CN105754235A - 改进的绝缘材料 - Google Patents
改进的绝缘材料 Download PDFInfo
- Publication number
- CN105754235A CN105754235A CN201610114684.7A CN201610114684A CN105754235A CN 105754235 A CN105754235 A CN 105754235A CN 201610114684 A CN201610114684 A CN 201610114684A CN 105754235 A CN105754235 A CN 105754235A
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- CN
- China
- Prior art keywords
- fire retardant
- dispensing
- elastomer
- dispensing according
- plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 55
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 28
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及改进的绝缘材料。具体来说,描述了可发泡的弹性体配料,其适于制备具有内部航空器板所需的绝缘和减振性质以及阻燃性的聚合物泡沫。
Description
本申请为申请日为2010年6月24日,申请号为201080027999.9,发明名称为“改进的绝缘材料”的发明专利申请的分案申请。
技术领域
本发明涉及在绝缘或与绝缘有关的改进,并且特别涉及用于提供声音绝缘和/或阻尼来减少由振动引起的噪音的改进材料。在优选的实施方案中,本发明提供材料,该材料为结构体提供声音绝缘、减振和强度。本发明进一步涉及赋予绝缘体以防火和阻燃性能。本发明进一步提供聚合物配料,其用于生产包括该配料的声音绝缘以及声音和振动阻尼材料,其具有改进的防火和阻燃性能并且此外提供防火和阻燃剂体系。
背景技术
车辆在运转中由于两个活动制造声音和振动。车辆穿过周围大气(通常为空气)的简单运动会制造声音和引起振动。车辆本身的操作通常由于发动机和配套设备也制造声音和引起振动。为了乘客的舒适性以及也为了车辆的可靠性和安全性,有必要提供抑制振动作用和提供声音绝缘的材料。这在所有航空器类型,小型和大型航空器以及直升机中尤为重要。其中与以前使用铝相反,航空器机身由碳纤维增强复合材料制造的当前趋势使得对减振和声音绝缘的需求增加。
在航空器中可存在三(或更多)种形式的振动和噪音传播。这些可以是由于航空器本身的结构产生的或由于周围大气的空气产生的。航空器舱室内的振动产生不适和安全性风险。振动也在航空器舱室内可以产生不希望有的噪音,并且本发明涉及这些类型的振动和噪音的阻尼。
对运输工业中使用的材料以及特别是对于航空器中使用的材料加以严格的阻燃规定。减少的易燃性、阻燃性、减少的烟浓度、燃烧时的低放热对用于运输车辆的材料是重要的。特别是用于航空器的机身的增压舱内部的吸音和阻尼材料应当符合FederalAviationAuthority(FAA)测试FARPart25§25.853(a)和FARPart25§25.853(d)的要求。
还希望在伴随对车辆或航空器重量最小的增加下提供这些阻尼和可燃性降低的性能。因此存在提供材料的需求,该材料提供在高的性能与增加的重量之比下这些性质。
本发明特别用于制备用于航空器内部的板,如内部舱顶板、内壁板、隔板、吊挂箱门,食品柜结构件和板。这些板可以是包括在两个饰面片材之间的蜂窝结构的层状板。这些产品通常通过叠合饰面片材、热活化粘合剂和蜂窝结构,并且在压机、反应釜或炉中加热将层结合在一起来生产。传统上通过可结合到结构物的一个表面或机身结构的其它地方的隔离层来提供任何吸音或声音绝缘,然而这占据了另外的空间并且需要另外的制造步骤。已知弹性体和橡胶提供减振和声音绝缘性能。然而这些材料基于烃并因此易燃。
在例如建筑物中,航空器中,如汽车、卡车和公共汽车的车辆中,船舶中和有轨车辆中广泛范围的结构件中,存在对声音绝缘和/或减振的需求。已知通过设有饰面片材的蜂窝结构来提供轻质声音绝缘。也已知可将蜂窝结构的小室分为隔板,其中部分小室具有消音材料。在许多情况下也需要减振,特别是用发动机作动力的交通工具,如汽车、航空器、卡车和公共汽车以及有轨车辆。在许多应用中同样重要的是绝缘材料具有良好防火和阻燃性能。
也希望用最小重量的增加来获得希望的绝缘和/或减振。因此希望产品以最小密度来提供绝缘和阻尼并且希望使这能实现的配料是可获得的。
板、例如用作隔墙或航空器舱室绝缘和/或地板材料的那些板的声音屏蔽功效可通过穿过平板的传播损耗(TL)、一般以分贝来测量。传播损耗越高,吸音越大和声音绝缘越好。传播损耗将随着涉及所关注的声音的频率而变化。减振度可通过结构插入损耗(SBIL)测试来测量。防火和阻燃性能可通过CTA或机场新科技研究中心(CentreofExcellenceforAirportTechnology(CEAT))(批准的实验室)测量,其使材料试样同时经过火焰(用给定的气体速率)和辐射炉(使用3.5kw/cm2),并且测量由2分钟处理释放的卡路里总量(称为以kw/m2/min的总放热)和在5分钟中释放的卡路里峰值(以kw/m2的峰值放热率)。
蜂窝结构用来提供轻质强度,然而存在的问题在于为了改进声音和振动阻尼性质,已发现需要增加结构物的密度,由此产生不希望的板重量的增加。
在PortiaR.Peters,ShankerRajaram博士和StevenNutt博士于2006年12月3-6日在Honolulu的Internoise2006作出的名称为“SoundTransmissionLossofDampedHoneycombSandwichPanels”的论文中,报导了在蜂窝结构的中间平面中设置声音绝缘材料如粘弹性层。尽管已发现这可改进结构物的声学性能,然而它被证实是繁重的和费时的方法,它需要将粘弹性材料放在两片蜂窝之间,可能通过横切蜂窝结构并将粘弹性材料固定于这两片蜂窝来获得。
已建议提供具有改进的声音和振动阻尼性能的板的其它方法在组合的蜂窝板之上设置粘弹性阻尼片材。组合的蜂窝结构物典型地包括在夹在两个饰面片材之间的蜂窝材料。当该板用于声音绝缘时,至少一个饰面片材通常具有孔或穿孔以使声音穿过。当该板用于减振时,这并非必要,尽管如果板用于声音绝缘和减振两者,希望存在穿孔。每个饰面片材可以是所谓的预浸料坯,其可以是用可固化树脂如环氧树脂或聚氨酯前体预浸渍的纤维材料如玻璃或碳纤维垫。将蜂窝结构在压机中组合和加热以将饰面片材固化并且形成饰面片材和蜂窝之间的结合。然后可将粘弹性阻尼材料粘到组合结构的一个或两个外表面。因此该方法包括另外的步骤来将阻尼材料胶粘到蜂窝板,并且胶粘层可能是脆性的并损害整体结构物的阻尼效果。另外的缺点是声音绝缘材料增加了最终结构物的重量和尺寸,但不利于最终结构物的刚性。在某些实施方案中,可将另外的限制层施加到阻尼材料上以进一步增强阻尼效果。可用作限制层的材料的实例包括纤维增强塑料、铝箔或厚橡胶泡沫。这再次增加了结构物的体积,对刚性几乎没有影响。
设置用于提供声音绝缘和减振的板的其它技术提供具有饰面片材在所述片材之间的柔软发泡芯材的板,所述饰面片材可以是预浸料坯。尽管这些板可具有良好的声学性能,泡沫不利于与可比重量和厚度的蜂窝结构同样的方式下的机械性能。
设计用来声音绝缘的各种蜂窝结构描述在美国专利公开US2007/0134466,美国专利6,267,838,美国专利6,179,086,WO2006/045723,美国专利公开US200/0194210和英国专利申请2252076A中。
PCT公开WO2006/132641和WO2007/050536描述了包括第一和第二板的板结构,具有给板结构提供增强、隔板、密封,吸音、阻尼、交替、绝热和它们的结合的材料。该材料可以是泡沫并且WO2007/050536的配料可包含阻燃剂。然而这些配料难以加工。在一个实施方案中,可将材料的支持体设置在第一和第二板之间,并且支持体可以是蜂窝结构。预期的是支持体和可以为泡沫的材料可填充两个板之间的全部或部分空间。板可通过将可活化材料设置在靠近板之一,将支持体如蜂窝置于靠近可活化材料并使可活化材料膨胀或发泡进入支持体的开孔。
在用于绝缘的聚合物泡沫中包括防火和阻燃剂是已知的。已建议的防火和阻燃剂的实例包括含磷化合物,金属水合物如三水合镁或三水合铝,各种石墨包括膨胀性石墨。也建议使用不同组合的阻燃剂。阻燃剂倾向于是较高密度的固体材料并且为了获得需要的阻燃剂性质,特别是航空器舱室板的低放热要求,可需要大量阻燃剂。这给减振和声音绝缘系统增加了的不希望有的附加的重量。此外该大量易于增加配料的熔体粘度,降低其加工性能和导致在挤出机中的不希望有的压力增大,特别是当在板形成声音绝缘和减振所需要的生产薄条材料时。
使用本发明的配料可在不需要改进现有的制造工艺下生产具有阻燃性质的板,其具有嵌入其中的声音阻尼或声音绝缘材料。提供嵌入板内的声音阻尼和声音绝缘材料的能力节省了车辆结构件中的空间。
发明内容
本发明提出了这些问题并且提供可用于提供减振和/或声音绝缘的配料,其具有降低的可燃性和特别是在最小的重量增加下符合FAA测试FARPart25§25.853(a)和FARPart25§25.853(d)。此外本发明提供可用于赋予板以减振和/或声音绝缘而不显著地改变目前用于板制造的方法的配料。
本发明涉及以下方面:
1.可发泡配料,其用于制备具有改进的阻燃性能的减振材料,该可发泡配料包括:
i)弹性体
ii)增塑剂或加工助剂
iii)发泡体系
iv)阻燃剂体系。
2.根据项目1的配料,其包含增粘剂。
3.根据项目1或项目2的配料,其中该增塑剂和该增粘剂是相同的材料。
4.根据前述任一项项目的可发泡配料,其中该弹性体可交联,并且该配料包含用于弹性体的交联剂。
5.根据前述任一项项目的配料,其中该弹性体以可发泡材料的5wt%-65wt%的量存在。
6.根据前述任一项项目的配料,其中该弹性体无卤素。
7.根据前述任一项项目的配料,其中该弹性体是具有高阻尼损耗因数的橡胶。
8.根据项目1-7任一项的配料,其中该弹性体是丁基橡胶。
9.根据项目1-5和项目7-8任一项的配料,其中该弹性体可交联并且是可选的卤代共聚物,所述卤代共聚物是异烯烃和烷基苯乙烯如C4-C7异烯烃和C1-C5烷基苯乙烯的卤代共聚物,特别优选的是异丁烃和对甲基苯乙烯的溴代共聚物。
10.根据前述任一项项目的配料,其包含基于配料重量的0.1wt%-5wt%的发泡体系。
11.根据前述任一项项目的配料,其包含基于配料重量的25wt%-70wt%的阻燃剂体系。
12.根据前述任一项项目的配料,其包含1-20wt%的该增塑剂。
13.根据项目12的配料,其中该增塑剂是液体聚丁烯。
14.根据前述任一项项目的配料,其包含辅助的增塑剂。
15.根据项目14的配料,其中该辅助的增塑剂是阻燃剂增塑剂。
16.根据前述任一项项目的配料,其中该阻燃剂包含i)、ii)和iii)的混合物
i)含磷阻燃剂
ii)金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属氢氧化物阻燃剂
iii)石墨。
17.根据项目16的配料,其中该石墨是热膨胀性石墨。
18.根据前述任一项项目的配料,其中发泡体系是物理发泡剂和化学发泡剂的混合物。
19.根据项目4-17任一项的配料,其中该发泡体系和该交联剂在100℃-180℃范围的温度下实现其各自的功能。
20.根据前述任一项项目的配料,包含:
i)基于配料重量的10%-60wt%的弹性体
ii)基于配料重量的0.1-5wt%的发泡体系
iii)基于配料重量的25%-75wt%的阻燃剂体系
iv)基于配料重量的1-20wt%的增塑剂或加工助剂
v)基于共聚物重量的0.1-5wt%的交联剂。
21.阻燃剂配料,包括:
i)含磷阻燃剂
ii)金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂
iii)石墨。
22.根据项目21的阻燃剂配料,包含:
a)20wt%-60wt%的含磷阻燃剂
b)5wt%-25wt%的金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂
c)5wt%-25wt%的石墨。
23.根据项目21或22的阻燃剂组合物,其中含磷阻燃剂选自红磷、磷酸铵如多聚磷酸铵,三聚氰胺磷酸酯或焦磷酸酯。
24.根据项目21-23任一项的阻燃剂,其中金属氧化物或金属氢氧化物为三水合铝或氢氧化镁。
25.根据项目21-24任一项的阻燃剂,其中使用的石墨是热膨胀性石墨(HEG)。
具体实施方式
在一个实施方案中本发明提供用于提供声音绝缘和/或减振,改进阻燃性质如阻燃性、减少的燃烧时间、减少的烟气密度和减少的放热的配料,其是轻质的并可用于板中以在具有最小空间需求的车辆中提供减振,并且其可用于常规的板制造方法。
因此本发明提供用于生产具有改善的阻燃性质的减振材料的可发泡配料,包含:
i)弹性体
ii)增塑剂
iii)发泡剂
iv)阻燃体系
增塑剂也可以用作增粘剂并且在这种情况下优选为增粘树脂。发泡体系优选为发泡剂并且阻燃剂特别是阻燃剂。
增塑剂改进了配料的加工性。在用于航空器的板制造中,可发泡材料的薄条需要求典型地为低于2毫米厚度、更典型地在0.5-1.5毫米范围厚度的条。条的宽度将取决于板的类型和大小,尽管典型的宽度为100-500毫米,更典型地为200-350毫米。无增塑剂的配料的挤出可在挤出模头产生不希望有的压力增大。当可使用任何合适的增塑剂时,我们已发现使用聚合物增塑剂如液体聚丁烯可进一步提供减振和声音绝缘,也可作为增粘剂起作用并改进配料的加工性能。如同弹性体一样,这些材料是易燃的并且它们的使用使得对阻燃剂的需求增加。也可包括辅助的增塑剂和我们特别优选使用阻燃增塑剂如磷酸酯系增塑剂、如Santicizer范围的磷酸酯系增塑剂作为辅助增塑剂。
优选弹性体是可交联的并且配料包含用于可交联的弹性体的交联剂,这样一旦发泡,可将其交联成保持小室结构的一体性并且避免崩塌。也优选当将配料加热来发泡时,可交联的弹性体除了发泡外还交联。
在本发明的又一个实施方案中,可发泡弹性体使当它加热时产生发泡,材料显现粘合性质。
如无另外说明,则在讨论中,本发明的配料中的百分比是指重量百分比。
本发明的可发泡材料将包括大量弹性体材料,其可以是一种弹性体或几种不同弹性体的混合物。弹性体材料为可泡沫材料的典型地至少约5wt%,更典型地至少10wt%,优选至少约14wt%,更加典型地至少25wt%,并且弹性体材料为典型地低于约可泡沫材料的65wt%,更典型地低于约60wt%和最典型地低于40wt%。
适于弹性体材料的弹性体包括但并不限于,天然橡胶、丁苯橡胶、聚异戊二烯、聚异丁烯、聚丁二烯、异戊二烯-丁二烯共聚物、氯丁橡胶、丁腈橡胶(例如丁基腈、如羧基封端的丁基腈)、丁基橡胶、多硫化物弹性体、丙烯酸类橡胶、丙烯腈弹性体、硅橡胶、聚硅氧烷、聚酯橡胶、二异氰酸酯-连接的缩合弹性体(diisocyanate-linkedcondensationelastomer)、EPDM(乙烯-丙烯二烯单体橡胶),氯磺化聚乙烯、氟代烃等。特别优选的弹性体是以商品名VISTALON7800和2504销售的可从ExxonMobilChemical商购的EPDM,,和ExxonMobilChemical的以商品名Exxpro销售的丁基橡胶。其它优选的弹性体是以商品名H-1500销售的聚丁烯异丁烯共聚物,其可从BPAmocoChemicals商购。优选的弹性体是异烯烃和烷基苯乙烯的共聚物,如C4-C7异烯烃和C1-C5烷基苯乙烯卤代共聚物,特别优选的是异丁烯和对甲基苯乙烯的溴化共聚物,如ExxonMobilChemical提供的Exxpro材料。虽然对于如航空器中的某些用途,优选弹性体无卤素。我们优选使用具有高振动损耗因数的橡胶,并且这里优选丁基橡胶,如可使用自ExxonMobilChemical或Lanxess得到的的橡胶。Exxpro3433和Lanxess402特别有用。这些弹性体的混合物也可使用并且在一些情况下是优选的。
可发泡材料包含发泡体系,其典型地包括一种或多种发泡剂。发泡体系可以是物理发泡剂和/或化学发泡剂。例如,发泡剂可以是热塑性塑料封装的溶剂,其在暴露到如加热的条件时膨胀。可替代地或此外,发泡剂可在暴露到如加热或湿度的条件时或暴露到另一种化学反应物时进行化学反应以使气体逸出。
发泡剂可包括一种或多种含氮基团,如酰胺,胺等。合适的发泡剂实例包括偶氮二碳酰胺,二亚硝基五亚甲基四胺,4,4i-氧基-双-(苯磺酰肼),三肼基三嗪和N,Ni-二甲基-N,Ni-二亚硝基对苯二甲酰胺。
我们优选使用包括化学发泡剂和物理发泡剂的混合物的发泡体系,如封装溶剂,因为虽然物理发泡剂具有良好的膨胀性质,由于存在烷烃它可增加产品的易燃性,因此优选使用该组合。
也可提供化学发泡剂的促进剂。各种促进剂可以用来增加发泡剂形成惰性气体的速率。一种优选的发泡剂活化剂是金属盐或是氧化物,例如金属氧化物,如氧化锌。其它优选的促进剂包括改性和未改性的噻唑或咪唑,脲等。
应当使用的发泡剂和发泡剂活化剂的量可根据希望的小室结构类型、希望的可发泡材料的膨胀量和希望的膨胀率而变化。在可发泡材料中的发泡剂和发泡剂活化剂的量的示例性范围为弹性体材料的约0.001wt%-5wt%。在优选的配料中,我们优选发泡剂包括10wt%-60wt%的化学发泡剂和90wt%-40wt%的物理发泡剂。为了产生减振,优选200%-1000%的膨胀度、更优选300-500%。也优选膨胀在10-180分钟在120℃-180℃、优选120℃-160℃、更优选120℃-140℃范围的温度发生,并且膨胀在小于15分钟内完成。
可将一种或多种固化或交联剂和/或固化剂促进剂可包括在可发泡材料中。如同发泡剂,固化剂和固化剂促进剂的量可根据希望的小室结构类型、希望的可活化材料的膨胀量、发泡材料的希望的膨胀率和希望的结构性能而广泛变化。可用于材料的固化剂或固化剂促进剂的示例范围为弹性体材料的约0.001wt%-约7wt%。特别是当弹性体材料可交联时,固化或交联剂将存在。在一个实施方案中丁基橡胶与交联剂同时使用。
当在配料中采用的弹性体材料可交联时,可包括交联剂,并且它们可选自脂肪族或芳香族胺或它们的各自加合物,氨基胺,聚酰胺,环脂族胺(例如酸酐,多羧酸聚酯,异氰酸酯,酚系树脂(如苯酚酚醛清漆树脂或甲酚酚醛清漆树脂,共聚物如萜酚、聚乙烯基酚或双酚-A甲醛共聚物,双羟基苯基烷烃等),硫或其混合物。特别优选的固化剂包括改性和未改性的多胺或聚酰胺如三亚乙基四胺,二亚乙基三胺,四亚乙基五胺,氰基胍,双氰胺等。也可以提供固化剂的促进剂(例如改性或未改性的脲如亚甲基二苯基双脲,咪唑或其组合)。固化剂促进剂的其它实例包括但不限于金属氨基甲酸酯(例如二甲基二硫代氨基甲酸铜,二丁基二硫代氨基甲酸锌,其组合等),二硫化物(例如二硫化二苯并噻唑)。也可以使用金属盐,并且当使用优选的异丁烯和对甲基苯乙烯的溴化共聚物作为可交联弹性体时,优选使用锌盐如氧化锌和/或硬脂酸锌作为交联剂。当嵌入包括预浸渍饰面片材的板的配料用来提供减振和/或声音绝缘时,优选使用将在固化期间与预浸渍材料相互作用的固化剂以改进泡沫和预浸料坯之间的粘结。同样如果板具有蜂窝内层,可选择可发泡配料中的固化剂来与蜂窝反应以进一步改进粘结。
尽管较长的固化时间也是可能的,对于本发明的可交联配料,小于5分钟、并且甚至小于30秒的固化时间是可能的。此外,该固化时间可取决于是否将另外的能量(例如热、光、辐射)应用到材料或是否材料在室温下固化。
如建议的,较快的固化剂和/或加速剂可特别期望用于缩短固化开始与基本完全固化(对于特定的可活化材料即至少90%的可能固化)之间的时间,并且在保持其自支撑特性时发泡材料固化。正如在此使用的,固化的开始用于表示基本完全固化的至少3%但不大于10%。对于其中弹性体材料是可交联的本发明的实施方案,一般期望固化的开始与基本完全固化之间的时间小于约30分钟,更典型地小于约10分钟,甚至更典型地小于大约5分钟,以及更典型地小于1分钟。应该注意到的是,弹性体材料的软化时间,固化时间和气泡形成或发泡的时间的更紧密相关可以有助于在其自支撑特性没有实质的损失的情况下使得可膨胀材料发泡。
也如此前建议的,可将可发泡材料配制成包括在材料发泡之前至少部分固化可发泡材料的固化剂。优选单独或与可发泡材料的其它性能或成分组合的部分固化赋予材料足够的自支撑特性,这样在发泡期间,可发泡材料在没有显著地失去形状或没有在重力下的显著流动下膨胀体积。
在一个实施方案中,可发泡材料包括第一固化剂和可选的第一固化剂加速剂、以及第二固化剂和可选的第二固化剂加速剂,所有这些优选为潜性的。第一固化剂和/或加速剂设计为在可发泡材料的加工(例如加工、混合、成形或以其组合)期间部分固化可发泡材料,以至少有助于给材料提供所希望的自支撑性质。第二固化剂和/或加速剂将在暴露于例如热、湿度等等的情况下时固化正在发泡和已发泡的材料。
作为本实施方案的一个优选的实施例,第二固化剂和/或加速剂在第二温度或温度范围将可发泡材料的弹性体材料固化。第一固化剂和/或加速剂也是潜性的,并且它们在暴露于低于第二温度的第一高温时,将可膨胀材料部分地固化。
在材料混合、成形或两者期间,可经历第一温度和部分固化。例如可在将可发泡材料的成分混合并将可发泡材料通过模头挤成特定形状的挤压机中,经历第一温度和部分固化。作为另一实施例,可在成形及可选地混合可发泡材料的成分的成型机(例如注塑、吹塑、压塑)中,经历第一温度和部分固化。
部分固化可通过各种技术完成。例如,可将第一固化剂和/或加速剂以低化学计量添加到可发泡材料,这样聚合物材料提供基本上比第一固化剂和/或加速剂的实际反应更多的反应点。第一固化剂和/或加速剂的优选的低化学计量典型地引起由聚合物材料提供的可获得的反应点的不超过60%,不超过40%或不超过30%、不超过25%或甚至不超过15%的反应。替代地,例如当提供多种不同的聚合物材料并且第一固化剂和/或加速剂仅仅与聚合物材料中的一种或其子集起反应时,部分固化可通过提供仅仅对一定百分比的聚合物材料起反应的第一固化剂和/或加速剂而实现。在该实施方案中,第一固化剂和/或加速剂通常与聚合物材料的不超过60wt%,不超过40wt%或不超过30wt%、不超过25wt%甚至不超过15wt%起反应。
与上述实施方案相似,单独或可活化材料的其它性能或成分组合的部分固化,赋予可活化材料足够的自支撑性能,这样在活化和/或发泡期间,可活化材料不经历沿重力方向的显著流动。
也与上述实施方案相似,在混合时的部分固化可以通过各种技术实现。例如,当第一组分和第二组分混合时第一固化剂和/或加速剂可在可发泡材料内以低化学计量存在,这样弹性体材料提供基本上比由第一固化剂和/或加速剂实际起反应更多的反应点。第一固化剂和/或加速剂的优选的低化学计量典型地引起由材料提供的可获得的反应点的不超过60%,不超过40%或不超过30%、不超过25%或甚至不超过15%的反应。替代地,例如当提供多种不同的聚合物材料并且第一固化剂和/或加速剂仅仅与聚合物材料中的一种或其子集起反应时,部分固化可通过提供仅仅对一定百分比的材料起反应的第一固化剂和/或加速剂而实现。在该实施方案中,第一固化剂和/或加速剂典型地能与材料的不超过60wt%,不超过40wt%或不超过30wt%、不超过25wt%或甚至不超过15wt%进行反应。
本发明的可发泡材料包括一种或多种阻燃剂。选择阻燃剂将取决于配料的预期用途和与火相关的规格和与用途有关的要求。当要求发泡材料满足火、烟和毒性测试,可使用一系列阻燃剂,并且有用的阻燃剂包括卤代聚合物,其它卤代材料,包括磷、溴、氯、氧化物和它们的结合的材料(例如聚合物)。示例的阻燃剂包括但不限于氯烷基磷酸酯,甲基膦酸二甲基酯,溴-磷化合物,多聚磷酸铵,溴化新戊基聚醚,溴化聚醚,锑氧化物,偏硼酸钙,氯化石蜡,溴化甲苯,六溴苯,三氧化锑,石墨(例如膨胀性石墨),其组合等。可使用的其它阻燃剂包括磷酸三甲苯酯和三水合铝。
本发明进一步提供包含特定阻燃剂组合的少放热的配料。如在航空器中的内部板的某些用途特别是对于放热具有更严格的要求,并且我们发现包含热膨胀性石墨的配料可减少放热。
从例如美国专利3,574,644和5,650,448,已知热膨胀性石墨作为阻燃剂,所述专利描述了在用于航空器座椅的聚合物泡沫的用途。PCT公开WO2005/101976建议其可在含烯烃聚合物中与含氮的阻燃剂、可选的25-50wt%量的金属氢氧化物使用作为磷阻燃剂一起使用。
可使用的含磷阻燃剂的实例包括红磷,磷酸铵如多磷酸盐,蜜胺磷酸酯或焦磷酸盐。金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂可以是任何已知的含金属阻燃剂。优选的材料包括三水合铝和氢氧化镁。
优选防火或阻燃剂无卤素。为了获得希望的阻燃性质,需要包括基于配料重量的最多75wt%的阻燃剂。优选的配料包含60wt%-75wt%的阻燃剂。优选的阻燃剂体系取决于所要将配料投入的用途。然而,在航空器中提供减振和声音绝缘的优选用途中,特别是如含蜂窝内层的板的板内嵌入的发泡材料,其中放热是主要因素,我们发现三组件防火或阻燃剂体系是特别有用的,本发明因此进一步提供阻燃剂配料的应用,包括:
i)含磷阻燃剂
ii)金属氧化物,氢氧化物或水合物阻燃剂
iii)石墨。
在本发明的配料中的优选的阻燃剂配料是
a)20wt%-60wt%的含磷阻燃剂
b)5wt%-25wt%的金属氧化物阻燃剂,金属氢氧化物阻燃剂或金属水合物阻燃剂
c)5wt%-25wt%的石墨。
本发明进一步涉及防火或阻燃剂体系本身的改进和特别是赋予声音绝缘和/或隔声材料以防火和阻燃性的用途。
本发明因此进一步提供阻燃体系,包括:
iv)含磷阻燃剂
v)金属氧化物阻燃剂,金属氢氧化物阻燃剂或金属水合物阻燃剂
vi)石墨
本发明优选的阻燃体系包括:
d)20wt%-60wt%的含磷阻燃剂
e)5wt%-25wt%的金属氧化物阻燃剂,金属氢氧化物阻燃剂或金属水合物阻燃剂
f)5wt%-25wt%的石墨。
含磷阻燃剂提供阻止燃焰蔓延的屏障,优选多聚磷酸铵。金属氧化物、金属氢氧化物或烃吸收热,是因为其包含水,但其不应该大量使用,是因为它可增加烟浓度。使用的石墨优选为热膨胀性石墨(HEG),其相对于加热膨胀以产生阻火层。膨胀性石墨可以是任一本领域已知的那些,如G.I.,Gelman,V.N.,Isaev,Yu.V和Novikov,Yu.N.在MaterialScienceForum,第91-93,213-218,(1992),Titelman,和美国专利6,017,987中描述的那些。
热膨胀性石墨在火焰下热分解成炭化膨胀石墨,提供绝缘热阻,其阻止进一步氧化。
热膨胀性石墨源自于天然石墨或人造石墨,并且当从室温快速加热到高温时,它在晶体的c-轴方向膨胀(通过所谓的剥落或膨胀方法)。除了在晶体的c-轴方向膨胀,热膨胀性石墨在a-轴以及b-轴方向稍微膨胀。剥落程度或HEG的膨胀性取决于在快速加热期间除去挥发性化合物的速率。在本发明中的膨胀值涉及在快速加热到500-700℃后获得的比体积与在室温下的比体积之比。在本发明中HEG的比体积改变优选为温度变化范围(室温到500-700℃)的不少于50倍。优选这样的膨胀度,是因为已发现,与是热可膨胀的但具有在上述加热条件中比体积增加低于50倍的石墨相比,具有在从室温到700℃的快速加热期间增加至少50倍的比体积的HEG产生程度远较高的阻燃度。
在从室温到高温如700℃的快速加热HEG期间,一般记录重量损失。10%-35%(优选15%-32%)的HEG重量损失一般是由于在上述加热条件中在50倍或更大的体积膨胀下除去挥发性化合物。在快速加热期间具有低于10%重量损失的HEG等级提供低于50倍的比体积增加。在快速加热期间具有大于35%重量损失的HEG等级提供较少量的膨胀石墨炭,并且因此HEG仅在更高的填充量获得阻燃性。
在上述的加热条件下显示出50倍或更高的体积膨胀的热膨胀性石墨的碳含量应该为65wt%-87wt%(优选67.5wt%-85wt%)用作良好的含碳隔绝物和用于与含氮阻燃剂组合而提供高水平的阻燃性。
具有大于87%的碳含量的HEG在快速加热期间提供低于50倍的比体积增加。在上述加热条件下将HEG中的碳含量至低于65%的降低提供较少量的膨胀石墨炭,并且因此可以仅以更高填充量的HEG而获得聚合物组合物的阻燃性。
在从室温到更低的温度(如约500℃)的快速加热HEG期间,HEG的比体积改变应该大于50倍并低于100倍。在更低的温度(如约500℃)具有太高比体积增加的HEG等级在燃烧下提供过快的HEG膨胀,并因此可以仅以更高填充量的HEG而获得阻燃性。
用于本发明的热膨胀性石墨可用不同的方法生产,并且该方法的选择不是关键的。例如可通过天然石墨或人造石墨的氧化处理获得。例如通过用氧化剂如过氧化氢、硝酸或在硫酸中的另一种氧化剂处理进行氧化。常见的常规方法描述在美国专利3,404,061或SU专利1,657,473和1,657,474中。而且,石墨可在含水酸性或含水盐电解质中阳极地氧化,如美国专利4,350,576中所述。实际上,大多数工业级热膨胀性石墨一般经由酸性工艺而制备。
由在硫酸中的氧化或如上所述的类似方法生产的热膨胀性石墨可根据工艺条件而略呈酸性。当热膨胀性石墨是酸性时,用于制备聚合物组合物的装置的腐蚀可能发生。为了防止这样的腐蚀,热膨胀性石墨应该用碱性材料(碱性物质,氢氧化铵等等)中和。
用于本发明的热膨胀性石墨的粒度影响HEG的膨胀度,并且反过来影响所形成的聚合物组合物的阻燃性。
具有优选粒度分布的热膨胀性石墨包含最多25wt%、更优选1wt%-25wt%的通过75-目的颗粒。包含通过75-目的大于25wt%的颗粒的HEG不提供需要的比体积的增加,并因此不提供足够的阻燃性。包含低于1wt%的含量的上述颗粒的热膨胀性石墨可略微损害所形成的聚合物组合物的机械性能。为了避免聚合物组合物的性质恶化,超过75-目的HEG最大颗粒的尺寸应该为本领域已知的。在优选的实施方案中,热膨胀性石墨颗粒的表面可用偶联剂如硅烷偶联剂或钛酸酯偶联剂表面处理,以便降低较大颗粒对阻燃聚合物组合物性质上的不利影响。同时可将偶联剂分别添加到组合物。
阻燃剂可以为可发泡材料的相当大的重量百分比。阻燃剂可占可发泡材料的大于2wt%、更典型地大于12wt%、更加典型地大于25wt%并且甚至可以大于35wt%。当将异丁烯和对甲基苯乙烯的溴化共聚物用作弹性体时,我们优选使用基于配料重量的40wt%-75wt%,更优选40-60wt%的阻燃剂,并且我们特别优选使用衍生自磷酸铵如多聚磷酸铵和硼酸锌并可选地含三水合铝的配混物。当可发泡弹性体为丁基橡胶时,我们优选使用本发明的优选的阻燃剂组合物的40%-75%。
本发明的可发泡材料可包括增粘剂,其为一种或多种组分的混合物。增粘剂可以是液体或固体或两者的组合,并且优选为在可发泡材料发泡时的温度显现粘合性质的材料。当使用增粘剂时,增粘剂典型地以可发泡材料配料的最少约1wt%,更典型地至少约4wt%,更加典型地至少8wt%,典型地以配料的10wt%-20wt%存在。可使用各种增粘剂,如含环氧化物的材料,聚丙烯酸酯,烃树脂和萜烯树脂。一个特别优选的增粘剂是以商品名SUPERNEVTAC99销售的烃树脂,其可从NevilleChemicalCompany商购。另一个特别优选的增粘剂是液体聚异丁烯,其可与丁基橡胶弹性体使用,此外用作增塑剂或加工助剂。优选的增粘剂包括萜烯树脂和优选为液体聚异丁烯如IndopolH300的聚异丁烯的共混物。
配料也包含加工助剂或增塑剂以改进在高温如经历挤出或注塑成型的那些温度下的配料的加工。含低分子量乙烯的聚合物是特别合适的。可以可选用另外的单体改性的乙烯/酯共聚物或三元共聚物如乙烯/乙烯基酯共聚物和乙烯/丙烯酸酯是优选的。我们发现引入基于配料重量的最多10%,更典型地3-7wt%的这样的聚合物是有益的。低分子量弹性体如IndopolH300也可用作该加工助剂或增塑剂。
可发泡材料也可以包括一种或多种填料,包括但不限于颗粒材料(例如粉末)、珠和微球。优选地,填料包括通常与存在于可发泡材料中的其它组分不起反应的密度相对低的材料。
可使用的填料的实例包括二氧化硅、硅藻土、玻璃、粘土、滑石、颜料、着色剂、玻璃珠或玻璃泡,玻璃、碳陶瓷纤维、抗氧化剂等等。特别是粘土的这样的填料能在材料流动期间帮助材料自身流平。可用作填料的粘土可包括来自可以被煅烧的高岭石、伊利石(illite)、绿泥石(chloriten)、蒙脱石(smecitite)或海泡石(sepiolite)群组的粘土。合适的填料的实例包括但不限于滑石、蛭石、叶蜡石、锌蒙脱石、滑石粉、绿脱石、蒙脱石或其混合物。粘土还可以包括少量的其他成分,例如碳酸盐、长石、云母和石英。填料还可包括氯化铵,例如二甲基氯化铵和二甲基苯甲基氯化铵。也可采用二氧化钛。
在一个优选的实施方案中,一种或多种矿物或石头类的填料例如碳酸钙、碳酸钠等可用作填料。在另一个优选实施方案中,硅酸盐矿物例如云母可用作填料。已发现除了实现填料的正常功能外,硅酸盐矿物和云母特别改善了固化并发泡的材料的抗冲击性。
当使用填料时,在可发泡材料中的填料为可发泡材料的10wt%-90wt%。根据一些实施方案,可发泡材料可包括约0.001wt%-约30wt%,和更优选约10wt%-约20wt%的粘土或类似填料。粉末(例如约0.01-约50微米,和更优选约1-25微米的平均粒径)矿物型填料可占可发泡材料的约5wt%-70wt%,更优选约10wt%-约20wt%,和更优选约13wt%。
预期材料的一种填料或其它组分可以是触变性的,以有助于控制材料流动以及如拉伸强度、压缩强度或剪切强度的性质。这样的触变性填料可另外给可活化材料提供自支撑特性。触变性填料的实例包括但不限于二氧化硅、碳酸钙、粘土、聚芳酰胺纤维或纸浆或其它。一个优选的触变性填料是合成的无定形的沉淀二氧化硅。
在可发泡材料中也可以按要求包括其他添加剂、试剂或性能改性剂,包括但不限于抗氧化剂,抗静电剂,抗UV剂,抗冲改性剂,热稳定剂,UV光引发剂,着色剂,加工助剂,润滑剂,增强剂(例如短切或连续玻璃,陶瓷,聚芳酰胺或碳纤维等)。
本发明的可发泡材料可包括加工油,其可以是一种或多种油的混合物。一种特别优选的加工油是以商品名SENTRY320销售的精炼石油固体,可从Citgooil商购。当使用加工油时,这样的油以约1wt%-约25wt%存在于可发泡材料中,但可以更高或更低的量使用。
本发明进一步提供优选使用可选卤代的共聚物作为声音绝缘板中的可交联的和可发泡的弹性体材料,该卤代共聚物为异烯烃和烷基苯乙烯的卤代共聚物,该声音绝缘板包括被蜂窝结构分隔的两个饰面板,蜂窝结构在蜂窝结构小室内含有发泡的交联弹性体材料。异烯烃优选为C4-C7异烯烃并且烷基苯乙烯是C1-C5烷基苯乙烯,卤素可以是氯、溴或氟,并且溴是优选的。异丁烯和对甲基苯乙烯的溴化共聚物是优选的。如上所述在如用于航空器的一些应用中,优选弹性体无卤素。
本发明进一步提供与增塑剂一起的这样的应用,增塑剂也可用作增粘剂。优选液体聚异丁烯。
在又一个实施方案中,本发明提供于与阻燃剂一起的这样的应用,阻燃剂优选包括源自磷酸铵或多聚磷酸铵和硼酸锌的可选包含三水合铝的配混物。
如上所述,已发现,发泡并可选卤代的共聚物特别用于提供声音绝缘和/或减振,该共聚物是异烯烃和烷基苯乙烯的共聚物。典型地共聚物包含2-8摩尔烷基苯乙烯/100摩尔异烯烃和20-50wt%基于烷基苯乙烯重量的卤素。这些材料可以Exxpro的商品名从ExxonMobilChemicalCompany商购,并且在美国专利5,162,445;5,430,118;5,426,167;5,548,023;5,548,029;5,654,379中描述。异烯烃优选为异丁烯,并且烷基苯乙烯可以是邻、间或对烷基苯乙烯,其中对烷基苯乙烯是优选的。烷基可以是C1-C5烷基,并且优选甲基,优选的烷基苯乙烯是对甲基苯乙烯。如果存在的话,卤素可以是氯、溴或氟,其中优选溴。
本发明因此进一步提供包括异烯烃和烷基苯乙烯的可选卤代的共聚物以及发泡剂的配料。发泡剂可以为物理发泡剂和/或化学发泡剂,并且优选以基于共聚物重量的最多5wt%的量存在,并且可与发泡剂活化剂一起存在。
在另一个实施方案中,配料包含阻燃剂并且因此提供包含异烯烃和烷基苯乙烯的可选卤代的共聚物、发泡剂和阻燃剂的配料。发泡剂优选以基于共聚物重量的最多5wt%的量存在并且可与发泡剂活化剂一起存在。尽管我们优选配料包含20-75wt%、更优选20-70wt%、最优选30-50wt%的阻燃剂,阻燃剂可以为此前描述的任一种材料并且应当根据所需的性质选择用量。
在另一个实施方案中,配料还包括如前所述的增粘剂。增粘剂可以是固体或液体,它赋予配料粘合性并且优选在可发泡材料发泡的温度下显现粘合性质。增粘剂也可起到配料的增塑剂或加工助剂的作用。
本发明因此进一步提供包括以下的配料:
i)异烯烃和烷基苯乙烯的可选卤代的共聚物
ii)发泡体系
iii)阻燃机体系
iv)增塑剂
在另一个实施方案中,配料还包含使异烯烃和烷基苯乙烯的卤代共聚物在高温交联交联剂。
本发明因此还提供
i)异烯烃和烷基苯乙烯的可选卤代的共聚物
ii)发泡体系
iii)阻燃剂体系
iv)增塑剂
v)异烯烃和烷基苯乙烯的卤代共聚物的交联剂
交联剂可以是前述的任一材料,并且优选以异烯烃和烷基苯乙烯的可选卤代的共聚物重量的0.1wt%-5wt%的量存在。
本发明优选的配料因此包括:
i)基于配料重量的10%-60wt%的异烯烃和烷基苯乙烯的共聚物
ii)基于共聚物重量的0.1-5wt%的发泡体系
iii)基于配料重量的25%-50wt%的阻燃剂体系
iv)基于配料重量的1-10wt%的增塑剂
v)基于共聚物重量的0.1-5wt%的交联剂
本发明进一步提供具有高阻尼损耗因数的可发泡橡胶如丁基橡胶在包括被蜂窝结构分隔的两个饰面板的声音绝缘板中的使用,蜂窝结构在蜂窝结构小室内包含具有高阻尼损耗因数的发泡的交联橡胶如丁基橡胶。配料优选包含10-60wt%、更优选25-60wt%的丁基橡胶。
本发明进一步提供同时应用也起增粘剂促进剂作用的增塑剂。优选液体聚丁烯是的。更优选聚丁烯和萜烯树脂。
在又一个实施方案中,本发明提供与阻燃剂一起的用途,优选包含磷酸铵、金属氧化物、金属氢氧化物或金属水合物和膨胀性石墨的包括三组分体系。
在本发明的又一个实施方案中本发明因此提供包括具有高阻尼损耗因数的橡胶如丁基橡胶、发泡体系和阻燃剂体系的配料。发泡体系可以是化学和/或物理发泡剂并且优选以基于如丁基橡胶的橡胶重量的最多5wt%的量存在,并且可与发泡剂活化剂一起使用。阻燃剂体系可以是任意的此前描述的材料并且应当根据所需要的性质选择用量,尽管我们优选配料包含20-70wt%、更优选30-50wt%的阻燃剂体系。
本发明因此进一步提供包括以下的配料:
i)具有高阻尼损耗因数的橡胶
ii)发泡体系
iii)阻燃剂体系
iv)增塑剂
高阻尼橡胶优选为丁基橡胶。
在又一个实施方案中,配料还包含交联剂,其使丁基橡胶在高温交联。
本发明因此进一步提供
i)丁基橡胶
ii)发泡体系
iii)阻燃剂体系
iv)增塑剂
v)交联剂
交联剂可以是任意的此前提到的材料并且优选以典型地为丁基橡胶的橡胶的0.1wt%-5wt%的量存在。
本发明优选的配料因此包括:
i)基于配料重量的10%-60wt%的具有高阻尼损耗因数的橡胶如丁基橡胶
ii)基于共聚物重量的0.1-5wt%的发泡体系
iii)基于配料重量的25%-70wt%的阻燃剂体系
iv)可选地基于配料重量的1-20wt%的增塑剂或加工助剂
v)可选地基于共聚物重量的0.1-5wt%的交联剂
在优选地实施方案中配料包括:
i)弹性体
ii)包括物理发泡剂和化学发泡剂的混合物的发泡体系
iii)至少50wt%的阻燃体系
iv)聚合物加工助剂
v)弹性体的交联剂
vi)阻燃剂
vii)可选地增粘剂
聚合物加工助剂和增粘剂可以是相同的材料。
本发明进一步提供这些配料的应用以提供泡沫绝缘或减振材料,该材料包括具有满足航空器内部组件所要求的阻燃性质的材料。特别是可在蜂窝结构内设置的泡沫。我们发现这些配料可提供具有最多为1000%、典型地最多为500%的膨胀度和低于0.20g/cc、甚至低于0.17g/cc的密度的具有希望的绝缘和阻尼性质的泡沫。
配料可包含其它添加剂如此前描述的那些。
附图说明
图1是多层组合件制备的测试板。
图2是根据本发明的板的横剖面视图。
图3描绘了五个板的测量的AMCF,结果以100Hz-4000Hz的1/3倍频带呈现(频率以对数刻度计)。
图4给出了测试板测量的Darning损耗因数(DLF)。
图5显示五个板的传播损耗。
在优选的实施方案中增塑剂也是增粘剂如液体聚异丁烯,并且因此为弹性体共混物的一部分。
在又一个实施方案中,采用配料来提供在包括被蜂窝结构分隔的两个饰面板的板中的泡沫,其中蜂窝结构小室包含源自本发明的可发泡的弹性体材料的泡沫,其粘结于至少一个饰面板以及蜂窝结构小室的壁。发泡的弹性体材料可填充蜂窝结构的部分/整体并且粘结于两个饰面板。优选发泡的弹性体材料是交联的。
在优选的板中饰面板的一个或两个是“预浸料坯”。当板用于声音绝缘时,优选至少一个饰面板具有孔或穿孔以使声音进入蜂窝小室结构。当面板用于减振时,可以不需要孔或穿孔,尽管如果板要完成两种功能时,孔或穿孔是优选的。可在一个或两个饰面板中提供孔或穿孔,并且当它们仅在一个饰面板中时,那应该为面对声源的那侧。预浸料坯(pre-preg)是预浸料pre-impregnation的缩写,预浸料坯由和纤维增强材料的组合组成的;可提供该组合作为片材,其可通过加热的作用固化成刚性的高强度、低重量的片材。因此优选选择本发明中使用的预浸料坯和可发泡材料,这样加热引起发泡和粘结同时随着预浸料坯固化而发生。用这种方法,可以简单的一步加热方法生产本发明的面板,而不需要另外的加工步骤以及其它粘合剂的使用。可使用的合适的预浸料坯的实例包括含玻璃,碳或纺织纤维的环氧树脂,酚醛树脂或聚氨酯前体基体。由Hexcel提供的Hegply产品和由Gurit提供的SP产品特别有用。预浸料坯在泡沫和饰面板之间固化形成结合时将与预浸料坯中的组分起反应的组分例如交联剂可包含在配料内。
根据面板的要求选择蜂窝结构。蜂窝以不同厚度,小室尺寸和密度可获得,并且也在如纸、金属、塑料等广范围的材料中可获得。
因此本发明的一个实施方案的本质是通过合适的选择可发泡弹性体材料和两个饰面板的(至少)四个组件结构使用的数量,蜂窝分隔层和嵌入面板的至少部分地填充的发泡阻燃剂弹性体吸声和/或减振层不是通过以往的多步操作、而是可以一道工序来生产。此外,通过调整配料,可使用制造设备和以往用于制备无泡沫板的制造条件如温度压力和时间来生产板。此外,通过调整配料来获得预期性能所需的发泡度和交联,可定制在声音绝缘和减振以及刚性两方面的板性能。
在优选的方法中,可通过将可发泡弹性体材料层直接施加到第一饰面板形成这样的板结构物,之后,活化该材料以软化、膨胀、可选地固化或其组合,从而将材料湿润和粘结于蜂窝的小室壁和第一板或两个板。增塑剂的存在利于生产层并且增强发泡。
一旦典型地自动地、手工地或其结合地进行组合,可将可发泡材料活化以软化、膨胀和可选地显现粘合性质,因此膨胀的可发泡材料为板提供减振、吸音或其组合与阻燃性一起,并且用于将板的组分结合在一起。
在优选的实施方案中,将可发泡材料配制成在平板压机中在将组合件加热的温度下膨胀和固化。在该方法中,将组合板结构物供应给平板压机,其经过典型地高于约65℃,更典型地高于约100℃并且甚至更典型地高于约130℃以及低于约300℃,更典型地低于约220℃并且甚至更典型地低于约175℃的温度。这样的放置典型地为至少约10分钟,更典型地至少约30分钟并且甚至更典型地至少约60分钟和低于约360分钟,更典型地低于约180分钟并且甚至更典型地低于约90分钟的时间段。当在压机中时,通常将压力施加到板结构物,促使结构物的组件朝向彼此。
可使用替代的制造工艺,如真空成型和烘烤,或典型地具有施加压力的反应釜。
本发明的包含源自配料的泡沫的板可用于一些不同制品,如运输车辆(例如机动车辆,有轨车辆,建筑物,家具等)。可使用板提供所希望的减振和声音阻尼与防火和阻燃的结合,而不需要另外的材料或层来提供这些性质。虽然不要求,但通常采用板结构物来形成这些制品之一的内部。在这样的实施方案中,将板结构物的至少一个饰面板置于制品的内开口面积和/或至少部分地限定它,而板结构的另一个饰面板靠近制品主体。例如在建筑物中,内部板或第一板将置于限定建筑物的房间内部和/或限定它,而外部板或第二板将靠近建筑物外部的建筑材料(例如砖块,外壁板等)。作为另一个实施例,在如航空器的运输工具中,内部板或第一板将置于车辆的内部舱室和/或至少部分地限定它,而外部板或第二板将靠近车辆主体。
板结构物对航空器是特别有用的,其中它们可用于航空器内部的一些位置。例如,板可形成门、上储藏柜、侧板、拱道、顶板或其结组合的部分或整体,并且可用于主舱、机组休息舱、隔墙、食品柜、厕所和驾驶间。板也可用于航空器机翼或航空器的舱室的楼板结构。当在航空器内采用该结构物时,第一或内部板将典型地置于和/或至少部分地限定航空器的内部舱室。当然,板可是反转的。此外,面板可位于远离机身并且可以或可以不置于飞机的内部舱室。例如板可完全密封(例如在飞机的内门内)或可用地毯覆盖(例如在飞机的舱底板中)。应当理解最靠近内部舱室的饰面板可由美观性覆盖物覆盖,如涂料,壁纸,塑料饰带,布,皮革或其组合,并且可以仍限定内部舱室。板结构物在构思上可设置为减少进入航空器的声传播和/或振动。通常航空器包括一个或多个开口(例如通孔,界面位置等),其可在航空器的内部和围绕航空器的外环境之间提供声音和/或流体流通。因此,预期板结构可邻近放置或覆盖这样的开口来促进噪音减弱(例如吸音,声衰减或两者)。
在板中,发泡弹性体材料可填充两个板之间的蜂窝结构小室的部分、大部分或基本上全部体积。填充的体积的量可取决于如预期强度、预期吸音和预期减振的考虑。
使用如挤出和手动设置材料的多种技术可应用于可发泡材料。在一个实施方案中,可从施涂器(例如挤出机)施加材料。在该实施方案中,可将施涂器相对于将其提供到如一个或多个板和/或支撑的表面移动,反之亦然,或其结合。对施涂器所希望的是基本上完全地自动化,但同时也可以包括某些手动的组件。增塑剂有助于应用可发泡材料。这些施涂器的示例系统公开在美国专利No.5,358,397和欧洲专利申请公开No.1131080中。
当使用如挤出机的施涂器时,将可发泡材料的温度升高到其流动温度但低于其发泡温度,以有助于材料粘结到基材如第一板上,这是所希望的。在冷却时,材料是未发泡的并优选为触摸时基本上无粘性的。或者,材料可以是仅仅稍微发粘的,使得材料可以处理而没有材料的任何显著部分因该处理而被除去。
在另一个实施方案中,首先可以使用工具和/或个人手工将发泡材料层手工地或自动地施加到基材如板上。通常根据前述的方案之一手工地施加一或多块的可发泡材料。
在一个特定的实施方案中,将可发泡材料条形式的一个单个块或多个块压靠在第一饰面板和蜂窝结构,使得由于可发泡材料的粘合性质,在压机下的材料变形或两者。也预期在压机或手动施加期间使得材料条轮廓符合(例如弯曲)一个或多个板和/或蜂窝的轮廓。在该实施方案中,对于可发泡材料条典型地需要的是充分地挠性的,以允许条从第一直的状况或第一线性状况或第一形状弯曲成第二角度状况或第二弧形状况或第二形状(例如使条的一部分相对于另一个部分为直角角度),而没有显著地条的撕裂或裂纹(例如破坏条的连续性或将一部分条拉离另一个部分的撕裂或裂纹)。在该实施方案中,在本发明的配料中使用增塑剂有助于挤出较薄的条。
有利地,可发泡材料可在活化前非常容易地成形。因而,可在多个位置容易地施加材料。作为一个实施例,可将材料压成或挤成蜂窝小室。
实施例
通过以下实施例说明本发明,其中在各种含蜂窝的板上进行传播损耗和结构插入损耗以及防火和阻燃性测试。
传播损耗测量是按照据ISO15186-1:2000的并且获得了令人满意的结果。
从以下材料通过构成图1所示的多层组合件制备测试板。
板由9.4mm厚、NOMEX材料(玻璃纤维浸渍纸)、3.2mm小室大小和29kg/m3总密度的蜂窝状芯制成,并且饰面板由预浸料坯制成,外部预浸料坯来自ISOVOLTAbrand,referenceAIRPREG2050/T0F1并且内部预浸料坯也来自ISOVOLTAbrandwithreferenceAIRPREGPY8150。
为了对比而制备板4,并且仅由蜂窝和饰面板制备。除了将本发明的可发泡、可交联的弹性体材料层在加热前放入在内部预浸料坯侧的压机中之外,板1,2和3是相同的。可发泡的可交联弹性体材料具有以下配料
i)40wt%的异丁烯和对甲基苯乙烯(EXXPRO3443)的溴化共聚物
ii)2wt%的氧化锌和硬脂酸锌的混合物作为异丁烯和对甲基苯乙烯的溴化共聚物的交联剂
iii)10wt%的液体聚异丁烯
iv)包括4wt%偶氮二甲酰胺和0.5wt%偶氮二碳化物(azodicarbonide)的胺基活化剂的发泡剂体系
vii)余量的衍生自磷酸铵和硼酸锌的化合物作为阻燃剂
将组分共混和挤出来提供在压机中使用的可发泡材料层。
在膨胀之前可发泡材料层的厚度为1.2mm以及膨胀后为约5mm,因此填充蜂窝小室的半高度。材料的膨胀度是400-500%。图2是板1的横截面,显示蜂窝内部的泡沫并有效地粘结到小室边界。板1、2和3确定为相同的,并且微小的重量差异反映了少小的工艺变动。
板5也是对比性的,它没有内部泡沫并且为设有通过自粘着带粘结于板的材料外部阻尼层的板4。使用的阻尼层为0.7mm厚和将该材料的两层胶合并粘到外部预浸料坯以得到1.4-1.5mm的总厚度。
在以下的压机中生产板。
a)对于大的板(1000x1500mm)
压机制造商:Langzauner
板的尺寸:1350x2750mm
控制:通过计算机引导(Touchscreen):通过压力
温度:通过计算机引导:加热和冷却系统(最大值2-3℃/min),
b)对于较小的板(250x250mm)
压机制造商:Langzauner
板的尺寸:1000x1300mm
与大的压机相比相同的控制,
温度:最多400℃(快速加热和冷却系统(10℃/min)。
实施例1
在大的平板压机中采用以下周期生产含泡沫的板1,2,3和4。
-用可发泡的可交联材料和蜂窝,没有预浸料坯的第一固化周期
-在压机中冷却整个板
-打开压机并且引入预浸料坯和在155℃进一步加热组合件30分钟。
-使得经过1小时的周期从155℃冷却到50℃。
实施例2
在大的平板压机中经过30分钟将温度从50℃增加到155℃,并且在155℃保持另外的30分钟。然后冷却到50℃来生产板5。
实施例3
采用较小的平板压机将.5mm厚的几片可发泡的可交联材料放在蜂窝上,并且使用实施例2中采用的固化周期生产板6。
使用具有金钢石刀刃的刀片的来自Altendorf(型号F45)的切割台,以4000rpm的切割速度将板切割以提供测试用试样。
图2是根据本发明的板的横剖面视图。
结构插入损耗(StructureBornInsertionLoss)测量提供有关板限制在环境中的由于振动产生的噪音的能力的信息,其中使用板和基于辐射功率和机械输入功率的对比。辐射功率与机械输入功率的比率是板的称为AMCF的“声音-机械换算因数”的测量。
两个具有可比结构的不同板的AMCF之差将产生结构插入损耗(SBIL),其是声音绝缘的量的测量,可期望将声音阻尼组件添加到无阻尼结构。
使用以下公式进行AMCF计算:
其中Pinj是机械地注入结构的功率并且Prad是辐射功率。
因此使用以下公式进行SBIL计算:
使用阻抗头测量机械输入功率,同时使用声强探头测量辐射功率。对于板上的3个不同的振动器位置测量输入功率和使用以下公式计算:
〈FV*>是在输入位置的力和速度之间的平均互谱图。经过时间和频率来完成平均数。
通过测量经过板的消音侧面的强度获得每个振动器位置的辐射功率。
对于每个振动器位置,使用具有四分之一英寸传声器和6mm间隔的强度探头覆盖100Hz-10kHz的频率范围以1/3倍频带来测量辐射功率。使用以下公式计算辐射功率:
Prad=〈I>*Area
〈I〉是平均声音强度。
按照此前为传播损耗测量描述的标准完成强度测定。
该结构安装在混响室和消声室之间。由于混响室在板的振动器侧,在房间中提供另外的消音材料以防止与房间的声学响应偶合。
用跳簧电缆负载的振动器来激发板。用胶水将阻抗头安装在板上。从一个振动器位置到另一个振动器位置,除去阻抗头并将其粘合到下一个位置。当测试五个板时,将阻抗头粘合在确切的相同的位置。
也在板上进行振动测量。加速计用来获得空间平均的二次的迁移率和阻尼损耗因数,使用板表面以上的衰减率方法。相同的位置用于全部板。
使用3个不同的振动器位置进行测试,以便从最可能的模式(在力位置的间隔的平均数)获得振型作用。
使用5个加速计移动到板上的6个不同的位置测定间隔平均的二次的迁移率(经过力的速度)。所有信号参考阻抗头测力传感器。经过20秒的周期的时间平均值进行振动测量。然后将激励信号关闭来测量加速计衰减信号。然后使用内部的Matlab代码使用衰减率方法计算阻尼损耗因数来将衰减信号后处理。
至于传播损耗测试,SBIL测量需要强度探头并且需要用于机械输入功率测量的阻抗头。在如下的测量之前校准每个传感器
测试传播损耗的板也测试结构插入损耗。
结果
图3描绘了五个板的测量的AMCF。结果以100Hz-4000Hz的1/3倍频带呈现(频率以对数刻度计)。
详细结果展示在表2中。
图4给出了测试板测量的Darning损耗因数(DLF)。由于将合适的功率在高频率输入结构物的困难和板的高阻尼,结果限制在1.6kHz。注意即使对于板4和5(具有本体层的板4),总有通过安装在测试窗上增加的1600Hz以上的另外的阻尼,板也是大大受到阻尼的,并且加速计信号太低以致于不能得到可靠的结果。
图5显示五个板的传播损耗。
表2:所有测试构型(dB)的AMCF结果。
实施例4
采用以下配料进行防火和阻燃性测试。
用如实施例1相同的方法使用材料来生产泡沫。
发现生产的泡沫具有0.15-0.17的发泡密度以及具有可接受的0.35-0.45的Tanδ的绝缘和阻尼性质。
实施例5-7
采用以下配料以与板1的生产类似的方式生产板。份数是配料的重量百分比。
IndopolH300同时起增塑剂和增粘剂的作用。
板具有与板1、2和3可比的传播损耗和结构性插入损耗性能。
FARPart25§25.853(a)和FARPart25§25.853(d)
将板的部分经过适用于加压航空器舱室内部的FAA放热和放热率测试(FARPart25§25.853(d)),并且发现如在两个测试中通过,加热不超过65Kwmin/m2。从每个配料制备的泡沫经过FAA火烟和毒性测试(FARPart25§25.853(a)),并且被发现全部符合以下要求
i.燃烧长度不超过152mm
ii.燃烧时间不超过15秒
并且
iii.烟浓度不超过150。
Claims (25)
1.可发泡配料,其用于制备具有改进的阻燃性能的减振材料,该可发泡配料包括:
i)弹性体,其中该弹性体无卤素,
ii)增塑剂或加工助剂,
iii)发泡体系,
iv)阻燃剂体系,和
增粘剂。
2.根据权利要求1的配料,其中该增塑剂和该增粘剂是相同的材料。
3.根据权利要求1的可发泡配料,其中该弹性体可交联,并且该配料包含用于弹性体的交联剂。
4.根据权利要求1的配料,其中该弹性体以可发泡材料的5wt%-65wt%的量存在。
5.根据权利要求1的配料,其中该弹性体是具有高阻尼损耗因数的橡胶。
6.根据权利要求1的配料,其中该弹性体是丁基橡胶。
7.根据权利要求1-5任一项的配料,其中该弹性体可交联并且是共聚物,所述共聚物是异烯烃和烷基苯乙烯的共聚物。
8.根据权利要求7的配料,其中所述共聚物是C4-C7异烯烃和C1-C5烷基苯乙烯的共聚物。
9.根据权利要求1-6任一项的配料,其包含基于配料重量的0.1wt%-5wt%的发泡体系。
10.根据权利要求1-6任一项的配料,其包含基于配料重量的25wt%-70wt%的阻燃剂体系。
11.根据权利要求1-6任一项的配料,其包含1-20wt%的该增塑剂。
12.根据权利要求9的配料,其中该增塑剂是液体聚丁烯。
13.根据权利要求1-6任一项的配料,其包含辅助的增塑剂。
14.根据权利要求13的配料,其中该辅助的增塑剂是阻燃剂增塑剂。
15.根据权利要求1-6任一项的配料,其中该阻燃剂包含i)、ii)和iii)的混合物
i)含磷阻燃剂
ii)金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂
iii)石墨。
16.根据权利要求15的配料,其中该石墨是热膨胀性石墨。
17.根据权利要求1-6任一项的配料,其中发泡体系是物理发泡剂和化学发泡剂的混合物。
18.根据权利要求16的配料,其中该发泡体系和该交联剂在100℃-180℃范围的温度下实现其各自的功能。
19.根据权利要求1-6任一项的配料,包含:
i)基于配料重量的10%-60wt%的弹性体
ii)基于配料重量的0.1-5wt%的发泡体系
iii)基于配料重量的25%-75wt%的阻燃剂体系
iv)基于配料重量的1-20wt%的增塑剂或加工助剂
v)基于共聚物重量的0.1-5wt%的交联剂,
和增粘剂。
20.阻燃剂组合物,包括:
i)含磷阻燃剂
ii)金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂
iii)石墨。
21.根据权利要求20的阻燃剂组合物,包含:
a)20wt%-60wt%的含磷阻燃剂,
b)5wt%-25wt%的金属氧化物阻燃剂、金属氢氧化物阻燃剂或金属水合物阻燃剂,
c)5wt%-25wt%的石墨,
其中各组分含量之和为100%。
22.根据权利要求20或21的阻燃剂组合物,其中含磷阻燃剂选自红磷、磷酸铵、三聚氰胺磷酸酯或焦磷酸酯。
23.根据权利要求22的阻燃剂组合物,其中磷酸铵为多聚磷酸铵。
24.根据权利要求20或21的阻燃剂组合物,其中金属氧化物或金属氢氧化物为三水合铝或氢氧化镁。
25.根据权利要求20或21的阻燃剂组合物,其中使用的石墨是热膨胀性石墨HEG。
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Also Published As
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CN102459434A (zh) | 2012-05-16 |
WO2010149353A1 (en) | 2010-12-29 |
WO2010149354A1 (en) | 2010-12-29 |
US20120153242A1 (en) | 2012-06-21 |
CA2764687A1 (en) | 2010-12-29 |
BRPI1015204A2 (pt) | 2018-02-20 |
EP2445955A1 (en) | 2012-05-02 |
EP2445708A1 (en) | 2012-05-02 |
BRPI1015191A2 (pt) | 2017-06-13 |
CA2764688A1 (en) | 2010-12-29 |
US20120177877A1 (en) | 2012-07-12 |
CN102802931A (zh) | 2012-11-28 |
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