CN1126138A - 用作保温材料的开孔硬质聚氨酯泡沫塑料的制造方法 - Google Patents

用作保温材料的开孔硬质聚氨酯泡沫塑料的制造方法 Download PDF

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CN1126138A
CN1126138A CN95105536A CN95105536A CN1126138A CN 1126138 A CN1126138 A CN 1126138A CN 95105536 A CN95105536 A CN 95105536A CN 95105536 A CN95105536 A CN 95105536A CN 1126138 A CN1126138 A CN 1126138A
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R·韦尔特
H·-J·索尔
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Abstract

通过对闭孔或部分闭孔的硬质聚氨酯泡沫塑料施加外压来制造完全开孔的硬质聚氨酯泡沫塑料。这些开孔泡沫塑料可用作保温板的填充材料或用作保温泡沫塑料。

Description

用作保温材料的开孔硬质聚氨酯
泡沫塑料的制造方法
本发明涉及制造开孔硬质泡沫塑料的新方法以及它们作为真空保温装置的填充材料和气密、闭合、充气的泡沫塑料的应用。
由于人们对氯氟烃(CFCs)的关注日益增加，最近的文献中报道了一些制造开孔硬质聚氨酯泡沫塑料的方法。新的保温材料和技术正在探索和试验之中。
EP-A0,188,806描述了用于制造真空镶板的开孔硬质聚氨酯泡沫塑料，它是由特定的异氰酸酯与特定的多元醇连同特定的稳定剂、开孔剂和作为发泡剂的一氟三氯甲烷(R11)反应制备的。因为据信R11会破坏大气的臭氧层，所以EP-A0,581,191公开了用HCFC(即一种含氢的氯氟烃)或二氯甲烷作发泡剂制造开孔硬质聚氨酯泡沫塑料的方法。
不用发泡剂制造开孔硬质聚氨酯泡沫塑料的方法也已在探索之中。
对于仅有空气成分的气体(如氧、氨或二氧化碳)释放到大气中的方法也进行了研究。这种方法之一公开于EP-A0,567,027中。在EP-A0,567,027中发泡剂是由水产生的CO2。但是，即使是用所公布的特定配方，得到的开孔率仅有90-96％。
但是，正如EP-A0,581,191所述(见第3页)，这些值完全不适用于真空镶板技术。含有少量残留气体的真空板随着气体的扩散最终将失去高真空。
本发明的一个目的是提供一种完全开孔的硬质聚氨酯泡沫塑料的制造方法。
本发明另一个目的是提供一种由常规的硬质聚氨酯泡沫塑料制造开孔的硬质泡沫塑料的方法。
本发明的再一个目的是提供一种由全部或部分闭孔或甚至基本上开孔的硬质泡沫塑料制造完全开孔的硬质聚氨酯泡沫塑料的方法。
本发明的再一个目的是提供一种不限定具体原料或具体助剂的制造完全开孔的硬质聚氨酯泡沫塑料的方法。
本发明还有一个目的是提供特别适用于制造保温板和保温泡沫塑料的完全开孔的硬质聚氨酯泡沫塑料。
这些和其它一些对本领域技术人员来说显而易见的目的是通过对有闭孔的硬质聚氨酯泡沫塑料施加外压来达到的。
本发明涉及完全开孔的硬质聚氨酯泡沫塑料的制造方法。在这个方法中，通过施加外压将闭孔或部分闭孔的硬质聚氨酯泡沫塑料转变成开孔的硬质聚氨酯泡沫塑料。这里所用的术语“完全开孔的”意指开孔率大于96％，相应于确定开孔率的方法的精确度内的完全开孔的情况。
在本发明的一个优选实施方案中，作为本发明方法的原料的闭孔或部分闭孔的硬质聚氨酯泡沫塑料是在模具中按本领域技术人员熟知的任何模制技术制造的。模具壁最好能对模具中的闭孔硬质泡沫塑料形成一个气密阻隔层(如膜或涂层)。通过施加外部压力将仍然在模具中的泡沫塑料的闭孔打开。
本发明也涉及用本发明的方法制造的开孔硬质聚氨酯泡沫塑料。这些开孔硬质泡沫塑料特别适合用作真空保温板的填充材料，当它们在抽空(即打开泡沫塑料的孔壁)前涂敷了一层由塑料或金属制成的气密膜、或由塑料以及金属的复合膜或玻璃或陶瓷材料制成的气密膜时尤为如此。
本发明的泡沫塑料也可用作耐收缩的保温泡沫塑料；当泡沫塑料的闭孔被打开后充入比空气重的保温气体(优选实际上不溶于泡孔材料的重保温气体)后可作为气密保温板的填充材料；作为保温材料用于冰箱、冷藏车、冷冻箱、冷冻车、容器、冷冻货柜、冷藏柜、热水容器和用于工业建设和配热系统的容器。
本发明也涉及一种真空保温板，它由下列物质组成：a)按本发明得到的开孔硬质聚氨酯泡沫塑料和b)由b1)塑料或金属或由b2)塑料及金属的复合膜或b3)玻璃组合物或b4)陶瓷组合物构成的气密性涂膜。
本发明还涉及一种填充有比空气重的保温气体的保温板，它由下列物质组成：a)通过对闭孔的硬质泡沫塑料施加外压制得的开孔硬质聚氨酯泡沫塑料和b)由b1)塑料或金属或由b2)塑料及金属的复合膜或b3)玻璃组合物或b4)陶瓷组合物构成的气密性涂膜。
令人非常惊奇的是，在按本发明进行压力处理时泡沫塑料并不破裂。对闭孔硬质泡沫塑料施加外压仅仅造成由于孔壁开裂而形成的所需的完全开孔。这就是说，孔壁仍然存在，但是这些孔壁因开裂而开通。
与本发明相反，在制造开孔聚氨酯泡沫塑料的先有技术方法的最后阶段，孔壁通过“吹除”被破坏。
用不同方法制造的开孔泡沫塑料的保温性能有很大差别。如果孔壁只是通过开裂而开通(例如本发明的情况)，孔内气体的有效自由路程长度主要限于孔的直径范围。这种自由路程长度限制可以改进保温效果。这种改进的保温效果使本发明的泡沫塑料尤其适用于真空镶板技术。
如果本发明的开孔硬质聚氨酯泡沫塑料的孔内充有重气体(即比空气重的气体)，如重稀有气体、有机挥发性气体、CFC或碳氟化合物，它们也可用作处在常压或高真空和常压之间的绝热板中的保温材料。
因为CFC发泡剂通过扩散或在器具毁坏或处理时进入大气，所以在常规的保温材料中不再使用。但是，CFCs用于具有气密的外涂层的开孔泡沫塑料却没有这种问题，因为CFCs不会扩散到大气中并且在处理时可通过抽空而容易地排出。
用于制造含至少一些闭孔的硬质聚氨酯泡沫塑料的本专业技术人员所熟知的任何原料都可用来制造用于本发明的实施的闭孔泡沫塑料。制造闭孔硬质聚氨酯泡沫塑料的方法和材料公开于例如《合成塑料手册))，VII卷“聚氨酯”，G.Oertel编(出版商Carl Hanser，Munich，1993)，第267页。
用作实施本发明的原料的闭孔或部分闭孔的硬质泡沫塑料通常的松密度在约20至约200kg/m3的范围内，优选为约30至约100kg/m3。
在本发明中通过施加外压(例如在压力室中)将闭孔硬质泡沫塑料转变成相应的完全开孔的硬质聚氨酯泡沫塑料。所施压力的大小和施压时间取决于所用的具体闭孔硬质泡沫塑料。施加压力的大小和持续时间可通过简单的预备实验很容易确定。通常，压力为约2至约20巴，时间为约1至约60秒是足够的。
在描述了本发明以后，通过下面的实施例进一步说明本发明。除非另有说明，实施例中所有的份数和百分数均是重量份和重量百分数。
实施例1
将松密度为50kg/m3、闭孔百分数大于90％(DIN-ISO 4590)的常规硬质聚氨酯泡沫塑料置于1巴的超压下5秒钟。然后测定开孔百分数，所得值大于96％，这个值在测定开孔率所用方法的精度范围内相应于完全开孔的情况。将停留时间延长至10秒、2分钟、10分钟或30分钟，所得泡沫塑料的开孔度相同。
实施例2
将与实施例1相同的泡沫塑料置于10巴压力下，对于第一个试样，压力的增加在5秒钟内完成，第二个试样在2分钟内完成，第三个试样在30分钟内完成。三个试样的开孔率相同，均在96％以上。
实施例3
将松密度为24kg/m3和34kg/m3、闭孔率大于90％的常规硬质泡沫塑料在5秒钟内加压至10巴，并保压10分钟。每种泡沫塑料的开孔率均在96％以上。
虽然为了说明的目的，前面已对本发明作了详细的描述，但是应该理解，这种详述只是为了说明的目的，本领域技术人员可在权利要求所限的范围内，在不偏离本发明的精神实质和范围的情况下进行各种变动。

Claims (8)

1.一种制造完全开孔的硬质聚氨酯泡沫塑料的方法，该方法包括对闭孔或部分闭孔的硬质聚氨酯泡沫塑料施加外压。
2.权利要求1的方法，其中在施加外压时闭孔或部分闭孔的硬质聚氨酯泡沫塑料处在模具内。
3.权利要求2的方法，其中在施加外压前使闭孔泡沫塑料具有气密阻隔层。
4.一种真空保温板，其制法如下：
a)对闭孔或部分闭孔的硬质聚氨酯泡沫塑料施加外压，形成开孔的硬质聚氨酯泡沫塑料，
b)用一种使开孔泡沫塑料不透气的材料涂敷a)中制成的开孔泡沫塑料。
5.一种制造气密性保温板的方法，该方法包括：
a)抽空权利要求4的保温板
b)将一种比空气重的气体充入真空板中。
6.权利要求5的方法，其中保温气体相对来说不溶于制备保温板的开孔泡沫塑料。
7.权利要求6的方法，其中用来制造保温板的涂敷材料选自塑料、塑料复合物、金属、金属复合物、玻璃组合物和陶瓷材料。
8.权利要求4的保温板，其中用于涂敷开孔硬质泡沫塑料的材料选自塑料、塑料复合物、金属、金属复合物、玻璃组合物和陶瓷材料。
CN95105536A 1994-05-27 1995-05-26 用作保温材料的开孔硬质聚氨酯泡沫塑料的制造方法 Pending CN1126138A (zh)

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CN108506646A (zh) * 2017-02-28 2018-09-07 芜湖美的厨卫电器制造有限公司 保温型材及热水器
CN111491799A (zh) * 2017-11-28 2020-08-04 陶氏环球技术有限责任公司 基于聚氨酯的隔热板
US11486135B2 (en) 2017-11-28 2022-11-01 Dow Global Technologies Llc Glass fiber-reinforced polyurethane/polyisocyanurate foam insulation board

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CN108506646A (zh) * 2017-02-28 2018-09-07 芜湖美的厨卫电器制造有限公司 保温型材及热水器
CN108506646B (zh) * 2017-02-28 2024-04-26 芜湖美的厨卫电器制造有限公司 保温型材及热水器
CN111491799A (zh) * 2017-11-28 2020-08-04 陶氏环球技术有限责任公司 基于聚氨酯的隔热板
US11486135B2 (en) 2017-11-28 2022-11-01 Dow Global Technologies Llc Glass fiber-reinforced polyurethane/polyisocyanurate foam insulation board
CN111491799B (zh) * 2017-11-28 2023-05-12 陶氏环球技术有限责任公司 基于聚氨酯的隔热板
US11745465B2 (en) 2017-11-28 2023-09-05 Dow Global Technologies Llc Polyurethane-based insulation board

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KR950032398A (ko) 1995-12-20
HU216068B (hu) 1999-04-28
CZ290983B6 (cs) 2002-11-13
SI0685512T1 (en) 2000-10-31
US5698601A (en) 1997-12-16
BR9502564A (pt) 1996-03-05
CA2149851A1 (en) 1995-11-28
PT685512E (pt) 2001-01-31
DE4418507A1 (de) 1995-11-30
EP0685512A1 (de) 1995-12-06
ES2151003T3 (es) 2000-12-16
JPH0859879A (ja) 1996-03-05
DE59508635D1 (de) 2000-09-21
CZ135695A3 (en) 1995-12-13
ATE195542T1 (de) 2000-09-15
EP0685512B1 (de) 2000-08-16
DK0685512T3 (da) 2000-10-23
HU9501545D0 (en) 1995-07-28
KR100349270B1 (ko) 2002-11-01

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