CN1292013A - 聚氨酯硬泡沫塑料的制造方法 - Google Patents
聚氨酯硬泡沫塑料的制造方法 Download PDFInfo
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- CN1292013A CN1292013A CN99803273A CN99803273A CN1292013A CN 1292013 A CN1292013 A CN 1292013A CN 99803273 A CN99803273 A CN 99803273A CN 99803273 A CN99803273 A CN 99803273A CN 1292013 A CN1292013 A CN 1292013A
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- pentane
- trimethylmethane
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- pentamethylene
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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Abstract
制造聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料的方法,该方法包含使一种有机多异氰酸酯与一种多官能团异氰酸酯反应性组分在一种发泡剂混合物存在下进行反应的步骤,该发泡剂混合物包含50～90wt%的环戊烷和10～50wt%的异戊烷和/或正戊烷与异丁烷和/或正丁烷的混合物,其中异戊烷和/或正戊烷对异丁烷和/或正丁烷的重量比为5/95～95/5。
Description
本发明涉及聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料的制造方法和由此方法所制得的泡沫塑料，还涉及此方法所采用的新型组合物。
聚氨酯和氨基甲酸酯改性的聚异氰脲酸酯硬泡沫通常的制造方法是，在发泡剂的存在下使适当的多异氰酸酯与异氰酸酯反应性的化合物(通常是多元醇)进行反应。这类泡沫塑料的用途之一是用作绝热材料，例如用作冷藏设备的结构材料。硬泡沫塑料的绝热性能取决于许多因素，对于封闭泡孔的硬泡沫塑料来说，其中包括泡孔的大小和泡孔内含物的导热率。
在生产聚氨酯和氨基甲酸酯改性的聚异氰脲酸酯泡沫塑料中已经广泛采用作为发泡剂的一类物质是全卤代的氟氯烃，尤其是三氯氟甲烷(CFC-11)。这些发泡剂，尤其是CFC-11因具有极低的热导率故能使所制备的硬泡沫塑料具备有效的绝热性能。近来人们关注氟氯烃对造成大气中臭氧消耗的潜在性，这就导致迫切需要开发能够替代氟氯烃发泡剂的反应体系，这类替代材料是环境保护所能接受的，而且由其所制造的泡沫塑料在许多应用领域中具有所必需的性能。
在先有技术中所提出的此类替代性发泡剂包括含氢氯氟烃、含氢氟烃以及特别是烃类即烷烃和环烷烃类，如异丁烷、正戊烷、异戊烷、环戊烷以及其混合物。
优选的是环戊烷和异丁烷的混合物。如在欧洲专利EP421269所述的那种；还有环戊烷和异戊烷或正戊烷的混合物，如WO94／25514中所述的那种。
本发明的目的在于提供一种烃发泡剂混合物，该混合物能够改善泡沫塑料的性能，同时又能使加工变得容易。
本发明的这些目的之所以能够达到，是因为在由多异氰酸酯和异氰酸酯反应性组分制造聚氨酯和氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料中使用了一种发泡剂混合物，该混合物包含50～90wt％的环戊烷和10～50wt％的异戊烷和／或正戊烷及异丁烷和／或正丁烷的混合物，其中异戊烷和／或正戊烷与异丁烷和／或正丁烷的重量比为5／95～95／5。
采用这种发泡剂混合物较之采用环戊烷与异丁烷的混合物能使加工变得更为容易，且能改善绝热性能。
较之采用环戊烷与异-或正戊烷混合物而言，采用本发明的混合物能够制得尺寸稳定性获得改善的泡沫塑料，这是因为能够获得较低密度的稳定泡沫体。
最好，在所说的发泡剂混合物中环戊烷的含量为60～90wt％、较优选的为60～80wt％、最优选的为70～75wt％；异戊烷和／或正戊烷与异丁烷和／或正丁烷的重量比优选为90／10～20／80、较优选的为75／25～25／75、最优选的为2／1～1／2。
在本发明的发泡剂混合物中，采用异戊烷要优于采用正戊烷，同样，采用异丁烷要优于采用正丁烷。
本发明中所用的优选发泡剂混合物的实例可列举如下：含70wt％环戊烷、20wt％异戊烷和10wt％异丁烷的混合物，含70wt％环戊烷、10wt％异戊烷和20wt％异丁烷的混合物，含75wt％环戊烷、15wt％异戊烷和10wt％异丁烷的混合物。
本发明中所要采用的合适的异氰酸酯反应性组分包括任何一种本领域中用于制造聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料的那些已知的异氰酸酯反应性组分。对于制备硬泡沫塑料特别重要的是多元醇类和多元醇混合物，其平均羟基数为300～1000、尤其是300～700mg KOH／g，且其羟基官能度为2～8、尤其是3～8。合适的多元醇在先有技术中已作充分论述，其中包括环氧烷烃类，如环氧乙烷和／或环氧丙烷与每个分子含2～8个活泼氢原子的引发剂反应的产物。合适的引发剂包括：多元醇类如甘油、三羟甲基丙烷、三乙醇胺、季戊四醇、山梨醇和蔗糖，多胺类如乙二胺、甲苯二胺(TDA)、二氨基二苯甲烷(DADPM)和多亚甲基多亚苯基多胺和氨基醇类如乙醇胺和二乙醇胺，以及此类引发剂的混合物。其它合适的聚多元醇类包括由适当比例的乙二醇和较高官能度的多元醇与二羧酸或多羧酸缩合而制得的聚酯。还有另一类合适的聚合多元醇，包括羟基封端的聚硫醚、聚酰胺、聚酰胺酯、聚碳酸酯、聚缩醛、聚烯烃和聚硅氧烷。拟用于烃发泡体系的特别优选的异氰酸酯反应性化合物是胺引发的聚醚多元醇，尤其是芳香胺引发的多元醇。如TDA-和DADPM引发的聚醚多元醇，正如在WO97／48748中所叙述的那些，该专利的内容并入本文作为参考。
用于本发明方法的合适的有机多异氰酸酯包括本领域中用以制造聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料已知的那些多异氰酸酯中的任何一种，尤其是芳族多异氰酸酯如以其2，4＇-、2，2＇-和4，4＇-异构体及其混合物形式提供的二苯甲烷二异氰酸酯；二苯甲烷二异氰酸酯(MDI)与其低聚物的混合物，该低聚物在本领域中称之为“粗的”或聚合的MDI(多亚甲基多亚苯基多异氰酸酯)，其异氰酸酯的官能度大于2；以其2，4-和2，6-异构体及其混合物形式提供的甲苯二异氰酸酯；1，5-亚萘基二异氰酸酯；以及1，4-亚苯基二异氰酸酯。可以提及的其它有机多异氰酸酯包括脂族二异氰酸酯，如异佛尔酮二异氰酸酯、1，6-己烷二异氰酸酯和4，4＇-二环己基甲烷二异氰酸酯。
多异氰酸酯组合物和要与之反应的多官能团异氰酸酯反应性组合物的用量取决于所要制造的聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料的性质，而这一点对于本领域的技术人员来说是很容易作出决定的。
用于制造聚氨酯硬泡沫塑料的已知的其它物理发泡剂也可与本发明的烃发泡剂混合物一起使用。这些物理发泡剂的实例包括其它的烃类、二烷基醚类、环亚烷基醚类和酮类、氟代醚类、含氯氟烃类、全氟烃类，以及尤其是含氢氯氟烃类和含氢氟烃类。
合适的含氢氯氟烃类的实例包括1-氯-1，2-二氟乙烷、1-氯-2，2-二氟乙烷、1-氯-1，1-二氟乙烷、1，1-二氯-1-氟乙烷和一氯二氟甲烷。
合适的含氢氟烃类包括1，1，1，2-四氟乙烷、1，1，2，2-四氟乙烷、三氟甲烷、七氟丙烷、1，1，1-三氟乙烷、1，1，2-三氟乙烷、1，1，1，2，2-五氟丙烷、1，1，1，3-四氟丙烷、1，1，1，3，3-五氟丙烷和1，1，1，3，3-五氟正丁烷。
通常将水或其它释放二氧化碳的化合物与所说的这些物理发泡剂一起使用。当使用水作为化学助发泡剂时，其用量一般为以异氰酸酯反应性化合物为基准计的0．2～5wt％，优选为0．5～3wt％。
在制造发泡聚合物材料的反应体系中所要用的发泡剂总量，由本领域的技术人员很容易做出决定，而一般为以反应体系总重量为基准计的2～25％。
除了多异氰酸酯和多官能团异氰酸酯反应性组合物及发泡剂混合物之外，制造泡沫塑料的反应混合物中一般还包含一种或多种在制造聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料配方中常用的助剂或添加剂。这类任选的添加剂包括交联剂如三乙醇胺之类的低分子量多元醇、泡孔稳定剂或表面活性剂如硅氧烷-氧化烯共聚物、氨基甲酸酯催化剂如辛酸锡或二月桂酸二丁基锡之类的锡化合物或二甲基环己基胺或三亚乙基二胺之类的叔胺、异氰酸酯催化剂、阻燃剂如磷酸三氯丙基酯之类的磷酸卤代烷基酯以及碳黑之类的填料。
在按照本发明方法制造硬泡沫塑料的操作中，可以将已知的一步发泡法、预聚物或半预物技术与常规的混合法结合起来使用，而硬泡沫塑料则可以制成板材、模塑件、空腔填充料、喷涂泡沫体、发泡泡沫体或包含诸如硬纸板、石膏板、塑料、纸张或金属等其它材料在内的层压板材。
在许多应用领域中方便的做法是，在以基于初级多异氰酸酯和异氰酸酯反应性组分各自的预混配料的形式为聚氨酯的生产提供各种组分。具体来说，许多反应体系都采用一种含有除了多异氰酸酯反应性组分或其多种组分之外的如发泡剂之类的主要添加剂的多异氰酸酯反应性组合物。
因此，本发明还提供了一种包含本发明发泡剂混合物的多异氰酸酯反应性组合物。
本发明用以下实施例加以说明，但不受这些实施例的限制。
实施例1～5
用含有下表1中所列各组分的聚氨酯配料填充冰箱内胆。
多元醇是一种OH值为390mg KOH／g的多元醇组合物；异氰酸酯是聚MDI组合物。
以乳白期(反应混合物开始发泡所需的时间)和拉丝时间(反应混合物由流体达到交联体的转变点所需的时间)来跟踪反应进程。
按照ISO845标准测定了泡沫塑料的自由起发密度。
流动指数的测定方法如下：将一定重量的参比泡沫塑料配料在一个特别管中流动的高度设定为1．00；再将相同重量的样品泡沫塑料配料在该相同管中流动的高度加以测定并同该参比泡沫塑料配料的高度进行比较。环戊烷发泡的泡沫塑料(实施例1)取作参比泡沫塑料。
按照ASTM C518方法测定了10℃下的λ值。
用目测法测定泡沫塑料的发泡程度。
填充重量表示填充有泡沫塑料的冰箱内胆与未填充的冰箱内胆之间的重量差，并对一个厚壁的且具有简单气流循环方式的型号1的单体积冰箱和一个具有复合气流循环方式的组合型的型号2的冰箱测定了该填充重量。
反向热泄漏决定了当达到稳定态(能量损失)率时通过冰箱内胆的能量损失(热传导)。其测量方法如下：对一个关闭的且调控好的冰箱内胆接通电源；从其内、外表面上形成热流；当确立起一种稳定状态(热平衡)之后，测定所消耗的功率；RHL值就是为保持内、外部预定温差(此时所用的温差为20℃)所需消耗的功率(以瓦特为单位)。在表1中，样品泡沫塑料的RHL是相对于参比泡沫塑料(实施例1)来表示的，后者的RHL设定为100。只对型号1的冰箱测定了其RHL值。
测定结果列示于下表1中。
表1
| 实施例序号 | 1 | 2 | 3 | 4 | 5 | |
| 多元醇 | 重量份 | 100 | 100 | 100 | 100 | 100 |
| 水 | 重量份 | 2.1 | 2.1 | 2.1 | 2.1 | 2.1 |
| 环戊烷 | 重量份 | 15 | 10.5 | 10.5 | 10.5 | 10.5 |
| 异戊烷 | 重量份 | 4.5 | 2.0 | 1.0 | ||
| 异丁烷 | 重量份 | 3.5 | 1.5 | 2.5 | ||
| 异氰酸酯 | 重量份 | 144 | 144 | 144 | 144 | 144 |
| 乳化时间 | 秒 | 4 | 4 | 3 | ||
| 拉丝时间 | 秒 | 38 | 37 | 38 | 37 | 38 |
| 自由起发密度 | kg/m3 | 23.2 | 22.5 | 22.7 | 22.9 | 22.7 |
| 流动指数 | 1.00 | 1.15 | 1.06 | 1.12 | 1.08 | |
| λ | mW/mK | 20.0 | 20.3 | 20.8 | 20.3 | 20.5 |
| 发泡程度 | 无 | 无 | 重度 | 无 | 轻度 | |
| 填充重量 | ||||||
| 型号1 | g | 3300 | 3000 | 2900 | 3000 | 3000 |
| 型号2 | g | 6600 | 6000 | 6000 | 5800 | 5900 |
| 反向热泄漏 | ％ | 100 | 101 | 104 | 101 | 103 |
表中结果表明，采用按照本发明的发泡剂混合物发泡的泡沫塑料(实施例4和5)较之仅用环戊烷(实施例1)发泡的泡沫塑料具有更低的密度；此外，本发明的泡沫塑料配料的流动性获得改善，从而导致较低的冰箱填充重量。与采用环戊烷／异戊烷混合物(实施例2)发泡的泡沫塑料相比，本发明的泡沫塑料也获得较低的填充重量。
与采用环戊烷／异丁烷混合物发泡的泡沫塑料(实施例3)相比，本发明的泡沫塑料配料也获得较好的流动性(较低的填充重量，尤其是对于复合型冰箱而言更为明显)和较好的绝热性能(λ和能量消耗)。
Claims (8)
1．制造聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料的方法，该方法包含使一种有机多异氰酸酯与一种多官能团异氰酸酯反应性组分在一种发泡剂混合物存在下进行反应的步骤，该发泡剂混合物包含50～90wt％的环戊烷和10～50wt％的异戊烷和／或正戊烷与异丁烷和／或正丁烷的混合物，其中异戊烷和／或正戊烷对异丁烷和／或正丁烷的重量比为5／95～95／5。
2．按照权利要求1的方法，其中在发泡剂混合物中环戊烷的含量为60～80wt％，而异戊烷和／或正戊烷与异丁烷和／或正丁烷混合物的含量为20～40wt％。
3．按照权利要求1或2的方法，其中异戊烷和／或正戊烷对异丁烷和／或正丁烷的重量比为75／25～25／75。
4．按照权利要求3的方法，其中异戊烷和／或正戊烷对异丁烷和／或正丁烷的重量比为2／1～1／2。
5．按照前述权利要求中任何一项的方法，其中所说的发泡剂混合物包含环戊烷、异戊烷和异丁烷。
6．按照权利要求5的方法，其中所说的发泡剂混合物选自下列混合物：由70wt％环戊烷、20wt％异戊烷、10wt％异丁烷构成的混合物，由70wt％环戊烷、10wt％异戊烷、20wt％异丁烷构成的混合物，由75wt％环戊烷、15wt％异戊烷、10wt％异丁烷构成的混合物。
7．按照前述权利要求中任何一项所规定的方法制得的聚氨酯或氨基甲酸酯改性的聚异氰脲酸酯硬泡沫塑料。
8．包含权利要求1～6中任何一项所定义的发泡剂混合物的异氰酸酯反应性组合物。
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| CN110343227A (zh) * | 2019-08-09 | 2019-10-18 | 南京红宝丽聚氨酯有限公司 | 一种超低密度的硬质聚氨酯泡沫及其制备方法 |
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| CN110343227A (zh) * | 2019-08-09 | 2019-10-18 | 南京红宝丽聚氨酯有限公司 | 一种超低密度的硬质聚氨酯泡沫及其制备方法 |
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| CA2318300A1 (en) | 1999-09-02 |
| KR20010041256A (ko) | 2001-05-15 |
| NZ505756A (en) | 2002-02-01 |
| ID25632A (id) | 2000-10-19 |
| BR9908189A (pt) | 2000-10-24 |
| TR200002470T2 (tr) | 2001-01-22 |
| AU2620699A (en) | 1999-09-15 |
| WO1999043742A1 (en) | 1999-09-02 |
| US20010014703A1 (en) | 2001-08-16 |
| JP2002504609A (ja) | 2002-02-12 |
| AR018565A1 (es) | 2001-11-28 |
| SK12712000A3 (sk) | 2001-02-12 |
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