CN1723107A - 机械发泡装置用-液型固化糊状材料 - Google Patents
机械发泡装置用-液型固化糊状材料 Download PDFInfo
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- CN1723107A CN1723107A CNA2004800019375A CN200480001937A CN1723107A CN 1723107 A CN1723107 A CN 1723107A CN A2004800019375 A CNA2004800019375 A CN A2004800019375A CN 200480001937 A CN200480001937 A CN 200480001937A CN 1723107 A CN1723107 A CN 1723107A
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Abstract
一种液型固化糊状材料,该材料用于对糊状材料和低压气体进行机械混合制造发泡材料并进行该发泡材料的排放和膨胀,从而可以通过使用适合进行该方法的发泡装置来获得含有致密而均匀封闭泡孔的固化产品的方法。具体而言,一种液型固化糊状材料,该材料显示在图1的曲线中所限定区域中包含的粘度特性,图1的曲线是显示剪切速率和表观粘度之间关系,其中低剪切速率区(0.43秒-1)中的点A和B处的表观粘度在50-30000泊之内(用布鲁克菲尔德旋转粘度计使用7号锭子,在2rpm、20℃下测量的),高剪切速率区(783秒-1)中的点C和D处的表观粘度在20-2000泊之内(按照JIS K2220,用表观粘度计在20℃下测量的)。
Description
技术领域
本发明涉及一种用于机械发泡装置的一液型(one-pack type)固化糊状材料,更具体而言,适合用于通过如下方法制造含有致密而均匀封闭泡孔的固化产品的一液型固化糊状材料:将低压气体机械混合和分散到糊状材料中,制造可膨胀材料,接着排放和膨胀该可膨胀材料,特别是通过使用适宜于实施该方法的机械发泡装置。
技术背景
迄今为止,通过将低压气体机械混合和分散到糊状材料中,制造可膨胀材料,接着将该可膨胀材料排放和膨胀的确定方法(排放和膨胀法)是已知的,该方法包含用活塞泵将该糊状材料和低压气体机械混合并分散,所述的活塞泵在气缸中往复运动,进行吸气冲程和排气冲程,在活塞泵的吸气冲程过程中和/或之后,将气体供应入气缸中,
通过分批方法,用该气体将糊状材料供应入气缸中,
在供应糊状材料后,通过使用活塞泵进行排气冲程,和
在排气冲程中将气体糊状材料排到管道中,
然后对所得到的可膨胀材料进行排放和膨胀,
以及适合用于实施该方法的机械发泡装置(参见,JP-B-3212533(JP-A-10-272344))。
发明内容
从增加处理安全性和气体注入的可靠性以及高度精确地控制成型放大倍数考虑,上面所述方法是非常有用的。但是,用排放和膨胀方法制造的固化产品(发泡产品)根据开始的糊状材料有时具有连续的泡孔(即大小不均匀的泡沫),因此,需要总能获得含有致密而均匀封闭泡孔(即均匀微孔)的稳定成型产品。
在这种情况下,本发明的发明人进行了深入研究,结果发现规定糊状材料的粘度特性能达到上面所述目的,从而完成了本发明。
即,本发明提供了一种排放和膨胀可膨胀材料来制造含有致密而均匀封闭泡孔的固化产品的方法,
该方法包含:将低压气体机械混合和分散到糊状材料中,制造出可膨胀材料,接着排放和膨胀可膨胀材料,
其中糊状材料是具有由在图1的曲线中的点A、B、C和D所限定区域中包含的粘度特性的一液型固化糊状材料,图1的曲线是显示剪切速率和表观粘度之间关系,所述的点A和B是在低剪切速率区(0.43秒-1)中表观粘度为50-30000泊的点(用布鲁克菲尔德旋转粘度计使用7号锭子,在2rpm、20℃下测量的),而点C和D是在高剪切速率区(783秒-1)中表观粘度为20-2000泊的点(按照JIS K2220,用表观粘度计在20℃下测量的)。本发明还提供一种可用于上面所述方法的具有上面所述粘度特性的一液型固化糊状材料。
对本发明一液型固化糊状材料的树脂种类或者固化方法没有限制,但是应当具有上面所述粘度特性,特别是该材料可以应用于上面所述的JP-B-3212533(JP-A-10-272344)中所述的机械发泡装置。
至于上面所述的粘度范围,当0.43秒-1下的表观粘度小于500泊时,由于泡沫崩溃而发泡放大倍数缩小,另一方面,当表观粘度大于30000泊时,排放球(discharge bead)周围部分的漏气增加,导致成型放大倍数至多为2倍。此外,当783秒-1下的表观粘度小于20泊时,发泡放大倍数由于在排放时泡孔塌陷而缩小,而当表观粘度大于2000泊时,由于材料难以液化而使排放变得不可能。
除了这样的低/高剪切速率外,中等剪切速率区(64秒-1)的表观粘度(按照JIS K2220,用表观粘度计在20℃下测量的)也被设置在27-3000泊的范围内。
一液型固化糊状材料指的是一液型、使用前在室温至加热温度下具有高粘度的粘性糊状的材料,这种材料的固化机理是基于通过如下方法而国固化:通过反应、通过从加热熔融状态冷却到室温、和通过施加热能、光、辐射能等。它们的实例为可湿固型、热固型、热熔型、溶胶凝胶型、硫化-交联型和可光/辐射固化型组合物;所述的组合物包含聚氨酯树脂、有机硅树脂、环氧树脂、合成橡胶、聚烯烃树脂、聚酯树脂、丙烯酸树脂、聚(氯乙烯)或者其他热塑性塑料或者热塑性弹性体;其可以从热塑性和热固性材料的单体、低聚物、聚合物等来制备。
在一个实施方案中,一液型固化聚氨酯糊状材料,包含含有活性异氰酸酯端基(NCO基)的氨基甲酸酯预聚物;或者封端氨基甲酸酯预聚物和/或封端聚异氰酸酯化合物,这些化合物被暂时封端,以钝化氨基甲酸酯预聚物和/或聚异氰酸酯化合物的活性异氰酸酯基。此外,该材料包含以下的那些材料:以氨基甲酸酯预聚物作为主要组分且还可以将其制备成可湿固型;
与潜固化剂组合的热固型;或者和封端聚异氰酸酯化合物组合的包含一般固化剂和/或潜固化剂的热固型。
用作如上组成的聚氨酯糊状材料的包含活性异氰酸酯基的氨基甲酸酯预聚物可以通过过量的聚异氰酸酯化合物和多元醇的反应而获得。
聚异氰酸酯化合物包括芳香族、脂肪族和脂环族聚异氰酸酯化合物,例如甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯、二异氰酸3,3’-二甲基-4,4’-联苯酯、1,4-苯二异氰酸酯、苯二甲撑二异氰酸酯、四甲代苯二甲撑二异氰酸酯、萘撑二异氰酸酯、二环己基-甲烷-4,4’-二异氰酸酯、粗TDI(crude TDI)、聚亚甲基聚异氰酸苯酯、异佛尔酮二异氰酸酯、1,6-己二异氰酸酯、苯二甲撑二异氰酸酯氢化物,以及这些异氰酸酯化合物的异氰脲酸酯、碳二亚胺或者缩二脲化合物,这些化合物可以单独使用或者其一种或者多种组合使用。
本发明中的多元醇组分包括,例如,
聚醚型多元醇,其是通过烯化氧例如环氧乙烷、环氧丙烷以及环氧乙烷和环氧丙烷混合物和多元醇例如1,2-亚乙基二醇、丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、蔗糖等的加聚反应而制备的;
1,2-亚乙基二醇、丙二醇及其低聚二元醇;
多元醇,例如丁二醇、己二醇和聚四亚甲基醚乙二醇;
聚酯型多元醇,例如聚己内酯多元醇和聚己二酸亚乙基酯;
聚烯烃多元醇,例如聚丁二烯多元醇和聚异戊二烯多元醇;
含有羟基的高级脂肪酸酯,例如蓖麻油;
含有丙烯酰基多元醇和/或一个或多个羟基的聚硅氧烷多元醇;以及
通过聚醚型多元醇或者聚酯和乙烯基单体的接枝聚合而制备的多元醇聚合物。
可以将多元醇组分和过量的聚异氰酸酯化合物,以聚异氰酸酯化合物NCO基/多元醇组分OH基的当量比为1.1-3.5的比例进行反应,制备含有活性异氰酸酯端基的氨基甲酸酯预聚物。反应可以在室温或者60-100℃的加热温度下,在催化剂(例如有机锡化合物如二月桂酸二丁锡,铋化合物如辛炔酸铋,叔胺化合物等)存在下,进行1-24小时。从而可以制备具有活性异氰酸酯端基(0.5-10%(w/w))和粘度(3000-50000厘泊/20℃)的氨基甲酸酯预聚物。
可以将一液型固化聚氨酯糊状材料制成可以通过氨基甲酸酯预聚物的活性异氰酸酯基和大气中的湿气反应而固化的可湿固型。对于可湿固型糊状材料,可以使用潜固化剂,例如酮亚胺化合物、烯胺化合物、醛亚胺化合物、噁唑烷化合物等,它们通过多胺化合物和羰基化合物的脱水缩合反应而可逆地制备。
另一方面,为了将氨基甲酸酯预聚物制成和潜固化剂组合的热固型,可以通过加热进行活化。优选的潜固化剂是钝化的固体多胺。室温下的固体多胺的优选制备方法可以是,例如将76.9重量份的平均粒子大小约为8微米的1,12-十二烷二胺(mp:71℃)和23.1重量份的平均粒子大小为0.02微米的二氧化钛混合;用喷磨机将混合物研磨,得到平均粒子大小约为8微米的微粉化多胺,该微粉化多胺和二氧化钛粘合在一起。
本发明的发明人在WO 95/26374中详细描述了制造一液型固化聚氨酯糊状材料的程序。该程序总结如下。糊状材料是通过下面的方法制备的:将钝化固体多胺的潜固化剂加入到通过多元醇和过量的聚异氰酸酯化合物反应而获得的单独的或者混合的含有活性异氰酸酯端基的氨基甲酸酯预聚物中,其中所述用作潜固化剂的固体多胺显示mp>50℃,并且是例如微粉化涂层的多胺,这种多胺是通过将平均粒子大小为2微米的微粉化粉末粘合在平均粒子大小为约20微米的固体多胺的表面上,从而钝化多胺的活性氨基而制备的。固体多胺和微粉化粉末是以1/0.001-0.5(固体多胺∶微粉化材料)的重量比使用的,从而表面的氨基被钝化。
本发明中使用的固体多胺包括熔点不低于50℃,室温下为固体的芳香族或者脂肪族多胺化合物,例如芳香族固体多胺,如4,4’-二氨基二苯甲烷、2,4’-二氨基二苯甲烷、3,3’-二氨基二苯甲烷、3,4’-二氨基二苯甲烷、2,2’-二氨基联苯、2,4’-二氨基联苯、3,3’-二氨基联苯、2,4-二氨基苯酚、2,5-二氨基苯酚、邻-苯二胺、间-苯二胺、2,3-甲苯二胺、2,4-甲苯二胺、2,5-甲苯二胺、2,6-甲苯二胺、3,4-甲苯二胺等;以及脂肪族固体多胺,如1,12-十二烷二胺、2,10-癸二胺、1,8-辛二胺、1,14-十四烷二胺、1,16-十六烷二胺等,这些多胺可以单独使用或者其两种或者多种组合使用。研磨固体多胺以将其平均粒子大小控制在20μm以下,优选3-15μm。
一种钝化潜固化剂中固体多胺的方法是将粒子表面的氨基涂覆钝化剂。可以使用有机或者无机微粉化粉末作为钝化剂,而且可以将其粘合在固体多胺的粒子表面。微粉化粉末还包括无机细粒,例如二氧化钛、碳酸钙、粘土、硅石、氧化锆、碳、矾土和滑石,以及有机细粒,例如聚(氯乙烯)、聚丙烯酸树脂、聚苯乙烯和聚乙烯。此处使用的微粉化粉末的平均粒子大小不超过2微米,优选不超过1微米。固体多胺的钝化程序是将固体多胺的粒子表面用上面所述微粉化粉末覆盖。在钝化程序中,固体多胺粉末/微粉化粉末的重量比在约1/0.001-0.5的范围内。在磨碎固体多胺以达到预定粒子大小的过程中,将微粉化粉末混合和分散其中,因而微粉化粉末可以粘合在固体多胺粒子的表面上。
当通过加热再活化时,将氨基甲酸酯预聚物和如上制备的钝化固体多胺潜固化剂以多胺中的氨基和氨基甲酸酯预聚物中的异氰酸酯基的当量比为1/0.5-2.0的比例混合。
可以通过加热使所获得的一液型固化聚氨酯糊状材料固化。特别是该材料在加热温度区间表现出临界固化特性。当温度低于60℃时,该材料不固化,但是当温度80℃或以上时,钝化的固体多胺将被再活化,然后开始固化反应,该反应在非常短的时间内就几乎反应完全。
用于热固型一液型热固聚氨酯糊状材料的封端氨基甲酸酯预聚物和/或封端聚异氰酸酯化合物是通过封端反应制备的,其中氨基甲酸酯预聚物和/或聚异氰酸酯化合物的活性NCO基可以用封端剂暂时钝化。封端剂包括酚(苯酚、甲酚、二甲苯酚、乙基苯酚等),内酰胺(ε-己内酰胺、δ-戊内酰胺、β-丁内酰胺、β-丙内酰胺等),肟类(氨基甲肟、乙酰氨基肟、丙酮肟、甲乙酮肟、二乙酰基单肟、二苯甲酮肟、环己酮肟等),活化亚甲基(丙二酸二乙酯、丙二酸二甲酯、乙酰乙酸乙酯、乙酰乙酸甲酯、乙酰丙酮等),醇(甲醇、乙醇、丙醇、异丙醇、丁醇、2-乙基己醇、乙二醇一甲醚、乙二醇一乙醚、乙二醇一丁醚等),苯并三唑,硫醇,酰胺,酰亚胺,胺,咪唑,脲等。酚、内酰胺和肟是特别优选的。氨基甲酸酯预聚物和/或聚异氰酸酯化合物的NCO基与封端剂的封端反应是在催化剂存在下,在加热温度(50-110℃)下,在封端剂的活性氢和NCO基的当量比为0.9-1.1的条件下进行的,得到活性NCO基被封端的封端氨基甲酸酯预聚物和/或封端聚异氰酸酯化合物。
用于上面封端产物的固化剂包括上面所述的作为多元醇成分用于制备氨基甲酸酯预聚物的活性氢化合物,以及聚氧化烯多胺,氨基醇的烯化氧加合物,亚烷基多胺的烯化氧加合物,聚氧化烯多胺的酮亚胺衍生物,多胺的酮亚胺衍生物等。固化剂的用量可以为活性NCO基当量数的0.5-1.5倍。
用于具有上面所述粘度特性的一液型固化聚氨酯糊状材料的填料实例为重质碳酸钙、处理过的碳酸钙、粘土、硅石、氧化锆、碳、矾土、滑石、云母、气球、有机塑料气球、塑料粉末、塑料纤维等。糊状材料可以任选包含适合数量的增塑剂(例如邻苯甲酸二丁酯、邻苯甲酸二辛酯、邻苯甲酸二环己酯、邻苯甲酸二异辛酯、邻苯甲酸二异癸酯、邻苯甲酸二苄酯、磷酸三辛酯、环氧增塑剂、聚酯增塑剂如己二酸酯),溶剂,触变剂,紫外线吸收剂,抗氧化剂,粘合促进剂,脱水剂,发泡调节剂,粘度调节剂等。
除了粘度特性以外,也可以协调主要组分氨基甲酸酯预聚物的其他性质,例如通过填料的种类、粒子大小和数量;表面处理的和未处理的填料;增塑剂的种类和数量;粘度调节剂等来调节和流动型与结构粘度之间关系有关的触变性质。
更具体而言,可以用如下方法制备本发明的一液型固化糊状材料:首先,可以将聚醚型多元醇和二苯甲烷二异氰酸酯在80℃的温度下反应2小时,得到含有活性异氰酸酯端基的氨基甲酸酯预聚物(NCO端基的数量为2.4%,粘度为100000cps/20℃)。潜固化剂的钝化固体多胺是通过将76.9重量份的平均粒子大小约为8微米的1,12-十二烷二胺(mp:71℃)和23.1重量份的平均粒子大小为0.02微米的二氧化钛混合,用喷磨机将混合物研磨成100重量份的平均粒子大小约为8微米的所需的微粉化涂层多胺而制备的。接着,向100重量份的含有上面所述异氰酸酯端基的聚氨酯预聚物中,加入2-10重量份的潜固化剂,并且向其中加入0-100重量份的填料。当需要得到不透明的白色或者透明的发泡固化产品时,任何填料都不要混合,而当需要形成刚性发泡固化产品时,混合大量的填料。为了获得具有本发明所需粘度特性的组合物,使用表面处理过的碳酸钙和未处理的重质碳酸钙作为填料。当需要韧性发泡固化材料时,则使用加强填料,例如碳和硅石。如果结合的上面所述加强填料的数量超过50重量份,则在低剪切速率区中的粘度增加且触变性变强,于是可能不具有本发明所需的粘度特性。为了避免这种不利情况,应当加入碳酸钙。当碳酸钙粒子大小小时,表现出的触变粘度特性类似于结合了加强填料的,于是使用粒子大小超过20μm的碳酸钙来调节粘度特性。例如,当以10重量份的重质碳酸钙(平均粒子大小:45μm)、10重量份的用脂肪酸处理过的碳酸钙(平均粒子直径:3μm)、10重量份的碳作为填料,将它们与20重量份的增塑剂混合时,获得的是糊状材料在低剪切区粘度为1000-5000泊,在高剪切区粘度为100-300泊,热固临界温度为约80℃的一液型热固糊状材料。可以任选混合硅油、非离子表面活性剂。
其次,在另一实施方案中,以聚硅氧烷可湿固型材料和热固型材料作为一液型固化硅氧烷糊状材料的示例。作为交联剂,在两端都有活性羟基的有机聚硅氧烷(聚硅氧烷)(硅烷醇)和含两个或者多个水解性官能团的硅烷或者硅氧烷化合物是基本成分,这些成分可以被介质中的或者大气中的湿气所水解并且缩合而固化。特别地,为了制备热固型糊状材料,可以任选使用含有自由基聚合的不饱和双键的聚硅氧烷或者不含硅氧烷键的单体、低聚物和/或聚合物,并加入聚合引发剂,例如过氧化物,得到所需的热固型糊状材料。在这种情况下,为了制备一液型固化聚氨酯糊状材料,可以加入增塑剂、填料、着色剂、粘合促进剂、固化反应促进催化剂、发泡调节剂、粘度调节剂等。
为了显示出本发明的特殊粘度特性,例如,可以加入50-90%(w/w)的聚硅氧烷,2-10%(w/w)的交联剂,5-50%(w/w)的填料,如果需要,还可以加入少量的催化剂和粘合促进剂。特别地,为了使低压气体更容易分散,为了使材料理想地膨胀成近似球形,并且为了防止破坏泡沫或者消泡,可以向具有这种粘度特性的一液型固化聚硅氧烷糊状材料中加入表面活性剂、硅油等。通过使用一液型固化聚硅氧烷糊状材料,尤其可以获得不透明的白色或者透明的固化产品。
除了上面所述聚氨酯和聚硅氧烷糊状材料外,可以使用如下材料作为一液型固化糊状材料:湿固型材料,其中主要组分是含有烷氧甲硅烷基端基的聚亚烷基醚聚合物,含有烷氧甲硅烷基端基的乙烯基聚合物;或者热固型材料。热固型的一液型固化糊状材料包括上面所述的聚氨酯,聚硅氧烷,以及不饱和聚酯树脂和环氧树脂,此外还有交联的过氧化物,交联的多胺化合物,交联的多酰胺化合物。
光/辐射固化性的一液型性固化糊状材料包括可UV固化的、可光固化的、可电子固化的等,其中主要组分是含有一个或多个不饱和双键的可固化单体和/或低聚物,这些材料中还可以加入橡胶、弹性体、其他聚合物、光反应引发剂等。对于透明的固化产品而言,可光/辐射固化性糊状材料是特别适合的。当填料等不透明时,光/辐射能很难穿透糊状材料,因而可以理解这样的可固化性质有其不利之处。
光固性单体包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸异癸酯、丙烯酸月桂酯、丙烯酸十八烷酯、丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、丙烯酸(甲氧乙基)酯、丙烯酸(正丁氧乙基)酯、丙烯酸(二甲基氨基乙基)酯、乙二醇丙烯酸酯、新戊二醇丙烯酸酯、1,6-己二醇丙烯酸酯、二甘醇丙烯酸酯、三甘醇丙烯酸酯(triethylene acrylate)、双丙甘醇二丙烯酸酯、乙基卡必醇丙烯酸酯、1,5-戊二醇丙烯酸酯、戊烷赤藓醇丙烯酸酯、丙烯酸四氢糠酯、丙烯酸缩水甘油酯、丙烯酸苄酯、丙烯酰磷酸(2-羟基乙基)酯、丙烯酸(2-羟基-3-苯氧丙基)酯、α,ω-二丙烯酰基双乙二醇邻苯二甲酸酯、α,ω-二丙烯酰基双乙二醇四氢邻苯二甲酸酯等。
光固性低聚物包括环氧丙烯酸酯树脂、氨基甲酸酯丙烯酸酯树脂、聚酯丙烯酸酯树脂。氨基甲酸酯丙烯酸酯树脂因为其固化后的挠性和弹性而是优选的。光固性低聚物是基础树脂(base resin),其可能是固化产品特性的一个决定因素。所用的光固性单体和/或低聚物的加载量为20-95%(w/w),优选为30-90%(w/w)。
橡胶、弹性体和其他聚合物包括天然橡胶、聚异戊二烯橡胶、聚异丁烯橡胶、聚丁二烯橡胶、丁基橡胶、丁腈橡胶(nitrilebutyl rubber)、聚氯丁二烯橡胶、丁苯橡胶、苯乙烯异戊二烯橡胶、丙烯醛橡胶、聚丁烯(polybutylene)、聚丁烯、聚苯醚、聚碳酸酯、乙烯基聚乙酸酯、甲基丙烯酸树脂、聚丙烯腈、热塑性聚酯、聚酰胺、聚乙烯醇缩丁醛、环氧树脂、乙烯基乙烯乙酸酯(vinyl ethylene acetate)共聚物等。这些是以光固性单体和/或低聚物的溶液或者均匀分散体形式使用的。
光反应引发剂包括苯偶姻甲醚、苯偶姻乙醚、α-甲基苯偶姻、二苯甲酮、苄基、乙酰苯、蒽醌、菲醌、苄硫醚、2-氯噻吨酮、2-甲基噻吨酮等。相对于100重量份的主组分,光反应引发剂的加载量为1-7重量份,优选2-5重量份。当必要时,可以加载聚合抑制剂等。
此外,热熔型的一液型固化糊状材料具有这样机理,其中将温室下的固体加热到熔融状态,然后冷却到室温而固化,这样的材料包括包含热塑性树脂的材料,该材料被加热而熔融,然后通过冷却到室温固化。热塑性树脂包括聚乙烯、聚丙烯、聚烯烃共聚物如乙烯丙烯共聚物,乙烯乙酸乙烯酯共聚物和SEBS(苯乙烯乙烯/丁烯苯乙烯),聚苯乙烯、聚酯树脂、丙烯酸树脂、聚(氯乙烯)、聚(1,1-二氯乙烯)、氟树脂、聚碳酸酯、聚缩醛、聚酰胺、苯乙烯丁二烯、聚丁二烯及它们的共聚物。可以将交联性官能团例如羟基、羧基、缩水甘油基、氨基、巯基、异氰酸酯基和烷氧甲硅烷基,结合到这些热塑树脂上,然后可以将所得到的树脂和含有能够和上面所述交联官能团反应的官能团的化合物结合,制备出一液型固化糊状材料。
溶胶凝胶型指的是增塑溶胶的一液型固化糊状材料,它是可以通过将细粒例如聚(氯乙烯)、丙烯酸树脂和聚氨酯树脂分散在增塑剂中而得到的形成溶胶的一液型固化糊状材料。该材料可以通过加热硬化从溶胶变成凝胶。
附图简述
图1、显示本发明糊状材料粘度特性的曲线图。
图2、机械发泡装置的线路图。
图3、显示活塞结构的前剖视图。
图4、图示活塞泵操作的时间图。
实施本发明的最佳方式
将对本发明一液型固化糊状材料的排放和膨胀方法参照附图进行说明。
首先,优选使用图2所示的机械发泡装置来实施该排放和膨胀方法,所述的机械发泡装置由气体供应装置10、一液型固化糊状材料供应装置11、活塞泵12、控制装置13、加压装置14、分散装置15和排放装置16组成。
气体供应装置10供应压力被调节到约0.1-5kg/cm2,优选0.1-3kg/cm2范围内的低压气体。
气体供应装置10包含用于接受来自压缩机的压缩空气的端口31,压力调节阀34和气体流量计35等。压缩气体不限于压缩空气,其中还可以使用二氧化碳气体、氮气等。
一液型固化糊状材料供应装置11在调节到约100-300kg/cm2,优选约150-250kg/cm2范围内的高压下,将一液型固化糊状材料PM供应到管道39A。在这种实施方案中,使用仿形圆盘型(follower-plate type)柱塞泵42A等作为泵送一液型固化糊状材料所用的泵。通过柱塞泵42A,装在容器中的一液型固化糊状材料PM在高压下被传送到管道39A。
活塞泵12包含两个交替操作的活塞泵45A和45B。活塞泵45A和45B包括分别通过电动机M2A和M2B作往复直线移动的活塞。因此,活塞在每个活塞泵中的气缸内往复移动,从而进行吸气冲程和排气冲程。活塞泵45A和45B位于管道39A和管道44A之间,从而将在压力下从糊状材料供应装置10供应的一液型固化糊状材料PM和由气体供应装置10供应的气体以分批方式在预定压力下引入。
下面参照图3来说明活塞泵45A(和45B)的结构。
活塞泵45A包含气缸451、在气缸451内密封接合并滑动的活塞452,以及固定在气缸451中的三个针形阀NV1、NV3和NV5。
针形阀NV5是用于控制排放的阀,被固定在活塞泵45A中排气冲程的冲程末端。针形阀NV3是用于控制气体供应的阀,被固定在邻近排气冲程的冲程末端的地方。针形阀NV1是用于控制一液型固化糊状材料PM供应的阀,被固定在邻近吸气冲程的冲程末端的地方。
针形阀NV1、NV3和NV5在结构上彼此是基本相同的。在每个针形阀中,针453通过气压缸轴向移动,从而使针453前端打开和关闭固定在气缸451内圆周表面或者端面上的孔454。阀体包括和阀室相通的端口455。
当针形阀NV1、NV3和NV5关闭时,针453的前端和气缸451内圆周表面或者端面在一侧处于相同水平,因而针453和活塞452之间的死空间基本为0。因此,当针形阀NV1、NV3和NV5关闭时,不可能有供应到气缸451中的部分气体或者糊状材料进入并残留在针形阀NV1、NV3和NV5的阀室中。当针形阀NV5打开进行排气冲程时,气缸451中的所有气体和一液型固化糊状材料被一起排出。
单向阀CV3和CV4被固定在管道39B中,而单向阀CV5和CV6被固定在管道44A中。每个活塞泵45A和45B的气缸体积(排放体积)是由活塞452的直径和冲程(活塞移动的距离)决定的。
控制装置13控制电动机M1A、M2A和M2B以及针形阀NV1、NV3和NV5,以在吸气冲程过程中和/或之后将气体供应到活塞泵45A和45B各自的气缸451中,在吸气冲程之后将一液型固化糊状材料PM供应到气缸451中,并在一液型固化糊状材料PM供应完成之后进行排气冲程,从而将气体和一液型固化糊状材料排放到管道44A中。
此外,基于图4的时间表来说明活塞泵的操作方式。
在活塞泵45A和45B任一个中,活塞452从排气末端移动到吸气末端,以此进行吸气冲程。在吸气冲程的过程中,当活塞452开始移动后过去时间T1时,针形阀NV1打开,从而将气体供应到气缸中。时间T1约1-2秒。在此期间,气缸451中的压力是负的。针形阀NV1在活塞到达吸气末端后很短的时间关闭。因此,在吸气冲程完成时,气缸451被具有规定压力的气体所充满。当测量的气体量小于预定值时,控制装置13发出警告信号。因此,吸气冲程过程中的气体供应量是被控制装置13所监控的。
当在针形阀NV1关闭后过去时间T3时,针形阀NV3打开。时间T3为约0.1-0.5秒期间。因此,可以防止同时打开针形阀NV1和NV3。针形阀NV3打开时的时长为T4。在此期间,将一液型固化糊状材料PM从一液型固化糊状材料供应装置11供应到气缸451中。由于一液型固化糊状材料的高压,在供应一液型固化糊状材料之前供应的低压气体以等同于气体压力和所给一液型固化糊状材料压力比的比例被压缩。因此,气体的体积变得几乎可以忽略不计。
例如,当低压气体的压力为1kg/cm2而一液型固化糊状材料的压力为200kg/cm2时,气体的体积变成了约1/200。在这种情况下,和气缸451体积相等的一液型固化糊状材料和1kg/cm2相同体积的气体混合。应当指出的是,和气缸451体积相等的1kg/cm2气体相当于大气压下(压力为0kg/cm2)两倍气缸451体积的气体。即,将1kg/cm2的气体供应到气缸中,等于向气缸施加1kg/cm2的压力,因为气缸在吸气冲程中供应气体之前处于约-1kg/cm2的负压。因此,低压气体和一液型固化糊状材料的混合比例R在将气体体积转化成大气压下的体积时为2∶1。混合比例R由通式R=(P1+1)∶1表示,其中P1表示低压气体的供应压力。即,通过调节低压气体的供应压力可以很容易地调节或者控制混合比例R。
当将低压气体和一液型固化糊状材料混合并将混合物分散时,一液型固化糊状材料在被排放到大气中时以3(=1+2)倍于气缸的体积发泡。换言之,一液型固化糊状材料的发泡比A是“3”。发泡比A用通式(P1+2)表示,其中P1表示低压气体的供应压力。
当在针形阀NV3关闭后过去时间T5时,针形阀NV5打开,并且活塞452从吸气末端向排气末端移动,从而进行排气冲程。时间T5在约0.1-0.5秒之内。在排气冲程的过程中,针形阀NV1和NV3是关闭的,因此针形阀NV1和NV3每一个的针453的前端都和气缸451内圆周表面在一侧处于相同水平,因此死空间为0,并且气缸451中的所有低压气体和所有一液型固化糊状材料都从针形阀NV5的孔454被排放出去。当排气冲程完成后过去时间T6时,开始随后的吸气冲程。时间T6在约0.1-0.5秒之内。
至于活塞泵45A和45B,在一个活塞泵的排气冲程结束后,另一活塞泵的排气冲程开始。因此,活塞泵45A和45B交替将混合了气体的材料(最佳可膨胀材料)排放到管道44A中。在管道44A中,来自活塞泵45A和45B的混合了气体的材料各自形成通过单个排气冲程排放的一液型固化糊状材料和压缩的低压气体的两层。因此,一系列两层材料被不连续地安排在管道44A中,而且混合了气体的材料以脉冲方式被安排在管道44A中。这种状态可以使随后的分散成功。
加压装置14包含:活塞泵51A、51B,每个活塞泵都包含被电动机往复直线驱动以对流体加压的活塞;开关阀52A、52B、53A和53B;以及压力传感器55A和55B。
排放到管道44A中的混合了气体的材料是通过交替操作的活塞泵51A和51B供应的,并且被传送到管道57A和57B中。例如,对于活塞泵51A的操作,当活塞在气缸内向上移动同时开关阀52A打开和开关阀53A关闭时,管道44A中混合了气体的材料被吸入气缸中。当活塞向下移动同时开关阀52A关闭和开关阀53A打开时,气缸中混合了气体的材料被挤压,成为受压状态。气缸中的压力是通过压力传感器55A检测的,由此将检测信号发送到控制装置13。活塞泵51A的挤压压力为150kg/cm2或者更大。驱动活塞的电动机是根据来自控制装置13的信号而控制的,从而控制活塞51A的吸气和挤压以及流速(挤压速度)。
分散装置15(和排放装置16)包含分散管道61和开关阀65、排放管道71、排放开关阀72和喷嘴73。分散管道61是长度约2-10m的软管。在分散管道61中,混合了气体的材料的压力为150kg/cm2或者更大,例如,200-250kg/cm2。在加压的混合了气体的材料通过分散管道61的过程中,气体以平均直径约0.01mm的小泡形式分散到糊状材料PM中。
当阀72打开时,来自开关阀65的可膨胀材料在大气压下从喷嘴73排放出去。一旦排出,细微分散的低压气体就开始膨胀,从而使一液型固化糊状材料发泡。成型放大倍数为1.5-5的可膨胀材料可用于通过将喷嘴73在预定的轨道上移动而进行泡沫涂覆。
泡沫涂覆的一液型固化糊状材料可以任其放置(在正常状态下固化)或者用合适的方式固化,得到含有致密而均匀封闭泡孔的固化产品(发泡产品)。
对于固化产品的泡沫泡孔的外形保持系数显示其吸水率不超过10%,且封闭泡孔的直径不超过500μm。
实施例
下面将通过如下实施例来举例说明本发明。
实施例1
在上面所述的排放和膨胀程序下,
将具有如下粘度特性的一液型固化糊状材料和1kg/cm2的低压气体机械混合,得到可膨胀材料,将此材料排放、膨胀,然后固化,得到封闭泡孔的固化产品,其中吸水率为2-3%,且泡孔直径为50-100μm。
表观粘度 | ||
一液型固化糊状材料* | (泊) | |
(0.43秒-1) | (783秒-1) | |
A、一液型热固性聚氨酯 | 2400 | 175 |
A1、一液型热固性聚氨酯 | 60 | 28 |
A2、一液型热固性聚氨酯 | 10000 | 1200 |
B、一液型湿固性聚氨酯 | 20000 | 400 |
C、一液型湿固性聚硅氧烷 | 3000 | 600 |
*)
A、PENGUIN FOAM PU-A,由SANSTER GIKEN KABUSHIKI KAISHA制造
A1、PENGUIN FOAM PU-A1,由SANSTER GIKEN KABUSHIKI KAISHA制造
A2、PENGUIN FOAM PU-A2,由SANSTER GIKEN KABUSHIKI KAISHA制造
B、PENGUIN FOAM PU-B,由SANSTER GIKEN KABUSHIKI KAISHA制造
C、PENGUIN FOAM SR-C,由SANSTER GIKEN KABUSHIKI KAISHA制造
工业适用性
从上面所述结果发现:可以用具有合适的粘度特性的一液型固化糊状材料制造含有致密而均匀封闭泡孔的发泡固化产品,而且这样制备的发泡固化产品可以应用于要求绝热、轻量化、减震、缓冲、隔音、减振、撞击吸收、保护、表层装饰、隔水和气密的各种产品领域;例如结构和建筑物材料、包装、电器和电子设备、汽车、家庭用品、运动用品和器具。
因此,本发明的可膨胀材料可以例如用作密封剂、粘合剂、涂料、垫圈、填充物、垫子、绝缘体、泡沫模制材料等。
Claims (6)
1、在机械混合和分散糊状材料和低压气体制造出可膨胀材料,随后通过排放和膨胀该可膨胀材料制造固化产品的方法中,
其中的改进包括使用具有在图1的曲线中的点A、B、C和D所限定区域中包含的粘度特性的一液型固化糊状材料作为所述的糊状材料,图1的曲线是显示剪切速率和表观粘度之间关系,所述的点A和B是在低剪切速率区(0.43秒-1)中表观粘度为50-30000泊的点(用布鲁克菲尔德旋转粘度计使用7号锭子,在2rpm、20℃下测量的),点C和D是在高剪切速率区(783秒-1)中表观粘度为20-2000泊的点(按照JIS K2220,用表观粘度计在20℃下测量的),并且机械混合和分散所述的一液型固化材料和低压气体,接着排放和膨胀所得到的可膨胀材料,制造出含有致密而均匀封闭泡孔的固化产品。
2、权利要求1的排放和膨胀方法,
其中所述机械混合和分散一液型固化材料和低压气体以制造可膨胀材料的方法包含:
在活塞泵的吸气冲程过程中和/或之后将低压气体送入气缸中,所述的活塞泵在气缸中往复运动进行吸气冲程和排气冲程,然后
通过分批方法将一液型固化糊状材料供应到气缸中,
在供应—液型固化糊状材料之后用活塞泵进行排气冲程,以及
在排气冲程中将低压气体和—液型固化糊状材料排放到管道中。
3、权利要求1或者2的排放和膨胀方法,其中所述制造可膨胀材料以及排放和膨胀该可膨胀材料的方法是使用机械发泡装置进行的,该装置包含,
活塞泵,所述的活塞泵包括活塞和气缸,其中活塞适合在气缸内作往复移动以进行吸气冲程和排气冲程;
气体供应装置,所述的气体供应装置用于在预定压力下将低压气体供应到气缸中;
糊状材料供应装置,所述的糊状材料供应装置用于在预定压力下将一液型固化糊状材料供应到气缸中;
控制装置,所述的控制装置用于对在活塞泵的吸气冲程过程中和/或之后将低压气体供应到气缸中,将一液型固化糊状材料供应到气缸中,在一液型固化糊状材料供应冲程之后进行活塞泵的排气冲程,以及将低压气体和一液型固化糊状材料排放到管道中进行控制;和
排放装置,所述的排放装置用于通过连接从控制装置获得的可膨胀材料管道而排放和膨胀可膨胀材料到管道中。
4、权利要求1至3任一项的排放和膨胀方法,
其中可膨胀材料适合用作密封剂、粘合剂、涂料、垫圈、填充物、垫子、绝缘体、泡沫模制材料等。
5、在权利要求1至4任一项的排放和膨胀方法中使用的一液型固化糊状材料,该材料具有在图1的曲线中的点A、B、C和D所限定区域中包含的粘度特性,图1的曲线是显示剪切速率和表观粘度之间关系,所述的点A和B是在低剪切速率区(0.43秒-1)中表观粘度为50-30000泊的点(用布鲁克菲尔德旋转粘度计使用7号锭子,在2rpm、20℃下测量的),点C和D是在高剪切速率区(783秒-1)中表观粘度为20-2000泊的点(按照JISK2220,用表观粘度计在20℃下测量的)。
6、权利要求5的一液型固化糊状材料,其中该材料为可湿固型、热固型、热熔型、溶胶凝胶型、硫化交联型和/或可光/辐射固化型,包含聚硅氧烷、聚氨酯、环氧树脂、合成橡胶、聚烯烃、聚酯、丙烯酸树脂、聚(氯乙烯)、热塑性塑料、热塑性弹性体。
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JP4731940B2 (ja) * | 2005-02-14 | 2011-07-27 | サンスター技研株式会社 | 発泡方法及びその装置 |
KR100777429B1 (ko) * | 2005-08-04 | 2007-11-28 | 에스케이씨 주식회사 | 저장성이 우수한 습기경화형 폴리우레탄 조성물 및 그제조방법 |
JP4397390B2 (ja) * | 2006-10-20 | 2010-01-13 | 行雄 土屋 | パッキン付き製造蓋の製造方法及び製造装置 |
JP4261586B2 (ja) * | 2007-01-15 | 2009-04-30 | 東洋ゴム工業株式会社 | 研磨パッドの製造方法 |
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JP2008213074A (ja) * | 2007-03-02 | 2008-09-18 | Disco Abrasive Syst Ltd | 駆動機構及び切削装置 |
CA2669439A1 (en) * | 2008-06-18 | 2009-12-18 | Elastochem Specialty Chemicals Inc. | Pre-reacted isocyanate product |
CN105397970A (zh) * | 2015-12-14 | 2016-03-16 | 长春富维—江森自控汽车饰件系统有限公司 | 聚氨酯高压浇注机浇注头料温自动控制方法 |
DE102016114898A1 (de) * | 2016-08-11 | 2018-02-15 | Ceracon Gmbh | Vorrichtung und Verfahren zum Schäumen eines viskosen Materials |
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CA2512150A1 (en) | 2004-07-22 |
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EP1591219A4 (en) | 2006-05-31 |
ATE477099T1 (de) | 2010-08-15 |
CN100491103C (zh) | 2009-05-27 |
EP1591219A1 (en) | 2005-11-02 |
JP4589232B2 (ja) | 2010-12-01 |
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US20060148909A1 (en) | 2006-07-06 |
AU2004203716A1 (en) | 2004-07-22 |
JPWO2004060628A1 (ja) | 2006-05-11 |
ES2347556T3 (es) | 2010-11-02 |
AU2004203716B2 (en) | 2009-10-29 |
WO2004060628A1 (ja) | 2004-07-22 |
KR20050111578A (en) | 2005-11-25 |
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