CN102712115A - 生产吸声柔性成型泡沫的方法 - Google Patents
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Abstract
本发明涉及一种生产吸声聚氨酯柔性成型泡沫构件的方法。
Description
本发明涉及一种生产吸声聚氨酯柔性成型泡沫构件的方法。
聚氨酯柔性成型泡沫主要也应用于吸声领域。通过开孔泡沫的性质,由吸声作用减小了所谓的空气载声。按照现有技术,将这种泡沫(这里也称作弹簧)与一种较重的材料(这里也称作质量(Masse))相组合,就能减小空气载声和结构声。将尽可能致密而且薄的质量层与尽可能厚的弹簧层相组合,即可获得极佳的吸声效果。
在DE 10 2004 054 646中,从两种聚氨酯制备质量和弹簧,这两种聚氨酯的基本聚醚配方和异氰酸酯并无区别,区别仅在于其混合比例。在该质量中使用的多元醇比例低于弹簧中的多元醇比例,并且质量中的多元醇还掺有重物质。该方法的缺点是生产过程中需要三个而不是两个半模。通过两个半模(A)和(B)适当压缩所填充的发泡聚氨酯系统形成质量,从而不存在或者几乎没有发泡空间,因此聚氨酯就会在反应后形成致密层。这种方法的缺点是需要增大锁模力。将半模(B)替换成半模(C)产生一个新的型腔,在半模(A)的侧面通过致密层形成该型腔的边界,在对侧面通过半模(C)自身形成边界。将聚氨酯系统适当充入型腔,使其在发泡过程中能够膨胀进入型腔的剩余容积之中并且产生泡沫。
M.Tavema(“高填充性聚氨酯配方-用于前围板的创新技术”2009年聚氨酯杂志六月/七月刊)报道了一种方法,其中将填料分散在多元醇之中,在混料头中与异氰酸酯混合,然后将其喷出形成质量。与之前所述的一样,在随后的反应注射成型(RIM)工艺过程中形成弹簧。缺点是与填充的多元醇接触的机器部件磨损严重,因此必须采取措施防止磨损。此外还必须大幅度加热原料来降低粘度,随之带来的缺点是:增大了对原料进行调温处理的技术费用,并且原料在配料机的日用储罐中承受高的热负荷。该方法的另一缺点是:需要两种聚氨酯系统来制备一个致密的质量和一个发泡的弹簧。此外还无法根据局部需要更改喷涂面中的填料含量,因为多元醇和填料以固定的混合比分散存在。仅改变多元醇和异氰酸酯之间的混合比是可能的,但会导致喷涂后的质量层中的基质出现局部改变的机械特性。
DE-A 101 61 600和DE-A 10 2004 039 438均描述了一种将质量层喷涂到三维成型表面上的方法。这里首先混合多元醇和异氰酸酯,然后进行喷涂。在喷头之外将重物质优选是硫酸钡定量加入到自由喷束之中。该方法的缺点在于:要么需要两种不同的聚氨酯系统来制备一个致密的质量层和一个弹簧层,或者必须执行使用三个半模而不是使用两个半模的生产步骤,与之前结合DE-A10 2004 054 646所解释的一样。
此外按照DE-A 101 61 600所述的方案,如果在混合头之外将用量高的填料定量加入到喷束之中,则无法完全湿润填料。如果填料含量比例高,就会有很多填料颗粒处在其它填料颗粒的滑流(Flugschatten)之中,从而使得聚氨酯反应混合物的液滴无法将其湿润或者湿润程度不够充分。此外由于湍流几乎不能促进喷束中的湿润过程,因此湿润不完全。相互碰撞的喷束液滴和填料颗粒将会具有遵循动量定律而改变的合成运动轨迹,并且可能会因为与尚未改变运动轨迹的相邻颗粒碰撞而引起轻微的湍流,但是逐渐扩大的喷束性质会迅速减小发生此类碰撞的概率,因为在呈锥形扩大的喷束中所有相邻颗粒均在相对远离而去。结果湍流将会迅速减弱,最终使得颗粒湿润不够充分。DE-A 10 2004039 438还提出了将填料定量加入到混料头之中的想法,但是并没有进一步解释以何种方式和方法来实现。
本发明的任务在于,提供隔音及消声衬里,其制备仅需要两个半模,并且仅需要一种由多元醇配方和异氰酸酯配方构成的聚氨酯系统,因此可以将模具的投资成本保持在低的程度,节约液体的仓储空间,并且简化液态原料的后勤工作。
按照本发明所述,完成这一任务的方式为:在混料头中将高密度固体物质(A)、任选地还将第二种物质(B)和/或者第三种物质(C)一起与异氰酸酯组分(E)和多元醇组分(D)混合,将该混合物喷涂到半模1上形成质量层。物质(B)和(C)减少或者阻止聚氨酯反应混合物发泡。因此可以省去一个半模,否则就要以形成相应小的型腔并且使模架形成高锁模力的方式来阻止发泡聚氨酯。在第二个步骤中混合不含物质(A)、(B)和(C)的异氰酸酯组分(E)与多元醇组分(D)来制备弹簧层,其中所用异氰酸酯与多元醇的比例大于制备质量层时的比例。聚氨酯发泡填充质量层与半模2之间的型腔。
本发明涉及一种生产聚氨酯柔性成型泡沫的方法,所述柔性成型泡沫包括含有固体颗粒的致密(massive)聚氨酯层和第二层发泡聚氨酯,所述方法的特征在于,
a)在混合室中(例如在室的混合喷嘴中)将含有固体颗粒的气流加入到聚氨酯反应混合物的液态喷束之中,
b)将步骤a)中含有固体颗粒的喷束喷入到两个半模构成的敞开模具的第一个半模之中,
c)利用第二个半模使得敞开模具闭合,
d)在聚氨酯反应混合物反应完全之后,将不含固体颗粒的聚氨酯反应混合物的第二股液态喷束注入到闭合的模具之中,从而注入到反应后的层上,
e)在第二种聚氨酯反应混合物完成反应之后,打开模具并且从模具中移去成型件。
优选适合用密度大于2000kg/m3、优选大于3000kg/m3、特别优选大于4000kg/m3的物质作为填料(A)。除了金属粉末之外,适用的材料还主要是:赤铁矿,钛铁矿,锡石,辉钼矿,白钨矿,黑钨矿,砂子,废弃的铬矿砂(铸造厂的垃圾),橄榄石,铬矿砂,铬铁矿,硅酸锆和闪锌矿,尤其是磁铁矿,氟石,重晶石和硫酸钡。
填料(A)优选含有直径为4μm~5mm的粒子。按照一种优选实施方式,填料(A)不含直径小于40μm的细微粒子,并且仅含有直径最多2mm的粒子。特别优选是直径为100μm~1000μm的粒子。最后提及的填料可以是例如市面上可以买到的固体物质的筛下物。
物质(B)是用来形成质量层的干燥剂。从新鲜混合的液态异氰酸酯组分(E)和多元醇组分(D)中脱除水分,并且阻止发泡反应,因为从反应混合物的两种液态组分中脱除了水分。
相对来看,在质量层中与定量异氰酸酯进行反应的多元醇用量大于弹簧层中的异氰酸酯的该用量。假定已通过干燥剂部分或者完全去除了质量层中的水。脱水使得多元醇配方的羟基数下降。当异氰酸酯指数不变时,需要将少的异氰酸酯用于多元醇配方,即可实现与弹簧层中一样的百分比转化率。异氰酸酯指数是异氰酸酯用量与用来和多元醇配方进行定量反应所需的化学计量异氰酸酯用量之间的比例乘以系数100。
按照一种优选实施方式,将弹簧层(F)和质量层(M)的异氰酸酯指数IF或IM调整为70~130。质量层(M)的异氰酸酯指数IM优选等于弹簧层(F)的异氰酸酯指数IF:
IM=IF
质量层(M)的异氰酸酯指数IM也可以具有比弹簧层(M)的异氰酸酯指数IF更加接近于100的值:
|100-IF|>|100-IM|
可以根据实施例部分中的表1可以看出,将不同比例的液态异氰酸酯组分(E)与多元醇组分(D)混合,即可制成弹簧层或质量层,其中这两个层的异氰酸酯指数均为100。
适合作为物质(B)的干燥剂例如有:硅胶、煅烧后的矾土、氯化钙、氧化钙、氯化镁、硫酸镁、氧化镁、硫酸钠、碳酸钙、硫酸铜、氧化钡、干粘土、硅酸铝、尤其是基于沸石的分子筛,例如UOP粉末,也称作Baylith(制造商UOP M.S.S.r.l.)、氧化铝、超级吸收剂,例如氢氧化钾中和的聚丙烯酸、膨润土、蒙脱石以及上述物质的混合物。特别优选使用基于沸石的分子筛。干燥剂(B)基于聚氨酯反应混合物的重量百分比用量为0.5~0%,优选为2~40%,特别优选为10~30%。
物质(C)可以是消泡剂,例如可以按照优选至多1%的重量百分比含量将其用来湿润物质(B)和/或物质(A)。但也可以例如通过注射模块将物质(C)定量加入到异氰酸酯组分(E)或者多元醇组分(D)的混料头进料管之中。但是这种方法存在危险:当从单步模式(Schussbetrieb)转换到循环运行模式时,部分物质(C)会经由混料头回流管进入日常储罐之中,从而不再能利用原料制成发泡弹簧层。因此优选采用定量加入到混料头之中的方式。如果定量加入到进料管或者混料头之中,则相对于多元醇组分(D)和异氰酸酯组分(E)总量的重量百分比用量优选为0.1~25%,特优选为1~20%,非常特别优选为5~15%。
可作为物质(C)使用的要么是将界面活性发泡剂从界面中排挤出来且自身不会产生泡沫的物质,或者是将气体、填料颗粒和聚氨酯反应混合物之间的表面张力减小的物质。这里包括天然脂肪和油、芳族和脂肪族矿物油、聚丁二烯、脂肪醇、长链皂类,例如山萮酸钠(二十二烷酸的钠盐)、聚乙二醇/丙二醇醚,例如Pluronic产品、以及混合醚或者端基团封闭的(大多数为醚化的)烷基聚乙二醇醚,尤其是基于硅酮的消泡剂,例如聚二甲基硅氧烷,以及其它有机改性或官能化聚硅氧烷。
可以将现有技术条件下熟知的多元醇组分和异氰酸酯组分作为用来制备弹簧层(F)和质量层(M)的聚氨酯柔性成型泡沫的组分(D)和(E)。事实证明,在多元醇组分中可以将一部分多元醇替换成可再生的原料,例如蓖麻油或者其它已知的植物油,其化学反应产物或衍生物。这种替换不会使得成品聚氨酯柔性成型泡沫体的特性变差,而且此类泡沫体具有有利于显著提高耐用性的优点。此外,多元醇组分除了可以含有已知的多元醇(例如聚酯多元醇,聚醚多元醇,聚碳酸酯二醇,聚醚酯多元醇)以及扩链剂和/或者交联剂之外,也可以含有其它本身已知的助剂和添加剂,例如催化剂、活化剂、稳定剂。异氰酸酯组分可以是一种有机异氰酸酯、改性异氰酸酯或者预聚物。
并非将含有固体物质的气流加入到已经分散的反应混合物喷束之中,而是在混合室中加入到尚且呈液态且没有分散的喷束之中。这里尚存在基本上分层流动的反应混合物。
本发明所述“聚氨酯反应混合物的液态喷束”指的是聚氨酯材料的这种液体喷束,尤其是用来混合液态反应组分的混合室区域内的液态喷束,该喷束以尚未细微分散在气流之中的反应混合物液滴的形式存在,尤其是处在粘的液相。
按照现有技术所述的方法,主要使用气流或者相应的喷嘴将聚氨酯反应混合物雾化,然后将含有固体物质的气流吹入到这种雾化的聚氨酯喷束之中,而本发明所述方法的特征在于:在混合喷嘴中使用含有固体物质的气流将从混合室出口流出的聚氨酯反应混合物液态喷束雾化。在这种情况下,每一个喷束中与喷束的主喷射方向正交的相邻喷射颗粒之间的距离随着与喷嘴之间距离的增大而增大。固体物质颗粒与聚氨酯液滴或者与已经湿润的填料颗粒之间发生碰撞从而使其湿润的概率必然会急剧减小。如果按照本发明所述的方法在混合室中混合填料和聚氨酯,这些关系就会发生变化。
本发明所述方法的特征在于,通过输送气流将固体物质送入混合室之中,并且在这里与聚氨酯反应混合物的液态喷束相遇。优选地,气流经由两个点或者更多的点进入混合室之中,并且特别优选相对而置,从而使得气流与固体物质在混合室中相互遇到。也可以切向送入气流。采用本发明所述的方法,颗粒不会相互偏离或者相互远离,因为受到混合室壁面的阻碍。因此按照本发明所述的方法,可在混合室内部使用聚氨酯反应混合物以无损方式强制湿润固体物质,形成一部分均匀的气体/固体物质/聚氨酯材料混合物。
优选在混合室中通过附加空气旋流再提高所得气体/固体物质/聚氨酯材料混合物的混合质量。通过切向空气喷嘴产生空气旋流,并且被空气喷嘴包围的圆表面与混合室中的主流动方向轴线形成直角。
优选通过叶轮计量装置中含有固体物质的计量槽送入气流,形成含有固体物质的气流。压缩空气流将溢出叶轮槽的固体物质带走,将其作为固体物质/空气或气体混合物输送给混合室/混料头。为了避免脉动,计量装置内部流道的直径应当经过适当设计,从而能够避免正遮盖。这种实施方式还在关闭叶轮计量装置或者叶轮计量装置的转速变化时保证有流量不变的空气可用来喷涂聚氨酯反应混合物,因此可以选择不使用或者使用可变的固体物质量进行喷涂。
采用没有压力差的方式提供固体物质,防止在进入气流之中时压实固体物质流化床。
还可通过压力平衡防止部分输送空气流经由计量装置(计量槽和间隙误差)回到储料罐之中。如果正好是有磨蚀作用的固体物质,则不可避免要设计比较大的间隙尺寸。
无论是密相输送还是稀相输送,进入混合喷嘴之中的气体与固体物质的最大可能体积比优选在20∶1~200∶1之间,特别优选在50∶1~100∶1之间。
例如可以通过改变固体物质输送速率的方式予以实现。
此外还优选使用氮气尤其是空气作为气体。这些气体的成本特别低廉,因此有助于相应降低本发明所述方法的成本。
以下将依据实施例对本发明进行详细解释。
实施例:
仅仅制备质量层(M)进行试验和测量。
在混料头(混合室)中,首先动态混合多元醇组分和异氰酸酯组分,然后然后将固体物质/气体流送入反应混合物之中,在空气旋流中使得聚氨酯反应混合物、固体物质和气体构成的混合物再次混合,然后通过喷嘴将其喷出。
按照所述的方式进行试验1,但是与其它试验的不同之处在于没有将固体物质/气体构成的气流送入混合室之中。
表1:所使用的聚氨酯反应混合物和填料
**-对比
计算多元醇与异氰酸酯混合质量比时不考虑有星号*标记的水,因为水将会被干燥剂吸收,并且在吸收后的形态下不再与异氰酸酯反应形成二氧化碳。
原料说明:
表2:试验数据
**-对比
Claims (8)
1.生产聚氨酯柔性成型泡沫的方法,所述柔性成型泡沫包括含有固体物质颗粒的致密聚氨酯层和第二发泡聚氨酯层,其特征在于,
a)在混合室中将一股含有固体物质颗粒的气流或者多股含有固体物质颗粒的气流送入到聚氨酯反应混合物的液态喷束之中,
b)将步骤a)中含有固体颗粒的喷束喷入到两个半模构成的敞开模具的第一个半模之中,
c)利用第二个半模使得敞开模具闭合,
d)在聚氨酯反应混合物反应完全之后,将同一个聚氨酯反应混合物的第二股不含固体物质颗粒的液态喷束注入到闭合模具之中,
e)在第二种聚氨酯反应混合物反应完全之后,打开模具并且从模具中移去成型件。
2.根据权利要求1所述的方法,其特征在于,步骤a)和步骤d)所使用的聚氨酯反应混合物具有相同组成,并且含有以下组分
i)有机异氰酸酯组分,以及
ii)多元醇组分。
3.根据权利要求1所述的方法,其特征在于,所述固体物质颗粒是
A)具有≥2000kg/m3的高密度的、作为填料的第一种固体物质,
B)作为干燥剂的第二种固体物质,以及任选地
C)作为消泡剂的第三种固体物质。
4.根据权利要求1所述的方法,其特征在于,所述固体物质颗粒是
A)具有≥2000kg/m3的高密度的、作为填料的第一种固体物质,其任选地用消泡剂湿润,以及
B)作为干燥剂的第二种固体物质,其任选地用消泡剂湿润。
5.根据权利要求1所述的方法,其特征在于,除了聚氨酯反应混合物之外,还将消泡剂引入混合室之中。
6.根据权利要求1所述的方法,其特征在于,含有固体物质颗粒的气流以气体与固体物质之间的体积比为20∶1~200∶1含有颗粒。
7.根据权利要求3所述的方法,其特征在于,填料(A)的固体物质颗粒直径为4μm~5mm,优选为40μm~2mm,特别优选为100μm~1000μm。
8.根据权利要求3或4所述的方法,其特征在于,相对于聚氨酯反应混合物定量加入干燥剂(B)的重量百分比为0.5~50%,优选为2~40%,特别优选为10~30%。
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US6100363A (en) * | 1998-03-13 | 2000-08-08 | Basf Corporation | Energy absorbing elastomers |
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US6100363A (en) * | 1998-03-13 | 2000-08-08 | Basf Corporation | Energy absorbing elastomers |
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