CN102179972A - 发泡聚合物的防火*** - Google Patents

发泡聚合物的防火*** Download PDF

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CN102179972A
CN102179972A CN2011100264326A CN201110026432A CN102179972A CN 102179972 A CN102179972 A CN 102179972A CN 2011100264326 A CN2011100264326 A CN 2011100264326A CN 201110026432 A CN201110026432 A CN 201110026432A CN 102179972 A CN102179972 A CN 102179972A
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fire
glass fibre
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insulation
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H·匡特
F·维尔梅耶
J·韦丁格
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Armacell Enterprise GmbH and Co KG
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Armacell Enterprise GmbH and Co KG
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Abstract

本发明涉及发泡聚合物的防火***，用于防燃目的的通用多层(A)(B)涂层***，特别用于保护发泡有机聚合物(C)，改善阻燃性质，降低产烟量，还涉及制造该***的方法、该***在基材方面的应用、该***的用途和所得复合物。

Description

发泡聚合物的防火***
技术领域
本发明涉及用于防燃和消烟目的的通用多层涂层***，特别用于保护发泡有机聚合物，改善阻燃性质，降低产烟量，还涉及制造该***的方法、该***在基材方面的应用、该***的用途和所得复合物。
背景技术
基于有机物的发泡或多孔高分子结构在很多应用领域，如温度梯度绝缘、噪声防护、振动衰减、轻型结构等中具有重要作用。然而，由于它们的有机性质，即表示可燃性，阻燃性和与此相关的问题一直阻碍将有机泡沫和海绵用于可燃性、火焰扩张和产烟可能成问题的任何用途从而拓宽其适用性。特别是产烟和烟密度是近年来讨论的问题。已为改善聚合物本身的阻燃性作出了很多努力，然而这些方法例如采用阻燃剂、不可燃填料等仅具有延迟作用而并不具有完全防止作用，甚至可严重影响聚合物的膨胀或发泡以及所需应用的其它最终性质；此外，只要出现真正的燃烧和/或跳火(温度会很容易持续超过900℃)，无论放入多少阻燃剂，有机聚合物都会继续燃烧，说到有机泡沫的泡沫泡孔内一直存在加速燃烧的氧气时，情况甚至更糟，且泡孔壁很薄，易受到攻击并分解。因此，已作了一定工作在发泡聚合物着火前对其进行保护，即避免其在可能发生火灾的一侧也就是发泡产物的表面上着火。非常关心可燃性问题的领域是电缆和建筑工业，而大部分检查也确实在这些应用领域中实施。可想到的有用特别的防燃聚合物形成外层的复合物，例如JP 2002167886、US 6066580或GB2122232所述，但最普遍的防火方法是采用由金属箔或板组成的外层，其中由于适用性和成本问题大多采用铝，常结合一个或多个不可燃或可燃性低的内层。以下专利对该技术的各种应用已达到几乎穷尽的程度：GB 2174335(用刚性泡沫填充的铝蜂窝结构)、GB 2161655(其下带有矿棉的金属箔)、EP 91255(箔层，其下是金属丝网)、GB 1454493、US 4292369和US 4296170(各种外箔)、DE 19815933(多孔箔，其下是纤维)、JP 2003055622和JP 11293894(结合发泡***的箔)。大部分发明人要求保护金属箔或板连同纤维(织造或非织造)的用途，其中纤维有时是如JP 200677551、JP4347252和CN 2557778(铝/聚酯或聚酰胺)中的低可燃性纤维，但大多是不可燃纤维：JP 9177200、JP 8199709、JP 2043034、JP 10034786、JP 1261588、KR 102006022043、KR 102004065138、KR 100517732、EP 2116753、CN201236395、US 4459334、US 4204019、US 4292361(均采用金属(Al)箔作为最外层，其下是(玻璃)纤维)，以及US 20030077419(带孔的箔，纤维)。以下专利也要求保护所述铝/纤维材料的组合，在JP 2002023763中用于隔音目的；在例如US 4937125、JP 2215521、GB 1110579和GB1128611中用于热绝缘；在FR 2792667和GB 1243136中同时用于以上两种目的；KR 102006115089要求保护单层铝箔用于防水；然而上述情况中并未均将燃烧性能作为目标。其它发明人要求保护低可燃性纤维(例如，JP 2008201079、JP 80868164、CN 200992175)或不可燃纤维(主要是玻璃纤维)仅作为外层的用途，有时结合其它层，如例如GB 882296(玻璃纤维涂层)、EP 778634(纤维在基质中，内层低可燃性材料)、DE 19815933和SE 514501(无机纤维层，部分用不可燃物质填充)、JP 10115045(不可燃纤维和竹层)、JP 8277586(纤维在泡沫填充蜂窝结构上)、GB 1386254(纤维增强外树脂层)、DE 102006055377和DE 19809973(纤维/箔在发泡层上)所述。US 4025686、US 4073997、US 4118533和其它专利要求保护作为外层的玻璃纤维，GB 1213010要求保护多个纤维层建造结构的用途，但二者并未均明确将燃烧性能作为目标。CN 1613640提到了浸渍阻燃剂的双毛毡层；DE 19640887要求保护用于防火目的的纤维增强硅酸盐层。所有这些方法确实包括大量关于阻燃性的要求，然而，其个体通用性有限，且其性能强烈依赖于基材、如何施涂所述层等。因此，大部分上述发明也要求或至少提到基材本身的阻燃性。建筑工业内的要求和可燃性测试相关的批准越来越全球化，但由于除可燃性外还考虑到产烟和烟密度，其也变得更精确并更具有应用相关性，因此更具有挑战性(例如ASTM E-84和EN13823)。相应地，我们在研究过程中发现，上述现有技术不适合安全达到有机物可能的最高阻燃等级(例如EN 13823/EN 13501-1的BS 1和UL 94的V-0等)，甚至不适合最普遍的聚合物发泡基料，在一些情况中，这些***甚至会导致性能更差(参见表1)。性能较好的***(例如至少分别达到BS 3或V-1等级)价格昂贵、复杂、不具有经济或生态方面的优势。上述材料通常的缺陷在于，采取的阻燃措施将引起不完全燃烧，由此烟中所含的颗粒可导致高烟密度以及部分高产烟量。以下是传统防火***失效的其它原因。一些现有技术并不基于传统***：KR 102006021127公开了铝箔层上具有保护聚合物层的复合物，而该铝箔层本身位于泡沫之上，然而，并未要求保护该***的防火性能，由于所述聚合物太容易燃烧，会不符合各自的要求。CH 650196描述了一种据称具有阻燃性的有趣的复合物，其中铝箔经穿孔且是第二层，由含阻燃剂的聚酯纤维外层涂覆。此外，以上提到的JP 8199709描述了金属箔不一定是最外层的***。然而，根据我们的研究，这些非典型***在灼烧度测试结果的一致性、再现性和适用性方面显示出缺陷。例如，JP 8199709正确地描述了含阻燃剂的缓慢燃烧的外层会借助其下的铝导体分散燃烧热，然而我们发现，从某个时间点开始，该分散能力出现饱和，金属层的过热会造成不希望出现的外层和基材的跳火，引起所述箔周围复合物的完全燃烧。CH 650196提到的复合物会在略迟的时间点显示该作用，但也会造成跳火的结果。这里跳火延迟的原因是由于所述箔的多孔结构能使热甚至分散到基材中，但并未达到形成可燃性气体的临界水平。最终，GB 2222185关于第一层可熔化而不燃烧将具有保护功能的正确假设在用于上述测试方法和批准时显示无效，因为熔化层会最终自发起火。此外我们观察到，在所有三种情况中，跳火之前和之后都明显产生黑的和/或浓的烟，这不利于批准。
发明内容
本发明的主要目的是提供通用、可靠、经济、易于应用和在各应用领域满足现代法规的防火***，其在火焰达到或转移至泡沫基材之前尽可能分散火焰及其热，从而以可能的最佳方式抑制烟形成。
令人惊奇的是，发现当改变现有技术***并采用玻璃纤维作为最外层，将金属箔层置于其下，或在第二玻璃或低可燃性到不可燃纤维层上采用玻璃纤维层来获得不显示上述缺点的此类通用材料，二者均具有适当的火焰扩散和热分散性质以及适当的透气性，但不透过固体烟颗粒的适当性质。
具体实施方式
参见图1，要求保护的材料包含复合体(A)，其为作为最外层即外保护层的至少一个玻璃纤维层，施涂在可能接触到火的基材的所有表面上，但至少施涂在例如平面基材如建筑和绝缘面板的一侧。所述玻璃纤维可以是可市售获得的任何种类的玻璃纤维，然而优选经非有机处理(例如基于硅烷)的玻璃纤维，因为广泛用于纱和纺织工业的有机加工助剂(如硬脂酸、动植物脂肪和油等)可对可燃性产生负面影响。所述纤维可以是织物或非织造状态。优选单向编织的薄纱网(tissue mesh)，因为其具有较好限定的渗透/网目尺寸，并具有提供表面强度和良好的内外部结合的机械性质。优选的薄纱的网目尺寸是0.01-0.80mm，特别优选0.04-0.25mm；优选的丝密度(thread density)是5-250根丝/厘米，特别优选20-60根丝/厘米。
参见图1，要求保护的材料还包含作为第二最外层即内保护层的复合体(B)，所述第二最外层为至少一层无孔金属箔，优选铝，因为其具有良好的导热性、良好的密封性和极佳的应用性质(结合/粘合、相容性等)，其中所述箔的优选厚度是1-400微米，特别优选2-50微米，或所述第二最外层为不可燃的纤维，如玻璃纤维或矿物纤维，或可燃性低的纤维，如聚芳酰胺、阻燃性聚酰胺或阻燃性聚酯组成的至少一层。优选经无机处理的玻璃纤维，特别优选如织物等纤维。优选的薄纱网目尺寸是0.01-0.80mm，特别优选0.08-0.5mm；优选的丝密度是5-250根丝/厘米，特别优选40-100根丝/厘米。
参见图1，要求保护的材料在(A)和(B)下面包含基材复合体(C)，其由至少一层处于交联或未交联状态的发泡聚合物组成，例如但并不仅是热塑性材料(例如，聚烯烃、聚酯包括聚氨酯和PET/PBT、聚醚等)、热固性材料(树脂，例如基于酚、丙烯酸、三聚氰胺等的树脂)、热塑性弹性体(包括PVC、PUR)、弹性体(主链仅包含碳，或还包含氧、硅等，例如，BR、SBR、NBR、IIR、ACM/AEM、FPM/FKM、EPM/EPDM、ECO、Q等)、胶乳等的有机泡沫和海绵(即开放泡孔和封闭泡孔的泡孔聚合物)。所述基材(C)可由上述一种或其任何组合组成。形成(C)的一种或多种基材复合体包含填料、纤维、交联***、增塑剂、稳定剂、着色剂、发泡剂等以及用于橡胶和塑料工业中的其它添加剂的任何组合，其可作为多个不同的材料层或由材料掺混物组成的一个层存在，即，(C)可由至少一个发泡层、零到多个发泡和未发泡层组成。
参见图1，要求保护的材料包含适合粘合的***(D)以将复合体(A)、(B)和(C)分别相互结合。粘合***优选与所述基材完全相容以确保良好的结合(表示基于基材聚合物化合物或与之相容的化合物)，或具有固有阻燃性。特别优选包含卤化或磷化合物的粘合剂，例如基于如氯丁二烯、PVC等的弹性体。所述粘合***(D)分别结合层(A)和层(B)或层(B)和层(C)的组成不必相同，可进行自由选择以可能的最佳方式符合个体要求。
参见图1，要求保护的材料还可在(B)和(C)之间包含额外的功能层(E)，其可有利于所需应用必需的机械强度以及阻燃剂性质。因此，用于(E)的复合体可以是各种形式的例如纤维、箔、纸、薄片等，但也可以是自陶瓷化、结焦或发泡化合物或在起火时释放阻燃、冷却或稀释物质如气体、蒸汽、液体、卤化物等的化合物。所述复合体(E)可通过(D)与所述材料的其它复合体结合或发生自身粘合。
参见图1，要求保护的材料还可包含涂覆在(A)上的额外功能层(F)以发挥例如防护、增强的作用或作为装饰层。优选本身具有阻燃性或易于燃烧或熔化，以免干扰(A)(B)(C)层***发挥作用。所述复合体(F)可通过(D)与所述材料的其它复合体结合或发生自身粘合。
参见图1，要求保护的材料还可包含所需应用必需的任何额外的元件(G)，如在电缆等情况中的金属丝嵌入物，用于建筑目的的木质、玻璃、金属或混凝土结构的大块部件。所述复合体(G)可通过(D)与所述材料的其它复合体结合或发生自身粘合。
要求保护的材料的主要优点是其适用于要求低火焰扩张和/或低产烟量的“火临界(fire critical)”应用(例如ASTM E-84和EN 13823/EN 13501-1，参见表1)。根据我们的结果，可燃性气体形成和迁移连同火焰分散和热分散后，要求保护的材料的诸层的特殊作用提供从阻燃到甚至防火的效果：
1.在火焰袭击织物的第一层时，火焰在高表面上分散，因此单位表面上产生的净热量与光滑和/或封闭表面如箔或薄片相比显著降低。由于存在所述分散，穿透到复合物中的热量也较低，但也是因为所述纤维与金属箔或聚合层相比较低的导热率。
2.在靠近第二层时，已变弱的热和火焰会：
a.被金属箔反射，或被第二织物层进一步分散。如果热更深地穿透到所述复合物的泡沫部分中，产生的可燃性气体会被所述箔截留(外纤维层可防止气压引起箔撕裂，这同样是现有技术未提供的现象)，由此避免可能发生的跳火；
b.或者，第二织物层会延缓这些气体移动到表面或火焰前缘。
效果2a和2b均会防止跳火，结合效果1会形成受控的缓慢燃烧(缓慢，但提供充足的氧)，其与标准阻燃剂***相比不会产生很多烟，而标准阻燃剂***会引起“抑制”燃烧(氧不充足)，伴有不完全燃烧造成的产烟量高(比较表1：SMOGRA和TSP值，表2：由应用要求保护的***改进的SMOGRA值)。
要求保护的材料的一个非常显著的优点是其关于灼烧度测试和结果的通用性几乎不依赖于基材(参见表2)。
要求保护的材料与上述优点相关的另一个优点是不必采取其它措施以使基材具有阻燃性(参见例如表2中的PET)。
这形成要求保护的材料的又一个优点，即自由、经济以及生态性地选择泡沫基材及其成分。
这形成要求保护的材料的另一个优点，因为不需要卤化阻燃剂来达到所需的耐火性。特别是溴化阻燃剂能造成危险的环境问题，其在起火时可产生有毒的烟。因此，溴化阻燃剂早已部分禁止。
要求保护的材料的另一个优点是其优选的组合物中不含纤维和PVC，此二者正处于调查阶段和有关环境和健康问题的讨论中。
要求保护的材料的另一个优点是其阻燃性几乎不依赖要防火部分的几何学特征。
要求保护的材料的另一个优点是可通过改变箔厚度和/或纤维直径、长度、薄纱密度、编织角等使其性质适应于所需的性质概况(关于机械、衰减、绝缘、操作弹性等)。
要求保护的材料的一个显著优点是其可以经济的方式在连续过程例如挤出和共层压过程中进行生产。其在制造和应用的可能性方面显示出通用性。可将其直接挤出、共挤出、层压、模塑、共模塑、重叠注塑(overmould)、焊接等而成为多层***，由此可采用无限制成型(unrestricted shaping)将其施涂于各种表面，用于汽车、运输、航空、建筑和施工、家具、机械工程和很多其它工业中，甚至可在所述材料制造过程之后采用热成型或其它成型方法。
要求保护的材料的另一个优点是其可通过工业中普遍采用的标准方法进行转变和成型，并不需要特定设备。
所述材料的另一个优点是复合体(C)可包含同种或其它材料的废料或再循环材料，且很高程度上并没有损失其阻燃性质(参见表2)。
要求保护的材料的另一个优点是其温度范围宽，仅由所述发泡聚合物决定。例如，具有发泡硅氧烷弹性体作为复合体(C)的要求保护的材料可在-100℃到最高+300℃下使用，热固性泡沫最高可在400℃下使用。
要求保护的材料的另一个优点是其适用于热和声音/振动绝缘应用，温度范围如上所述从非常低到非常高的温度，额外的优点在于铝箔会用作蒸汽防护栅和反射器，玻璃纤维会用作额外绝缘层。
要求保护的材料的另一个优点是对机械负荷、压力、缺口形成、切口和锯口、包括啮齿动物或白蚁等的攻击具有抗冲击性，是用于户外绝缘目的另一个优点。
实施例
在以下实施例和比较例中，购买获得所需泡沫(等级
Figure BSA00000425973700081
阿玛赛尔公司，奥尔德姆(Armacell Ltd.，Oldham)；
Figure BSA00000425973700082
阿玛赛尔公司，明斯特(Armacell GmbH，Münster)；聚合物基料相同，但添加剂不同)或根据现有技术方案生产厚度为25mm的样品。采用可购得的粘合剂等(
Figure BSA00000425973700083
防火多层织物***，哈普弗兰公司，泽莱塔尔(Hapuflam GmbH，Zellertal)；Flammotect：防火涂料/涂层，b.i.o布兰德舒茨公司，塞沃塔尔(b.i.o.Brandschutz GmbH，Seevetal)，二者均为自粘合剂，其它：粘合剂520，阿玛赛尔公司，明斯特)通过轻微恒定的压力将所述保护层放置在泡沫部分上。在比较例的情况中，按照各文献分别提供的加工方法尽可能紧密地施加各层。
表1：根据EN 13823/EN 13501-1(单个燃烧物/圆角(round corner)测试)的泡沫化合物的可燃性测试结果：可燃性和根据EN 13823测定热释放总量(Total Heat Release，THR)、燃烧增长率(Fire Growth Rate，FIGRA)、烟生成率(Smoke Growth Rate，SMOGRA)和总产烟量(Total SmokeProduction，TSP)；根据EN 13501进行可燃性分级(最佳个体分级：B，S1，d0)。不带星号的实施例包含要求保护的材料。
Figure BSA00000425973700084
Figure BSA00000425973700091
表2：根据EN 13823/EN 13501-1采用具有不同泡沫层(C)的要求保护的***(A)(B)(C)在薄片成型材料上进行的灼烧度试验。不带星号的实施例包含要求保护的材料。
Figure BSA00000425973700092
Figure BSA00000425973700101
1)已根据ASTM E84标准(烟道燃烧测试)对基于NBR/PVC、EPDM和PET的***进行了测试，分级达到25/50(最佳等级)。

Claims (17)

1.一种由发泡聚合物作为核心组成的材料，所述发泡聚合物用至少一个由金属箔或玻璃纤维组成的内保护层和至少一个由玻璃纤维组成的外保护层涂覆。
2.如权利要求1所述的材料，其特征在于，所述金属箔是铝箔。
3.如权利要求1-2中任一项所述的材料，其特征在于，所述铝箔的厚度是1-400微米，优选2-50微米。
4.如权利要求1或2所述的材料，其特征在于，所述玻璃纤维采用编织物、针织物或单向编织物的形式。
5.如权利要求4所述的材料，其特征在于，所述玻璃纤维用非有机物质涂覆。
6.如权利要求1-4中任一项所述的材料，其特征在于，所述网目尺寸是0.01-0.80mm，特别优选0.04-0.25mm。
7.如权利要求1-4中任一项所述的材料，其特征在于，所述优选的丝密度是5-250根丝/厘米，特别优选20-60根丝/厘米。
8.如权利要求1-7中任一项所述的材料，其特征在于，所述各层用粘合剂结合。
9.如权利要求8所述的材料，其特征在于，所述粘合剂具有阻燃性。
10.如权利要求9所述的材料，其特征在于，所述粘合剂基于氯丁二烯。
11.如权利要求1-10中任一项所述的材料，其特征在于，施加其它层用于增强和装饰目的。
12.一种在连续过程中制造如权利要求1-11中任一项所述材料的方法。
13.一种在连续的两步挤出和层压过程中制造如权利要求1-11中任一项所述材料的方法。
14.如权利要求1-11中任一项所述的材料对于保护目的的应用。
15.如权利要求1-11中任一项所述的材料在需要针对温度和/或火和/或噪声/振动进行保护的用途中的应用。
16.如权利要求1-11中任一项所述的材料在热和/或声绝缘和/或声和/或振动衰减绝缘和/或防火绝缘中的应用。
17.如权利要求1-11中任一项所述的材料在结构、器皿、容器和管线，如墙壁、天花板、地板、屋顶、储罐、管子和管道内部和外部的热和/或声绝缘和/或防火绝缘中的应用。
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US20110174509A1 (en) 2011-07-21
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BRPI1107232A2 (pt) 2015-08-04
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