CN104004215B - 绝热模塑物及其制备方法 - Google Patents
绝热模塑物及其制备方法 Download PDFInfo
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- CN104004215B CN104004215B CN201410062017.XA CN201410062017A CN104004215B CN 104004215 B CN104004215 B CN 104004215B CN 201410062017 A CN201410062017 A CN 201410062017A CN 104004215 B CN104004215 B CN 104004215B
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- polyether polyol
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Landscapes
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Abstract
本发明涉及绝热模塑物的制备方法,特别是用于制冷设备的模塑物的制备方法,其中,所述模塑物通过如下方式提供:在开口盒状模具(M)的内壁和外壁之间的腔室填充聚氨酯反应混合物,并使该聚氨酯反应混合物固化为含有聚氨酯的聚合物C,所述内壁和外壁彼此以固定距离布置,且每个壁均包括一个底面(3)和多个侧面(1、2、4、5),聚氨酯反应混合物通过置于所述外壁的底面(3)的中间区域的入口(I)加入,其中,在将聚氨酯反应混合物填入所述腔室之前,将模具(M)旋转,使其外壁的底面向下,从而使得聚氨酯反应混合物向上发泡以填充所述腔室,所述方法的特征在于,聚氨酯反应混合物含有与乳液反应的异氰酸酯组分B,所述乳液包含:(I)异氰酸酯活性组合物A,其含有由至少三种多元醇A1a、A1b和A1c组成的多元醇混合物A1作为连续相和(II)至少一种物理发泡剂T作为分散相,其中:(i)A1a为羟值为15mg KOH/g至550mg KOH/g且官能度为1.5至6.0的聚醚多元醇,其通过将环氧化物加成至一种或多种起始化合物得到,所述起始化合物选自碳水化合物和双官能或更高官能度的醇;(ii)A1b为羟值为100mg KOH/g至550mg KOH/g且官能度为1.5至5.0的聚醚多元醇,其通过将环氧化物加成至芳族胺得到;(iii)A1c为羟值为100mg KOH/g至450mg KOH/g且官能度为1.5至3.5的聚酯聚醚多元醇,其通过将环氧化物加成至芳族二羧酸衍生物与双官能或更高官能度的醇的酯化产物得到。本发明还涉及由该方法制备的绝热模塑物。
Description
本发明涉及一种绝热(insulation)模塑物的制备方法,特别是用于冷藏柜的模塑物的制备方法,其中,所述模塑物通过如下方式提供:在开口盒状模具的内壁和外壁之间的腔室填充聚氨酯反应混合物,并使该聚氨酯反应混合物固化为含有聚氨酯的聚合物C,所述内壁和外壁彼此以固定距离布置,且每个壁均包括一个底面和多个侧面,聚氨酯反应混合物通过置于所述外壁的底面的中间区域的入口加入,其中,在将聚氨酯反应混合物填入所述腔室之前,将模具旋转,使其外壁的底面向下,从而使得聚氨酯反应混合物向上发泡以填充所述腔室。本发明还涉及由上述方法制备的模塑物及其用于绝热目的的用途。
已知在使用物理发泡剂由异氰酸酯组分和含多元醇的异氰酸酯活性组分制备泡沫的过程中,如所述物理发泡剂在异氰酸酯活性组合物中以细小液滴的形式乳化,则对待制备泡沫的绝热效果具有积极影响。这种对待制备泡沫的绝热效果的积极影响由以下事实产生:形成的乳化液滴作为后续发泡过程的成核剂。存在的液滴越多且这些液滴越细小,则后续发泡过程中的泡孔也就越多,且尤其是所述泡孔也越小。这一事实对以此方法获得的泡沫的绝热性能具有直接影响,这是因为形成的泡沫泡孔越小,这些性能就越好。良好的绝热性能体现在低热导率方面。然而,所述乳液的制备和加工的难点在于其稳定性。该稳定性定义如下:这种乳液在常规条件下简单储存后,在几个小时至几天的时间内不施加外部载荷的情况下,直至在通过由温度影响和加压以及剪切力的影响而施加的载荷下,多元醇组分和物理发泡剂未分离。因此,只有至少在常规条件下能够提供这种稳定性,但优选在涉及温度变化、压力变化和/或剪切力的条件下也能提供这种稳定性的乳液才在工业上具有实用性。这些成熟的方法通常被粘度急剧上升至液态多元醇相的粘度的两倍而抵消。然而,在任何情况下,由于乳化过程因其非牛顿行为而更复杂,因此粘度的过度升高是不希望的。
EP0905160A1记载了含有发泡剂且加入官能度大于1.5且羟值为10mg KOH/g至100mg KOH/g的聚醚醇的稳定乳液,所述聚醚醇在用于制备异氰酸酯基硬质泡沫的多元醇组分(见第[0001]段)中作为活性乳化稳定剂(见第[0014]段)。所述乳液含有聚醚醇,其通过向OH-官能化和/或NH-官能化起始物质例如糖醇和芳族胺加入低级环氧烷烃(优选环氧乙烷和/或环氧丙烷)而制备(见第[0025]段)。还优选向聚醚醇加入由多官能羧酸和多官能醇制备的聚酯醇(见第[0026]段)。发泡剂在多元醇混合物中乳化,并得到稳定的乳液(见第[0021]段)。然而,发泡剂还可在混料头中或在混料头之前加入至多元醇混合物,但是,该文献未公开前言中提及的三种多元醇A1a、A1b和A1c的具体结合。具体而言,未公开聚酯聚醚多元醇。
US2002/0169228A1要求保护一种相稳定的多元醇混合物,其含有由蔗糖和二丙二醇共同开始制备的环氧丙烷-聚醚多元醇、聚酯多元醇和作为发泡剂的含4-6个碳原子的烃,其在至少24小时内为相稳定的(参见权利要求1)。还可向所述混合物中加入由甲苯二胺开始制备的OH官能度介于3.5-4.5之间的聚环氧丙烷-聚醚多元醇(见第[0020]段)。聚酯多元醇由邻苯二甲酸酐开始制备(见权利要求3)且优选为基于邻苯二甲酸酐和二乙二醇的STEPANPOL2352(见第[0022]段)。环戊烷可用作发泡剂(见第[0029]段),其或者以微乳液的形式存在于多元醇混合物中(见第[0006]段)且在混料头之前加入至多元醇混合物中,或者作为分离料流进料至混料头中(见第[0027]段)。所述多元醇混合物与有机多异氰酸酯反应而形成聚氨酯泡沫(见权利要求17)。该申请所指的术语“微乳液”暗示发泡剂为溶于多元醇混合物中;见第[0006]段。这清楚示于第[0013]段,其中公开了,如多元醇混合物呈“浑浊状”,则其不再属于相稳定的。所述多元醇组合物应在至少24小时内保持相稳定的表述(见第[0006]段)表明,该申请中错误地使用术语“微乳液”。真的微乳液处于热力学最小值的状态且因而是无限稳定的,条件是组分和温度不变。与这种微乳液不同,乳液首先是温度敏感的,且为物质敏感的。将乳液加热并随后冷却至起始温度通常导致分散结构中的不可逆变化,这种变化可导致乳液破坏。因此,保持本发明的“真”乳液的稳定性比保持“微乳液”的稳定性难得多。
申请US2002/0169228A1也涉及发泡剂在多元醇混合物中的溶液。根据该文件,应避免不利地影响发泡剂的溶解性的所有因素,这就是在聚醚多元醇的制备中仅使用环氧丙烷的原因(见第[0018]段)。
WO00/24813A1公开了用于例如冷藏箱绝热的硬质聚氨酯泡沫的制备方法(第1段,第3-5行)。所述泡沫由有机多异氰酸酯、含有聚醚和/或聚酯多元醇的多元醇混合物、发泡剂和其他助剂和添加剂组成(见权利要求1)。由环戊烷和水组成的发泡剂分散在多元醇混合物中(见权利要求1)。聚醚多元醇通过多羟基醇与聚环氧乙烷和/或聚环氧丙烷的加成聚合制备(第4页,第11-15行)且优选具有3-6个羟基(第5页,第13-15行)。例如,丙三醇、山梨醇、蔗糖和芳族胺可用作多羟基醇(第5页,第1-3行和第6-7行)。所述聚酯多元醇可由二羧酸酐(例如邻苯二甲酸酐)和二元醇(例如二乙二醇)制备(第5页第16-31行)且优选具有两个官能团(第6页,第4-6行)。在该文件的对比实施例中公开了由芳族胺开始制备的聚醚多元醇(“多元醇K”)。在这些对比实施例中,将戊烷溶解于多元醇组分中而不是在多元醇组分中将其乳化(见第13页的表1)。相对于存在的所用多元醇而言,多元醇K的含量相对较高,分别为40%(对比实施例1)和50%(对比实施例2)。
就制备方法而言,用于冷藏箱和/或冷冻箱的模塑物通常通过使用具有所需几何形状的模塑物并经由入口注入PUR/PIR-组分制备,所述入口通常置于箱体的靠下的后壁与底部之间的边缘处。
EP0289764A2中采用了不同的方法,其中,应用上述方法(即大致经由冷藏箱的靠下的后壁的中点注入聚氨酯反应混合物),但是,在发泡过程中使模塑物翻转为后侧向下,从而使得后壁基本水平。虽然就泡沫注入而言,经由置于箱体的靠下的后壁与底部之间的边缘处的入口注入,可实现一些改进,但绝热性能并不总是令人满足的。特别是泡沫的均匀性有时不理想。
本发明的目的在于提供一种绝热模塑物的制备方法,特别是用于冷藏柜的模塑物的制备方法,所述方法提供改进的绝热性能,且特别地,这些绝热性能在模塑物的所有位置处应是大致相同的。
这一目的通过绝热模塑物的制备方法,特别是用于制冷设备的模塑物的制备方法实现,其中,所述模塑物通过如下方式提供:在开口盒状模具的内壁和外壁之间的腔室填充聚氨酯反应混合物,并使该聚氨酯反应混合物固化为含有聚合物C的聚氨酯,所述内壁和外壁彼此以固定距离布置,且每个壁均包括一个底面和多个侧面,聚氨酯反应混合物通过置于所述外壁的底面的中间区域的入口加入,其中,在将聚氨酯反应混合物填入所述腔室之前,将模具翻转,使其外壁的底面向下,从而使得聚氨酯反应混合物向上发泡以填充所述腔室,所述方法的特征在于,所述聚氨酯反应混合物含有与乳液反应的异氰酸酯组分B,所述乳液包含:
(I)异氰酸酯活性组合物A,其含有由至少三种多元醇A1a、A1b和A1c组成的多元醇混合物A1作为连续相
和
(II)至少一种物理发泡剂T作为分散相,
其中:
(i)A1a为羟值为15mg KOH/g至550mg KOH/g且官能度为1.5至6.0的聚醚多元醇,其通过将环氧化物加成至一种或多种起始化合物得到,所述起始化合物选自碳水化合物和双官能或更高官能度的醇;
(ii)A1b为羟值为100mg KOH/g至550mg KOH/g且官能度为1.5至5.0的聚醚多元醇,其通过将环氧化物加成至芳族胺得到;
(iii)A1c为羟值为100mg KOH/g至450mg KOH/g且官能度为1.5至3.5的聚酯聚醚多元醇,其通过将环氧化物加成至芳族二羧酸衍生物与双官能或更高官能度的醇的酯化产物得到。
在本申请的上下文中,与本发明的组分例如某种多元醇结合使用的词语“一种”不应理解为数值。若明确说明该词语理解为数值,则表述例如“一种多元醇”或类似表述仅指“恰好一(=1)种多元醇”。可想而知,例如,可存在两种A1a类的多元醇。
本发明上下文中的“乳液”应理解为分散良好的两种液体的混合物,其中,一种液体(即物理发泡剂T)以细小液滴的形式分散在另一种液体(即多元醇混合物A1中)中,所述细小液滴的平均尺寸为≥0,1μm至≤20μm,液滴尺寸通过使用在亮场透射模式下运行的光学显微镜测定。这种乳液既不同于真溶液也不同于微乳液。微乳液具有如此分散良好的分散相,使得光不再发生折射。因此,这种微乳液在可见光范围内呈澄清且透明的,而本发明意义内的乳液呈浑浊状且表现出强光折射。此外,微乳液可仅借助乳化助剂制备,虽然原则上在本发明的乳液的制备过程中不排除使用乳化助剂,但其并非是绝对必要的且因此并非优选的。根据本发明,发泡剂T的液滴尺寸优选为≥0.1μm至≤15μm,且更优选为≥1μm至≤15μm。液滴尺寸使用亮场透射光学显微镜测定。用于光学检测的样品的合适层厚为20μm至40μm。
本发明上下文中的“物理发泡剂”应理解为因其物理性质而具有高挥发性的且不与异氰酸酯组分反应的化合物。
“羟值”意指以毫克计的氢氧化钾的量,所述量相当于1克物质乙酰化所耗乙酸的量。在本发明的上下文中,羟值按照1971年12月版的标准DIN53240确定。
本发明上下文中的“官能度”意指由所用的已知物质及其比例计算的理论官能度。
本发明还提供了含有聚氨酯的聚合物C的制备方法,其中,异氰酸酯组分B与本发明的乳液反应。
本文中,“含有聚氨酯的聚合物C”应理解为代表仅含聚氨酯基(PUR基)的聚合物和还含有脲基和/或多异氰酸酯基(PIR基)的聚合物这两者。
本发明还提供了通过本发明的方法制备的绝热模塑物,特别是用于冷藏柜的绝热模塑物。
原则上,本发明的方法对应于EP0289764A2中记载的制备方法,EP0289764A2的全部内容在此以参引的方式纳入本文中。本发明制备方法的布置——经由呈卧位(lyingposition)(即基本水平的)的盒状模塑物的底壁的中间区域注入聚氨酯反应混合物——也称作“顶流法(top-flow-process)”。现已令人惊奇地发现,较之与物理发泡剂形成溶液的现有技术的异氰酸酯活性组合物(多元醇混合物),通过使用包含多元醇A1a、A1b和A1c的聚氨酯反应混合物,可使异氰酸酯活性组合物的总粘度降低,且因而也可使乳液的总粘度降低。此外,现已发现,通过优化某些参数(例如所用多元醇中氧乙烯基(oxyethylene group)的含量),本发明的乳液的稳定性可显著提高。此外,通过经优化的多元醇乳液与合适的NCO封端的预聚物的合适组合,可提高所达到的热导率值。特别地,现已惊奇地发现,在模塑物任意位置的热导率是高度一致的且分布均匀,这视为与顶流法结合的快速固化多元醇混合物的协同效应。
在下文中,将参考本发明的各种实施方案和实施例描述这些发现和其他发现,其中,只要本文中未明确给出相反教导,则各个实施方案可彼此自由结合。
原则上,本发明可用的多元醇A1a至A1c(以及任选的其他多元醇,见下文)的制备方法为本领域技术人员已知的,且已多次描述。聚酯多元醇通过二羧酸等同物与低分子量多元醇的缩聚制备。聚醚多元醇通过环氧化物加成聚合(阴离子或阳离子)至合适的起始化合物制备。将环氧化物加成至聚酯多元醇,生成本发明的聚酯聚醚多元醇。如必要,聚合反应在本领域技术人员已知的合适的催化剂的存在下进行。
在优选的实施方案中,聚醚多元醇A1a由以下物质开始制备:蔗糖;蔗糖和丙二醇的混合物;蔗糖和乙二醇的混合物;蔗糖、丙二醇和乙二醇的混合物;山梨醇;或山梨醇与丙三醇的混合物。优选的环氧化物为1,2-环氧丁烷、2,3-环氧丁烷、环氧乙烷和环氧丙烷,其单独或混合使用。特别优选环氧乙烷和环氧丙烷,其可单独使用或两者一同使用,其中,在两者一同使用的情况下,源自环氧乙烷和环氧丙烷的氧化烯单元的随机分布以及具有特定结构的嵌段共聚物的选择性制备可想而知。蔗糖、丙二醇和乙二醇的混合物特别优选作为起始物。特别优选仅将环氧丙烷用作环氧化物。A1a的羟值特别优选为100mgKOH/g至450mgKOH/g且官能度为2.5至5。
在优选的实施方案中,聚醚多元醇A1b由以下物质开始制备:邻甲苯二胺、间甲苯二胺或对甲苯二胺或同分异构甲苯二胺的混合物。特别优选将邻甲苯二胺用作起始物。邻甲苯二胺可呈2,3-异构体和3,4-异构体的混合物的形式。然而,原则上,也可以使用其他芳族胺,例如苯二胺(所有异构体)或亚甲基联苯二胺(所有异构体)。优选的环氧化物为单独或混合形式的1,2-环氧丁烷、2,3-环氧丁烷、环氧乙烷和环氧丙烷,其单独或混合使用。特别优选环氧乙烷和环氧丙烷,其可单独使用或两者一同使用,其中,在两者一同使用的情况下,源自环氧乙烷和环氧丙烷的氧化烯单元的随机分布以及具有特定结构的嵌段共聚物的选择性制备可想而知。特别优选使用环氧丙烷,既可以单独使用也可以以与环氧乙烷的混合物使用。在使用环氧丙烷与环氧乙烷的混合物的情况下,环氧丙烷与环氧乙烷的质量比为0.25:1至4:1,最特别优选为0.5:1至2:1。在嵌段共聚物的情况下,其优选以环氧丙烷封端。
在优选的实施方案中,在多元醇A1c的制备中使用的芳族二羧酸衍生物为邻苯二甲酸衍生物,特别优选邻苯二甲酸酐。
在多元醇A1c的制备中,优选的双官能或更高官能度的醇为乙二醇和二乙二醇及其高级同系物;1,2-丙二醇、二丙二醇及其高级同系物、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇及其高级同系物、2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇、丙三醇、季戊四醇、1,1,1-三羟甲基丙烷和含5至12个碳原子的碳水化合物(例如异山梨醇)。最特别优选乙二醇和二乙二醇。
在多元醇A1c的制备中,优选使用的环氧化物为环氧乙烷和环氧丙烷。它们的使用量使得氧乙烯基的含量为5质量%至50质量%,优选10质量%至40质量%,特别优选15质量%至30质量%,相对于多元醇A1c的总质量计。
在某些实施方案中,多元醇混合物A1还可包含其他多元醇。因此,还可存在(iv)由脂族胺或多羟基醇开始制备的短链聚醚多元醇A1d,所述聚醚多元醇的羟值为500mg KOH/g至1000mg KOH/g,优选为600mg KOH/g至950mg KOH/g,特别优选为700mg KOH/g至900mgKOH/g,且官能度为1.5至5.0,优选为2.0至4.5,特别优选为2.5至4.0。A1d特别优选通过将环氧化物加成至乙二胺或三羟甲基丙烷而获得。优选的环氧化物为环氧乙烷和环氧丙烷,特别优选环氧丙烷。
多元醇混合物A1还可包含(v)双官能至四官能胺类或醇类扩链剂或交联剂A1e。A1e优选选自丙三醇、丁二醇、乙二醇、二乙二醇、丙二醇、乙二胺、乙醇胺、三乙醇胺、三羟甲基丙烷和季戊四醇。
此外,聚醚碳酸酯多元醇A1f也可用在多元醇混合物A1中,所述聚醚碳酸酯多元醇A1f例如可通过在H-官能起始物质的存在下环氧化物与二氧化碳的催化反应得到(参见例如EP2046861A1)。这些聚醚碳酸酯多元醇的官能度通常大于或等于1.0,优选为2.0至8.0,特别优选为2.0至7.0,且最特别优选为2.0至6.0。数均摩尔质量优选为400g/mol至10,000g/mol且特别优选为500g/mol至6000g/mol。
根据本发明方法的其他优选实施方案,多元醇混合物A1还包含由多羟基醇开始制备的聚醚多元醇A1g,所述聚醚多元醇A1g的羟值为15mg KOH/g至550mg KOH/g且官能度为1.5to5.0,特别是羟值为20mg KOH/g至530mg KOH/g且官能度为1.5至4.0,更优选羟值为25mg KOH/g至515mg KOH/g且官能度为1.5至4.0。这是特别有用的,原因在于这种聚醚多元醇A1g能改善聚氨酯反应混合物的流动性,从而实现表面处呈非均匀的泡沫的量更少、气泡(air pocket)产生的量更少且泡沫粘附性更好。
在本发明的上下文中,数均摩尔质量Mn根据2007年8月版的DIN55672-1通过凝胶渗透色谱法测定。
原则上,物理发泡剂T不受限制,条件是,其在一般条件范围(温度、压力)下不溶于多元醇混合物A1中(否则随后无法制备乳液)。用于本发明的物理发泡剂优选选自烃(例如正戊烷、异戊烷、环戊烷、丁烷、异丁烷)、醚(例如甲缩醛)、卤代醚、含1至8个碳原子的全氟烃(例如全氟己烷)及其相互的混合物。在特别优选的实施方案中,将戊烷异构体或各种戊烷异构体的混合物用作物理发泡剂T。极特别优选地将环戊烷用作发泡剂T。
在特别优选的实施方案中,本发明的乳液恰好含有多元醇A1a、A1b和A1c中的各一种以及恰好含有A1d、A1e和A1f(如果每一种均存在)中的各一种。更优选的是,除A1a、A1b和A1c以及A1d、A1e和A1f(如果每一种均存在)之外,不存在其他多元醇,换言之,在优选的实施方案中,多元醇混合物A1由最多六种多元醇组成。
通常有利的是,异氰酸酯活性组合物A除多元醇混合物A1外,还含有其他组分。这些组分原则上为本领域技术人员已知的,且包括例如水、泡沫稳定剂、催化剂、阻燃剂和任选的其他助剂和添加剂。在特别优选的实施方案中,异氰酸酯活性组合物A还包含:
(vi)水A2;
(vii)至少一种泡沫稳定剂A3,其选自聚醚-聚二甲基硅氧烷共聚物,优选以含有氧亚丙基和/或氧亚乙基的聚醚侧链官能化的共聚物;
和
(viii)至少一种催化剂A4,其选自三亚乙基二胺、N,N-二甲基环己胺、二环己基甲胺、四亚甲基二胺、1-甲基-4-二甲基氨基乙基哌嗪、三乙胺、三丁胺、二甲基苄胺、N,N',N"-三-(二甲基氨基丙基)六氢化三嗪、三-(二甲基氨基丙基)胺、三(二甲基氨基甲基)苯酚、二甲基氨基丙基甲酰胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基丁二胺、四甲基己二胺、五甲基二亚乙基三胺、五甲基二亚丙基三胺、四甲基二氨基乙基醚、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷、双-(二甲基氨基丙基)脲、N-甲基吗啉、N-乙基吗啉、N-[(2-羟基-5-壬基苯基)甲基]-N-甲基氨基乙酸钠、N-环己基吗啉、2,3-二甲基-3,4,5,6-四氢嘧啶、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、二甲基乙醇胺、
如必要(如需要高多异氰脲酸酯含量),还包括至少一种选自如下的催化剂:乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)、月桂酸锡(II)、二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡、二乙酸二辛基锡、三-(N,N-二甲基氨基丙基)-s-六氢三嗪、氢氧化四甲基铵、乙酸钠、辛酸钠、乙酸钾、辛酸钾、氢氧化钠。
水的功能为化学共发泡剂,即与异氰酸酯基反应释放出二氧化碳,二氧化碳作为除T之外的物理发泡剂。
为了建立稳定的乳液,还有利的是,使一定比例的发泡剂T粘附至多元醇混合物A1。在优选的实施方案中,本发明因而涉及一种乳液,其中A1:T的质量比优选为≥5:1至≤12:1,更优选为≥10:1至≤5:1,最优选为≥9:1至≤6:1。
在本发明的乳液的优选实施方案中,异氰酸酯活性组合物A的组分以如下质量百分比存在,所述质量百分比彼此独立且在各个情况下基于异氰酸酯活性组合物A的总质量:
多元醇A1a,5质量%至60质量%、优选15质量%至50质量%,
多元醇A1b,5质量%至60质量%,优选10质量%至50质量%,
多元醇A1c,5质量%至60质量%,优选15质量%至50质量%,
任选地多元醇A1d,1质量%至20质量%,优选1质量%至15质量%,
任选地多元醇A1e,1质量%至20质量%,优选1质量%至15质量%,
任选地多元醇A1f,1质量%至20质量%,优选1质量%至15质量%,
任选地多元醇A1g,1质量%至20质量%,优选1质量%至15质量%,
水A2,0质量%至5质量%,优选0.5质量%至3质量%,
泡沫稳定剂A3,1质量%至10质量%,优选1.5质量%至8质量%,
催化剂A4,0.5质量%至5质量%,优选1质量%至4质量%。
本发明的乳液优选含有80质量%至90质量%的多元醇混合物A1和10质量%至20质量%的物理发泡剂T,在各个情况下基于乳液的总质量计。
若每种组分存在几个代表(例如,两种物理发泡剂T(T1和T2)的混合物),上述质量百分比适用于各个组分的多个代表的总和(即,在上述两种物理发泡剂T的实例中,乳液中T1和T2的质量百分比之和为10质量%至20质量%)。
在特别优选的实施方案中,不存在其他组分,换言之,乳液特别优选由至多A1a、A1b、A1c、A1d、A1e、A1f、A2、A3、A4和T组成。乳液极特别优选由A1a、A1b、A1c、A2、A3、A4和T组成。
本发明的乳液的制备优选以如下方式进行:通常在大气压力和温度下,将多元醇混合物A1(即,至少多元醇A1a、A1b和A1c;任选的如上定义的其他多元醇和任选的如上定义的助剂和添加剂)的各个组分以任意顺序混合在一起,并随后将发泡剂T加入至由此得到的多元醇混合物A1。
乳液可通过如下方式制备:通常在室温和环境压力下,将A的组分以任意顺序混合,并随后加入发泡剂T。乳化可使用高剪切混合器(例如喷射式解胶器(dispergator)和转子解胶器)进行。代表性实例包括Schubert,H.(编辑);Emulgiertechnik;R.Behr’sVerlag,Hamburg,2005中公开的那些。
本发明的乳液的特征在于高稳定性,所述高稳定性不以过度上升的粘度为代价。本文中,“稳定”应理解为意指,在室温和常压下,乳液可储存至少2小时,优选至少1天,特别优选至少3天,最特别优选至少5天,且多元醇混合物A1与发泡剂T不发生相分离。在25℃下,本发明的多元醇混合物的粘度≥1000mPas至≤18000mPas,特别优选≥1500mPas至≤12000mPas,且最特别优选≥2000mPas至≤12000mPas。粘度根据1994年10月版的ENISO3219测定。
本发明还提供了含聚氨酯的聚合物C的制备方法,其中,异氰酸酯组分B与本发明的含有多元醇混合物A1和物理发泡剂T的乳液反应。在发泡剂和任选的其他助剂和添加剂的存在下,由异氰酸酯组分和异氰酸酯活性组分制备含聚氨酯的聚合物原则上为本领域技术人员已知的,且已多次描述。含聚氨酯的聚合物C优选通过本领域技术人员已知的方法制备。实例描述于下列文件中:US2,764,565;G.Oertel(Ed.)"Kunststoff-Handbuch",卷VII,Carl Hanser Verlag,第3版,Munich1993,第267至354页和K.Uhlig(Ed.)"PolyurethanTaschenbuch",Carl Hanser Verlag,第2版,Vienna2001,第83至102页。原则上,组分发泡形成含聚氨酯的聚合物C可通过例如所引用的现有技术已知的方法进行。
在本发明方法的优选实施方案中,异氰酸酯组分B为:
a)至少一种异氰酸酯B1,其选自
甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、多苯基多亚甲基多异氰酸酯(PMDI)、苯二甲基二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯、二异氰酸基二环己基甲烷和异佛尔酮二异氰酸酯,
或
b)由至少一种多异氰酸酯B1和至少一种异氰酸酯活性化合物制备的异氰酸酯封端的预聚物B2,所述异氰酸酯活性化合物选自多元醇A1a、A1b、A1c、A1d和A1f中的至少一种,
或
c)B1和B2的混合物。
异氰酸酯B与乳液A的反应优选在异氰酸酯指数为95至180、优选95至150、特别优选100至130下进行。“异氰酸酯指数”应理解为实际使用的异氰酸酯基的量[mol]与所有异氰酸酯活性基团完全反应化学计量学所需的异氰酸酯基的量[mol]之商乘以100。由于1mol异氰酸酯活性基团反应需要1mol异氰酸酯基,
异氰酸酯指数=(异氰酸酯基的mol/异氰酸酯活性基团的mol)·100
本发明还提供可由上述本发明的方法获得的含聚氨酯的聚合物C。所述含聚氨酯的聚合物C可通过连续和非连续加工方法制备,且特别适合用作绝热材料。
非连续制备的含聚氨酯的聚合物C为模塑泡沫,其顶部和底部均通过装饰层划界(delimit)。金属、塑料、木材和纸特别适合作为装饰层。可特别地引用的上述非连续制备的PUR组合单元的应用领域为设备的工业绝热,设备例如冷藏箱、冷冻箱、组合的冷藏冷冻箱以及热水器、冷冻容器(chill container)和冷却箱以及冷却管。
连续制备的含聚氨酯的聚合物C为连续制备的具有限定宽度和各种厚度的PUR泡沫块,其在顶部和底部优选用装饰层限界。然而,在某些应用领域(例如在建筑领域),还可完全不使用装饰层。金属、金属箔、塑料、木材和纸主要适于作为装饰层。可特别地引用的所述连续制备的含聚氨酯的聚合物C的应用领域为冷藏库的工业绝热和建筑领域的绝热。
在这些领域中,含聚氨酯的聚合物的用途原则上为本领域技术人员已知的且已多次描述。本发明的含聚氨酯的聚合物C非常适于这些目的,原因在于,其特征为低热导率值,且在泡沫的制备过程中或其应用于合适的基底(例如冷藏箱壳体或冷气管)的过程中,不存在因过高的粘度而带来加工问题的风险。
在本发明的方法中,进一步优选的是,中间区域同心布置在底面的二维投影中。这是有利的,原因在于,就模塑物的相对位置而言,注射点是等距的。
原则上,本发明的方法不需要注射点是数学上准确的中间点(即底面的二维投影的几何中心),尽管这种实施方案为本发明的一部分。但对于大多数应用,用底面的一部分来定义外壁底面的中间区域是足够的,所述底面的一部分由底面的二维投影的几何中心向各个方向延伸不超过二维投影的纵向范围的10%、优选不超过5%。
用于本发明方法的模具可为任何类型的模具,特别是用于制备冷藏柜的模具。在本发明方法的实施方案中,所述模具提供有至少一个通风孔,从而使来自模具的空气在其被腔室中膨胀的泡沫移位时能够排出。
在本发明方法的进一步优选的实施方案中,将腔室抽真空至低于环境压力的压力,特别将压力减少≥1mbar至高达≤900mbar,特别是减少≥20mbar至≤600mba,且优选减少≥50mbar至≤300mbar。这是有利的,原因在于发泡过程由抽真空的腔室支撑。这种真空支撑(vacuum-supported)的方法可通过将整个模具置于真空室中实施。或者,可将模具本身抽真空,然而在此情况下,应使用不具有通风孔的模具或具有可密封的通风孔的模具。
聚氨酯反应混合物优选通过布置在入口处的注射喷嘴注入腔室中,入口或注射喷嘴特别地提供有挡板和/或分配头。所述分配头可提供有多个卸料出口和/或多个卸料出口形成于分配头与外壁的底面之间。在这种布置中,聚氨酯反应混合物通过卸料出口以基本上为层流的方式注入腔室中,所述卸料出口优选的形状为狭缝状。特别优选使用分配头,这是因为其喷入剖面和几何形状可精确匹配于腔室的形状,从而优化注入过程。特别地,对于本发明的快速固化体系,这是有利的,原因在于,聚氨酯反应混合物在其粘度开始上升之前,其在表面上铺展的时间更短。
分配头可布置在入口处,且优选固定至外壁的底面并支撑在内壁的底面上。换言之,分配头为模具的组成部分,将其固定至外壁的底面并支撑在内部的底面上使其在制备过程中于所需位置处保持安全。
卸料出口可例如以如下方式布置:使聚氨酯反应混合物基本上平行于外壁的底面注入至腔室中。这种布置具有以下优势,注入的反应混合物的撞击点(impact point)主要由注射压力确定,或者换言之,由注射速率确定。
实施例
将通过图1和如下实施例更详细地描述本发明。唯一的附图表明
图1打开的开口盒状模具的顶视图。
使用的材料
使用如下物质:
多元醇1:聚醚多元醇,OH值为450mg KOH/g,理论官能度为4.7,且25℃下的粘度为15000mPas(Bayer MaterialScience);
多元醇2:聚醚多元醇,OH值为380mg KOH/g,理论官能度为4.6,且25℃下的粘度为5350mPas(Bayer MaterialScience);
多元醇3:聚醚多元醇,OH值为400mg KOH/g,理论官能度为4.0,且25℃下的粘度为26500mPas(Bayer MaterialScience);
多元醇4:聚醚多元醇,OH值为235mg KOH/g,理论官能度为3,且25℃下的粘度为250mPas(Bayer MaterialScience);
多元醇5:芳族聚醚多元醇,OH值为300mg KOH/g,理论官能度为2.0,且25℃下的粘度为6500mPas,由邻苯二甲酸酐与二乙二醇反应(implementation)并随后乙氧基化制备(Bayer MaterialScience);
多元醇6:聚醚多元醇,OH值为112mg KOH/g,理论官能度为2,0且25℃下的粘度为140mPas(Bayer MaterialScience);
添加剂:三乙基磷酸酯(Brenntag GmbH);
稳定剂:
胺催化剂:叔胺,其熟知于PUR-化学标准催化剂以及本领域技术人员;
异氰酸酯:聚合MDI(44V20L,Bayer MaterialScience)
羟值(OH值)根据DIN53240(1971年12月)测定。
粘度根据1994年10月版的EN ISO3219测定。
性能和试验分析
本发明的PUR硬质泡沫根据本领域技术人员已知的一步法制备,其中,组分连续反应或非连续反应,并随后以合适的形式或在合适的基底上固化。实例在如下文件中提及:US2,761,565A;G.Oertel“Kunststoff-Handbuch”,卷VII,Carl Hanser Verlag,第3版,Munich1993,第267页及以后页和K.Uhlig“Polyurethan Taschenbuch”,Carl HanserVerlag,第2版,Vienna2001,第83-102页。
在实施例中,冷藏箱壳体使用相应模具通过顶流法形成(将进一步描述)。对于模塑物,通过常规高压设备(Hennecke的HK1250)和高压混合头(Cannon的FPL)在约1770g/s的卸料性能下加工由发泡剂多元醇制剂(见表1)和异氰酸酯组成的双组分制剂。
对于试验,使用模具M,其在图1中以展开的二维平面方式示出,其具有常规尺寸和冷冻箱的形状。模具M为开口盒状且具有内壁和外壁,内壁和外壁之间提供有填充PUR/PIR-配方的腔室。内壁和外壁彼此以固定距离布置,在图1中,为清楚的原因,仅示出外壁。每个壁均包括底面3和多个侧面1、2、4、5。小侧面1、5对应于冷冻箱的上壁和下壁,较大的侧面2、4对应于冷冻箱的左侧壁和右侧壁,面3对应于冷冻箱的后壁。
在底面3的中间区域,布置有一个入口I,入口I中固定有供聚氨酯反应混合物注入腔室中的分配头D。分配头D支撑在内壁(未示出)的底面上且提供有两个狭缝状的卸料出口。所述卸料出口指向较小侧壁1、5,以使聚氨酯反应混合物在各自的方向上注入棒形停料(landing)区域6、7,所述停料区域6、7从分配头D分别延伸至面3和面1的边缘以及面3和面5的边缘。
在填充腔室之前,将模具翻转,使其外壁的底面3向下,从而使得聚氨酯反应混合物向上发泡以填充所述腔室。
用8000g各种PUR/PIR-反应混合物填充模具M。所述反应混合物通过顶流法经由分配头注入,所述分配头固定在壳体后壁的中心。所述壳体平置,即平置于后壁上。模具温度为33–36℃,原料温度为20–22℃。
加工配方(以重量份计)和产品性能列于表1中:
表1:加工配方
结果
热导率值根据2001年5月版的DIN EN12664测定,且除另有说明外,在10℃的中心温度下测定。
在切口试样上测量指定的核心密度,以根据2001年5月版的DINEN12664通过测定相应的质量计算热导率。
对于实施例1和实施例3,本发明的各个多元醇制剂以环戊烷或环戊烷和异戊烷(70/30)的混合物作为物理发泡剂,用≤25秒的短凝胶时间加工。为进行直接比较,实施例2和实施例4的多元醇制剂分别以≥30秒的慢得多的凝胶时间加工。这些对比实施例对应于设备工业中通常使用的多元醇制剂。为与本发明的实施例1直接比较,实施例2中使用环戊烷作为发泡剂。为与本发明的实施例3直接比较,实施例4中使用环戊烷和异戊烷(70/30)的混合物作为物理发泡剂。
为分析使用顶流法的本发明快速固化多元醇制剂的效果,对模塑物进行有关泡沫热导率和泡沫产品密度的测试,所述泡沫为图1中所示的底面3和侧面1、2、4、5位置处的泡沫。结果列于表2中。
表2:机械测试结果
所述结果清楚地表明,通过顶流法与本发明的快速固化多元醇制剂的结合,实施例1与实施例2相比,热导率提高约5%,并且实施例3与实施例4相比,热导率提高最高达约10%。此外,显而易见的是,所述热导率的提高与物理发泡剂无关,这是因为对于环戊烷以及对于环戊烷与异戊烷(70/30)的混合物而言,均可实现所述提高。
参考数字列表:
1 侧面
2 侧面
3 底面
4 侧面
5 侧面
6 棒形停料区
7 棒形停料区
M 模具
I 入口
D 分配头
Claims (25)
1.绝热模塑物的制备方法,其中,所述模塑物通过如下方式提供:在开口盒状模具(M)的内壁和外壁之间的腔室填充聚氨酯反应混合物,并使该聚氨酯反应混合物固化为含有聚氨酯的聚合物C,所述内壁和外壁彼此以固定距离布置,且每个壁均包括一个底面(3)和多个侧面(1、2、4、5),而聚氨酯反应混合物通过置于所述外壁的底面(3)的中间区域的入口(I)加入,其中,在将聚氨酯反应混合物填入所述腔室之前,将模具(M)旋转,使其外壁的底面向下,从而使得聚氨酯反应混合物向上发泡以填充所述腔室,
其特征在于,所述聚氨酯反应混合物含有与乳液反应的异氰酸酯组分B,所述乳液包含:
(I)异氰酸酯活性组合物A,其含有由至少三种多元醇A1a、A1b和A1c组成的多元醇混合物A1作为连续相
和
(II)至少一种物理发泡剂T作为分散相,
其中:
(i)A1a为羟值为15mg KOH/g至550mg KOH/g且官能度为1.5至6.0的聚醚多元醇,其通过将环氧化物加成至一种或多种起始化合物得到,所述起始化合物选自碳水化合物和双官能或更高官能度的醇;
(ii)A1b为羟值为100mg KOH/g至550mg KOH/g且官能度为1.5至5.0的聚醚多元醇,其通过将环氧化物加成至芳族胺得到;
(iii)A1c为羟值为100mg KOH/g至450mg KOH/g且官能度为1.5至3.5的聚酯聚醚多元醇,其通过将环氧化物加成至芳族二羧酸衍生物与双官能或更高官能度的醇的酯化产物得到。
2.权利要求1所述的方法,其特征在于,绝热模塑物是用于制冷设备的模塑物。
3.权利要求1所述的方法,其特征在于,物理发泡剂T的液滴的平均尺寸为≥0.1μm至≤20μm,所述液滴尺寸通过使用在亮场透射模式下运行的光学显微镜测定。
4.权利要求3所述的方法,其特征在于,物理发泡剂T的液滴的平均尺寸为≥0.1μm至≤15μm。
5.权利要求1至4中任一项的方法,其特征在于,所述聚醚多元醇A1a是由以下物质开始制备的聚醚多元醇:蔗糖;蔗糖和丙二醇的混合物;蔗糖和乙二醇的混合物;蔗糖、丙二醇和乙二醇的混合物;山梨醇;或山梨醇与丙三醇的混合物。
6.权利要求1至4中任一项的方法,其特征在于,所述聚醚多元醇A1b为由以下物质开始制备的聚醚多元醇:邻甲苯二胺、间甲苯二胺或对甲苯二胺或同分异构甲苯二胺的混合物,和/或
其特征在于,所述聚酯聚醚多元醇A1c为通过将环氧化物加成至邻苯二甲酸衍生物与双官能或更高官能度的醇的酯化产物得到的聚酯聚醚多元醇,所述双官能或更高官能度的醇选自
1,2-丙二醇、二丙二醇及其高级同系物、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一烷二醇、1,12-十二烷二醇及其高级同系物、2-甲基-1,3-丙二醇、新戊二醇、3-甲基-1,5-戊二醇、丙三醇、季戊四醇、1,1,1-三羟甲基丙烷和含5至12个碳原子的碳水化合物,和/或
其特征在于,所述多元醇混合物A1还包含:
(iv)由脂族胺或多羟基醇开始制备的聚醚多元醇A1d,所述聚醚多元醇的羟值为500mgKOH/g至1000mg KOH/g且官能度为1.5至5.0,和/或
其特征在于,所述多元醇混合物A1还包含由多羟基醇开始制备的聚醚多元醇A1g,所述聚醚多元醇A1g的羟值为15mg KOH/g至550mg KOH/g且官能度为1.5至5.0。
7.权利要求6的方法,其特征在于,所述聚醚多元醇A1g的羟值为20mg KOH/g至530mgKOH/g且官能度为1.5至4.0。
8.权利要求6的方法,其特征在于,所述聚醚多元醇A1g的羟值为25mg KOH/g至515mgKOH/g且官能度为1.5至4.0。
9.权利要求1至4中任一项的方法,其特征在于,所述多元醇混合物A1还包含:
(v)双官能至四官能胺类或醇类扩链剂或交联剂。
10.权利要求1至4中任一项的方法,其特征在于,所述物理发泡剂T为选自下列的至少一种:烃、卤代醚和含1至8个碳原子的全氟烃。
11.权利要求1至4中任一项的方法,其特征在于,所述异氰酸酯活性组合物A还包含:
(vi)水A2;
(vii)至少一种泡沫稳定剂A3,其选自聚醚-聚二甲基硅氧烷共聚物,
和
(viii)至少一种催化剂A4,其选自三亚乙基二胺、N,N-二甲基环己胺、二环己基甲胺、四亚甲基二胺、1-甲基-4-二甲基氨基乙基哌嗪、三乙胺、三丁胺、二甲基苄胺、N,N',N"-三-(二甲基氨基丙基)六氢化三嗪、三-(二甲基氨基丙基)胺、三(二甲基氨基甲基)苯酚、二甲基氨基丙基甲酰胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四甲基丁二胺、四甲基己二胺、五甲基二亚乙基三胺、五甲基二亚丙基三胺、四甲基二氨基乙基醚、二甲基哌嗪、1,2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷、双-(二甲基氨基丙基)脲、N-甲基吗啉、N-乙基吗啉、N-[(2-羟基-5-壬基苯基)甲基]-N-甲基氨基乙酸钠、N-环己基吗啉、2,3-二甲基-3,4,5,6-四氢嘧啶、三乙醇胺、二乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和二甲基乙醇胺。
12.权利要求1至4中任一项的方法,其特征在于,A1:T的质量比为≥5:1至≤12:1。
13.权利要求1至4中任一项的方法,其特征在于,多元醇组分A1根据EN ISO 3219在25℃下测定的粘度为≥1000mPas至≤18000mPas。
14.权利要求1至4中任一项的方法,其特征在于,所述异氰酸酯组分B为
a)至少一种异氰酸酯B1,其选自
甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、多苯基多亚甲基多异氰酸酯、苯二甲基二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯、二异氰酸基二环己基甲烷和异佛尔酮二异氰酸酯,或
b)由至少一种多异氰酸酯B1和至少一种异氰酸酯活性化合物制备的异氰酸酯封端的预聚物B2,所述异氰酸酯活性化合物选自下列多元醇中的至少一种:
b.1)羟值为15mg KOH/g至550mg KOH/g且官能度为1.5至6.0的聚醚多元醇,其通过将环氧化物加成至一种或多种起始化合物得到,所述起始化合物选自碳水化合物和双官能或更高官能度的醇(A1a);
b.2)羟值为100mg KOH/g至550mg KOH/g且官能度为1.5至5.0的聚醚多元醇,其通过将环氧化物加成至芳族胺得到(A1b);
b.3)羟值为100mg KOH/g至450mg KOH/g且官能度为1.5至3.5的聚酯聚醚多元醇,其通过将环氧化物加成至芳族二羧酸衍生物与双官能或更高官能度的醇的酯化产物得到(A1c);
b.4)羟值为500mg KOH/g至1000mg KOH/g且官能度为1.5至5.0的聚醚多元醇(A1d);
b.5)官能度≥1.0至8.0且数均摩尔质量为400g/mol至10,000g/mol的聚醚碳酸酯多元醇(A1f);
b.6)官能度1.5至5.0且羟值为15mg KOH/g至550mg KOH/g的聚醚多元醇(A1g)
或
c)B1和B2的混合物。
15.权利要求1至4中任一项的方法,其特征在于,异氰酸酯组分B与乳液的反应在异氰酸酯指数为95至130下进行。
16.权利要求1至4中任一项的方法,其特征在于,中间区域同心布置在底面(3)的二维投影中,和/或,其特征在于,将外壁的底面(3)的中间区域定义为底面(3)的一部分,所述底面(3)的一部分由底面(3)的二维投影的几何中心向各个方向延伸不超过二维投影的纵向范围的10%。
17.权利要求16的方法,其特征在于,所述底面(3)的一部分由底面(3)的二维投影的几何中心向各个方向延伸不超过二维投影的纵向范围的5%。
18.权利要求1至4中任一项的方法,其特征在于,模具(M)提供有至少一个通风孔,和/或,其特征在于,将腔室抽真空至低于环境压力的压力。
19.权利要求18的方法,其特征在于,将腔室抽真空至压力减少≥1mbar至高达≤900mbar。
20.权利要求18的方法,其特征在于,将腔室抽真空至压力减少≥20mbar至≤600mbar。
21.权利要求18的方法,其特征在于,将腔室抽真空至压力减少≥50mbar至≤300mbar。
22.权利要求1至4中任一项的方法,其特征在于,聚氨酯反应混合物通过布置在入口(I)处的注射喷嘴注入腔室中,入口(I)或注射喷嘴提供有挡板和/或分配头(D),而所述分配头(D)提供有多个卸料出口和/或多个卸料出口形成于分配头(D)与外壁的底面(3)之间,聚氨酯反应混合物通过卸料出口以基本上为层流的方式注入腔室中,所述卸料出口形状为狭缝状。
23.权利要求22的方法,其特征在于,分配头(D)布置在入口(I)处,并固定至外壁的底面(3)并支撑在内壁的底面上,和/或,其特征在于,卸料出口以如下方式布置:聚氨酯反应混合物基本上平行于外壁的底面(3)注入至腔室中。
24.通过权利要求1-23之一的方法得到的绝热模塑物,其特征在于,所述模塑物在任意位置处的热导率是高度一致的且分布均匀的。
25.权利要求24的绝热模塑物,其特征在于,所述绝热模塑物为冷藏箱用模塑物。
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EP13156635.8 | 2013-02-25 | ||
EP20130156635 EP2770002A1 (en) | 2013-02-25 | 2013-02-25 | Insulation moulding and method for its manufacture |
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EP (2) | EP2770002A1 (zh) |
KR (1) | KR102139385B1 (zh) |
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US10507621B2 (en) * | 2014-06-11 | 2019-12-17 | Basf Se | Polyurethane compound for producing an integrated insulation component |
WO2024043844A1 (en) * | 2022-08-25 | 2024-02-29 | Boa Maki̇ne Üreti̇m İthalat İhracat İnşaat Ti̇c. Ve San. Ltd. Şti̇. | Composite panel production method |
CN116589740B (zh) * | 2023-07-14 | 2023-09-22 | 山东理工大学 | 用于制备绝热性能优异的聚氨酯硬质泡沫的聚合物多元醇组合物 |
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US2764565A (en) | 1951-12-24 | 1956-09-25 | Bayer Ag | Process and apparatus for the manufacture of polyurethane plastics |
US2761565A (en) | 1954-03-19 | 1956-09-04 | Clyde E Hutchinson | Filter units |
EP0289764A3 (de) | 1987-04-07 | 1989-10-18 | Liebherr-Hausgeräte Gmbh | Verfahren zum Ausschäumen des glockenförmigen Hohlraums zwischen Behälteraussen- u. Behälterinnenwandungen o.dgl., vorzugsweise des Hohlraums zwischen den Innenwandungen und den Ausenwandungen von Kühl- und/oder Gefriergeräten |
DE19623065A1 (de) * | 1996-06-10 | 1997-12-11 | Bayer Ag | Verfahren zur Herstellung von Polyurethan Hartschaumstoffen mit geringer Wärmeleitfähigkeit |
DE19742011A1 (de) | 1997-09-24 | 1999-03-25 | Basf Ag | Lagerstabile, treibmittelhaltige Emulsionen zur Herstellung von Hartschaumstoffen auf Isocyanatbasis |
JP2000128951A (ja) | 1998-10-26 | 2000-05-09 | Sumitomo Bayer Urethane Kk | 硬質ポリウレタンフォームの製造方法 |
US6472446B1 (en) | 2001-03-09 | 2002-10-29 | Basf Corporation | Phase stable polyol composition containing hydrocarbon as the blowing agent |
JP2003042653A (ja) * | 2001-07-27 | 2003-02-13 | Hitachi Ltd | 冷却装置の断熱体 |
US7977501B2 (en) | 2006-07-24 | 2011-07-12 | Bayer Materialscience Llc | Polyether carbonate polyols made via double metal cyanide (DMC) catalysis |
ITMI20081867A1 (it) * | 2008-10-22 | 2010-04-22 | Dow Global Technologies Inc | Processo per lapreparazione di schiume poliuretaniche rigide a celle chiuse |
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BR102014004175B1 (pt) | 2020-06-02 |
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BR102014004175A2 (pt) | 2016-05-24 |
EP2770003A1 (en) | 2014-08-27 |
US20140242313A1 (en) | 2014-08-28 |
MX350517B (es) | 2017-09-08 |
US9713886B2 (en) | 2017-07-25 |
CN104004215A (zh) | 2014-08-27 |
EP2770003B1 (en) | 2018-09-12 |
KR102139385B1 (ko) | 2020-07-29 |
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