酸。二羧酸可以单独使用或彼此混合使用。用于制备聚酯多元醇的二元醇和多元醇的实例为乙二醇、二乙二醇、1,2-丙二醇和1,3-丙二醇、二丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,10-癸二醇、甘油和三羟甲基丙烷。还可用的是改性芳香族聚酯多元醇,例如美国专利第6,359,022号中描述的,其含有一个或多个在直链或支链中具有6个或更多碳原子的侧链脂肪族烃基。此外,也可以采用由内酯例如ε-己内酯或羟基羧酸,这类ω-羟基己酸和氢苯甲酸制成的聚酯多元醇。如在例如WO 2011/137011中描述的杂化聚醚-聚酯多元醇也是可用的。
另一种可用的多元醇是羟基当量超过560的聚酯多元醇或聚醚多元醇。
组分c)是氨基甲酸酯催化剂,即催化醇基或水与异氰酸酯基反应的材料。合适的氨基甲酸酯催化剂为锡(II)和锡(IV)催化剂、含有其他III族至XV族金属的催化剂、叔胺化合物、脒、叔膦等。可用的氨基甲酸酯催化剂为例如三甲胺、三乙胺、N-甲基吗啉、N-乙基吗啉、N,N-二甲基苄胺、N,N-二甲基乙醇胺、二烷基咪唑化合物、2,2'-二吗啉代二乙醚、N,N,N',N'-四甲基-1,4-丁二胺、N,N-二甲基哌嗪、1,4-重氮双环-2,2,2-辛烷、四烷基胍化合物、2,2,2-二甲基氨基乙氧基乙基甲基氨基乙醇、N,N-二甲基环己胺、1,3,5-三[3-(二甲基氨基)丙基]六氢-1,3,5-三嗪、三亚乙基二胺、其中烷基含有4至18个碳原子的二甲基烷基胺、五甲基二亚乙基三胺、四甲基乙二胺、二月桂酸二丁基锡、二月桂酸二甲基锡、辛酸亚锡、油酸亚锡、氯化锡、氯化亚锡、双(巯基乙酸异辛酯)二正丁基锡和式SnRn(OR)4-n的其他有机锡化合物,其中R是烷基或芳基并且n是0-2,
一种或多种氨基甲酸酯催化剂以催化有效量使用。一种或多种氨基甲酸酯催化剂可以例如构成组分b)、c)、d)和e)的组合重量的至多5%或至多4%。
组分d)是一种或多种泡沫稳定表面活性剂。合适的表面活性剂包括但不限于硅酮如硅油和有机硅酮-聚醚共聚物,包括聚二甲基硅氧烷和聚二甲基硅氧烷-聚氧化烯嵌段共聚物,诸如在美国专利4,483,894中描述。其它合适的表面活性剂是平均分子量为至少30,000的线性硅氧烷-聚氧化烯嵌段共聚物,如美国专利4,022,722中所公开的。其它合适的表面活性剂包括有机表面活性剂,如壬基苯酚乙氧基化物和环氧乙烷/环氧丁烷嵌段共聚物。合适的表面活性剂可广泛购自赢创工业(Evonik Industries)、迈图高新材料集团(Momentive Performance Materials)和陶氏化学公司(The Dow Chemical Company)。
组分d)可以构成例如组分b)、c)、d)和e)的总重量的至少0.25%且至多10%。在相同的基础上,优选量为至少0.5%或至少1%且至多5%或至多3%。
组分f)是1,1,1,4,4,4-四氟丁-2-烯的顺式或反式异构体或任何比例的顺式和反式异构体的混合物。每100重量份的组分b)、c)、d)和e)中,组分f)以1-6重量份的量存在。在相同的基础上,优选的量是1至4重量份或2至4重量份。
组分g)是具有4到6个碳原子的一种或多种烃。此类烃的实例包括正丁烷、异丁烷、环丁烷、正戊烷、异戊烷、新戊烷、环戊烷、正己烷、2-甲基戊烷、3-甲基戊烷、环己烷、2-乙基丁烷、2,2-二甲基丁烷和2,3-二甲基丁烷以及其中任何两种或更多种的混合物。优选一种或多种戊烷,并且特别优选环戊烷。每100重量份的组分b)、c)、d)和e)中,组分g)以8至30重量份、优选10至20重量份或12至20重量份的量存在。
除了已经提到的那些之外,反应体系可包含各种任选的成分。此类任选成分可以包括异氰酸酯三聚催化剂。异氰酸酯三聚催化剂的实例包括强碱,如碱金属酚盐、碱金属醇盐、碱金属羧酸盐、季铵盐等。另一种任选成分是一种或多种阻燃剂,如含磷阻燃剂、卤化阻燃剂和三聚氰胺。反应体系还可以含有一种或多种填料和/或增强剂,如玻璃纤维、碳纤维、鳞片玻璃、云母、滑石和碳酸钙;一种或多种颜料和/或着色剂,如二氧化钛、氧化铁、氧化铬、偶氮/重氮染料、酞菁、二噁嗪和炭黑;一种或多种杀生物剂;一种或多种防腐剂;一种或多种抗氧化剂;等。
根据本发明,通过将成分a)-g)与任何任选成分组合以产生反应系统,然后在使成分g)挥发并使聚聚异氰酸酯与多元醇、水和其他异氰酸酯反应性成分反应的条件下固化该反应系统来制备泡沫,以产生聚合物泡沫。顺式-和/或反式-1,1,1,4,4,4-六氟丁-2-烯也可在发泡过程期间挥发。异氰酸酯指数(向反应混合物提供的异氰酸酯基团与异氰酸酯反应性基团之比的100倍)为至少90,优选地至少100或至少110。当期望聚氨酯-异氰脲酸酯泡沫时,异氰酸酯指数优选地为至少200、至少250或至少300。在一些实施例中,异氰酸酯指数可以为至多1000、至多600、至多500、或至多450、至多250、至多200、至多150或至多125。
组分a)-g)的混合顺序不是特别关键,尽管通常优选当所有其他组分已经存在时将聚异氰酸酯与水和多元醇组合。组分b)-e)、b)-f)或b)-g)可以首先组合,以形成配制的多元醇组分,然后将其与剩余成分组合,以产生反应体系。在一个具体实施例中,将组分b)-e)或b)-f)组合,以形成配制的多元醇组分,并且然后将配制的多元醇组分同时或依次与组分f)(如果需要)、g)和a)混合,以产生反应体系。然而,通过一次性将各种组分全部聚集在一起或以各种子组合的形式将各种组分聚集在一起来产生反应混合物都在本发明的范围内。
聚异氰酸酯、多元醇和水在混合时甚至在室温下通常会自发反应,并且反应放热通常足以产生使烃发泡剂(组分g))和组分f)挥发所需的温度。因此,通常仅需要在如10℃至35℃的室温或约室温下形成反应混合物,并在无需进一步施加热量的情况下允许反应完成。然而,如果需要,则可以在形成反应混合物时或之前加热组分,和/或可以将反应体系加热到高温以促进固化反应。
泡沫可以以自由发泡工艺(free-rise process)产生,在所述自由发泡工艺中,泡沫配制物分配到开阔区域中并且允许在竖直方向上自由发泡以产生块料(bunstock)。在其它实施例中,通过将反应混合物连续分配到移动带或基材上在连续工艺中产生泡沫。基材可以是饰面片材或面板,并且饰面片材或面板的第二层可以连续地放置在反应混合物的顶部以形成夹层结构。将反应混合物固化以形成粘附到(一个或多个)基材的泡沫。
在特别感兴趣的实施例中,通过将反应混合物引入到发生膨胀和固化的空腔或限定空间中来产生泡沫。空腔或限定空间可以例如由绝热板的壁或各种壁(例如冰箱、冰柜、冷却器、洗碗机、热水器或其他电器的壁)限定。空腔或限定空间可以是诸如用于制造预绝缘管的环形模具或空腔。具体地,可以通过定位外壳构件和内衬构件以在它们之间限定空间来形成空腔。例如,外壳层可以形成需要绝热的电器的外壁。例如,内衬可以形成这种电器的内壁。外壳和内衬各自可以由金属如钢或铝以及各种结构热塑性或热固性树脂如聚苯乙烯、高抗冲聚苯乙烯(HIPS)、丙烯腈-丁二烯-苯乙烯互聚物、聚酰胺、聚酯、硬质聚氨酯树脂等形成。在一个具体实施例中,所述电器是冰箱或冰柜;外壳是金属并且内衬是结构热塑性树脂,如聚苯乙烯、高抗冲聚苯乙烯(HIPS)、丙烯腈-丁二烯-苯乙烯互聚物、聚酰胺、聚酯或硬质聚氨酯树脂。
外壳和内衬被定位以形成空腔,向所述空腔中引入反应体系,并且反应体系在所述空腔中固化以形成聚氨酯泡沫。可以使用夹具或其他机械装置将外壳和内衬保持在它们各自的位置。
反应体系被引入到空腔中,例如通过透过一个或多个注入端口倾倒或注入。引入的反应体系的量至少足以使反应体系在空腔内膨胀和固化时填充空腔。一旦反应混合物膨胀,就可以通过引入超出填充空腔所需的最低限度的过量反应混合物来“过度填充”空腔。例如,一旦反应混合物膨胀,就可以使空腔过度填充5%至40%,即引入超过填充空腔所需的最低限度的多于5至40重量%的反应体系。
反应系统一旦被引入,就会膨胀并固化,从而在空腔中产生聚氨酯泡沫。聚氨酯泡沫通常粘附到外壳和内衬上,并为最终的组件提供机械强度和稳定性,并提供绝热。
在填充步骤和任选地至少一部分固化步骤期间,可以在空腔中保持次气压,例如在WO 2007/058793和WO 2010/044361中所述。减压可以为例如300至950mbar(30-95kPa)实际值,优选地400至950mbar(40-95kPa)实际值并且甚至更优选地700至950mbar(50-95kPa)实际值,在将泡沫形成组合物装入到模具中之前或之后立即进行。优选保持减压直到反应体系被引入到模具中,并且更优选地直到诸如反应体系膨胀和胶凝(即,形成三维聚合物网络)的时间。
根据本发明制备的泡沫的泡沫密度可以为例如20至120kg/m3、24至80kg/m3、28至64kg/m3或28至40kg/m3,如根据ASTM 1622-88所测量的。泡孔可以是至少约70%封闭、至少约80%封闭或至少约85%封闭。如根据EN-12667在10℃平均板温度下测量的,泡沫的λ值通常不大于20.0、不大于19.0、不大于18.5或甚至不大于18.25mW/m-°K。
提供以下实例以说明本发明而非限制本发明的范围。除非另外指明,否则所有的份数和百分比均按重量计。
配制的多元醇A是聚醚多元醇、氨基甲酸酯催化剂、硅酮表面活性剂和水的混合物。它含有1.8重量%的水和25重量%的官能度为4且羟值为约440mg KOH/g的o-TDA多元醇。配制的多元醇A的羟值为395mg KOH/g。
配制的多元醇B是聚醚多元醇、氨基甲酸酯催化剂、硅酮表面活性剂、甘油和水的混合物。它含有1.5重量%的水和59重量%的官能度为4且羟值为370至440mg KOH/g的o-TDA多元醇。配制的多元醇B的羟值为418mg KOH/g。
PMDI是异氰酸酯含量为约31重量%的聚合MDI。
实例1和比较样品A
为了制备实例1,将100重量份的配制的多元醇A在约23℃下与3重量份的反式-1,1,1,4,4,4-六氟丁-2-烯、13.2重量份的环戊烷混合并且然后与140份的PMDI(122指数)混合,以形成反应混合物。将一部分反应混合物立即注入到尺寸为200cm X 20cm X 5cm(约6'6"X 8"X 2")的矩形“Brett”模具中。Brett模具以垂直定向的200cm方向定向并预热至45±5℃。Brett模具处于大气压下。允许组合物克服其自身重量膨胀并在模具内固化。选择聚氨酯形成组合物的量,以使所得泡沫恰好填充模具。然后测量所得泡沫的密度并将其报告为最小填充密度(MFD)。将泡沫脱模并重复实验,除了模具被过度填充10%。所得泡沫的λ值根据EN 12667使用10℃平均板温度确定。
将另一部分反应混合物倒入到20cm×20cm×20cm的盒中,并目视评估乳白时间。将抹刀压在固化反应混合物的表面,以评估凝胶时间(混合后一系列聚合物线粘在抹刀上的时间)和表干时间(混合后聚合物不再粘在抹刀上的时间)。
使用实例1的配制物重复上述实验,除了在填充和泡沫膨胀期间在Brett模具上抽真空(-0.2气压表,实际80kPa)直到反应体系胶凝。
通过将100重量份的配制的多元醇A与14.5重量份的环戊烷和140重量份的PMDI(1.22指数)组合来以类似方式制备比较样品A。如前所述测量乳白时间、胶凝时间和表干时间。如关于实例1所述,确定在Brett模具中在环境压力和减压下制造的泡沫的最小填充密度和λ值。
前文测试的结果如表1中所指示。
表1
如表1中的数据所示,通过向配制物中添加3重量份的1,1,1,4,4,4-六氟丁-2-烯并将环戊烷的量减少约10%来获得λ的显著减小。用实例1获得的λ值非常低,特别是考虑到泡沫配制物含有相当低比例的o-TDA引发的多元醇。没有观察到乳白时间、胶凝时间或表干时间的显着变化。
实例2和3以及比较样品B
通过将100份配制的多元醇B与3份反式或顺式1,1,1,4,4,4-六氟丁-2-烯、14.8份环戊烷和PMDI(119指数)以与先前实例中描述的相同的一般方式组合来制备泡沫实例2和3。通过将100份配制的多元醇B与16份环戊烷和PMDA(121指数)组合并以类似方式使所得反应混合物发泡来制备比较样品B。在每种情况下测量乳白时间、胶凝时间和表干时间,以及在Brett模具中在环境压力和减压条件下生产的泡沫的最小填充密度和λ。泡沫测试的结果如表2中所指示。
表2
表2中的数据表明,本发明使用1,1,1,4,4,4-六氟丁-2-烯的顺式或反式异构体实现了λ值的显着减小。在这种情况下,即使在含有大部分o-TDA引发的多元醇的泡沫配制物中,也可以实现绝缘能力的改进。以前已知此类泡沫具有非常低的λ值;进一步的显着减少是出乎意料的,并且也是非常有益的。
实例4和比较样品C和D
通过将100重量份的配制的多元醇A与14.5份的环戊烷和PMDI(112指数)组合并以与先前实例中所述相同的一般方式使用减小的模具压力和10%的过度填充将所得反应混合物加工成泡沫来制备比较样品C。通过将100重量份的配制的多元醇A与6.6份的环戊烷、18份的顺式-1,1,1,4,4,4-六氟丁-2-烯和PMDI(112指数)组合来以类似方式制备比较样品D。
通过将100份的配制的多元醇B、3份的顺式-1,1,1,4,4,4-六氟丁-2-烯、14.8份的环戊烷和PMDI(112指数)组合来以相同的一般方式制备实例4。
测量λ。在每种情况下,泡沫密度为约35g/L。每种情况下的成分和泡沫测试的结果如表3所指示。
表3
通过比较比较样品C和D可以看出,通过包含18份顺式-1,1,1,4,4,-六氟丁-2-烯并将环戊烷的量减少到6.6份来获得λ的5.8%减小(相对于比较样品C)。该结果需要大量昂贵的1,1,1,4,4,4-六氟丁-2-烯材料,这导致成本劣势较大;需要18份顺式-1,1,1,4,4,4-六氟丁-2-烯来产生1.1mW/m-°K的λ减小。实例1和4表明,在两种不同的多元醇体系中,根据本发明通过仅添加六分之一(3份)的量的1,1,1,4,4,4-六氟丁-2-烯,可以获得超过一半至几乎75%的该益处。在实例1中,仅使用3份1,1,1,4,4,4-六氟丁-2-烯即可获得0.6mW/m-°K的减小;在实例4中,当使用3份1,1,1,4,4,4-六氟丁-2-烯时获得0.8mW/m-°K。通过本发明,使用1,1,1,4,4,4-六氟丁-2-烯的大部分优点仅以一小部分使用水平和一小部分成本获得。

Claims (6)

1.一种制备聚氨酯泡沫的方法,其包括形成反应体系并固化所述反应体系以产生聚氨酯泡沫,其中所述反应体系包含:
a)至少一种聚异氰酸酯;
b)至少一种多元醇;
c)至少一种氨基甲酸酯催化剂;
d)至少一种泡沫稳定表面活性剂;
e)按组分b)、c)、d)和e)的组合重量计0至3重量百分比的水;
f)每100重量份的组分b)、c)、d)和e)中的2至4重量份的顺式-和/或反式-1,1,1,4,4,4-六氟丁-2-烯;以及
g)每100重量份的组分b)、c)、d)和e)中的12到20重量份的一种或多种具有4个到6个碳原子的烃类,
其中按组分b)、c)、d)和e)的组合重量计,所述反应体系含有不超过30重量百分比的烷氧基化邻甲苯二胺多元醇,
其中将所述反应体系引入到空腔中并在所述空腔中固化,并且当所述反应体系被引入到所述空腔中时,在所述空腔中保持700至950毫巴的实际压力。
2.一种聚氨酯泡沫,其以根据权利要求1所述的方法制备。
3.根据权利要求2所述的泡沫,如根据EN 12667在10℃平均板温度下测量的,所述泡沫表现出至多18.5mw/m·K的λ值。
4.根据权利要求2所述的泡沫,如根据EN 12667在10℃平均板温度下测量的,所述泡沫表现出至多18.25mw/m·K的λ值。
5.根据权利要求2-4中任一项所述的泡沫,如根据ASTM 1622-88所测量的,所述泡沫的密度为28至40kg/m3
6.一种制造绝热柜的方法,其包括
A)定位外壳构件和内衬构件以便限定在它们之间的空腔;
B)将所述反应体系引入到空腔中;和
C)固化所述反应体系,使其膨胀并反应以产生填充所述空腔并粘附到所述外壳构件和所述内衬构件的聚氨酯泡沫,其中所述反应体系包含:
a)至少一种聚异氰酸酯;
b)至少一种多元醇;
c)至少一种氨基甲酸酯催化剂;
d)至少一种泡沫稳定表面活性剂;
e)按组分b)、c)、d)和e)的组合重量计0至3重量百分比的水;
f)每100重量份的组分b)、c)、d)和e)中的2至4重量份的顺式-和/或反式-1,1,1,4,4,4-六氟丁-2-烯;以及
g)每100重量份的组分b)、c)、d)和e)中的12到20重量份的一种或多种具有4个到6个碳原子的烃类,
其中按组分b)、c)、d)和e)的组合重量计,所述反应体系含有不超过30重量百分比的烷氧基化邻甲苯二胺多元醇,
其中至少在步骤B)期间在所述腔中保持700至950毫巴的实际压力的次气压。
CN202080061364.4A 2019-09-02 2020-08-14 用烃类发泡剂和1,1,1,4,4,4-六氟丁-2-烯制备的硬质聚氨酯泡沫 Active CN114341238B (zh)

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