CN112552460A - 一种热塑性聚氨酯弹性体发泡材料组合物及发泡材料 - Google Patents
一种热塑性聚氨酯弹性体发泡材料组合物及发泡材料 Download PDFInfo
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- CN112552460A CN112552460A CN201910850054.XA CN201910850054A CN112552460A CN 112552460 A CN112552460 A CN 112552460A CN 201910850054 A CN201910850054 A CN 201910850054A CN 112552460 A CN112552460 A CN 112552460A
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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Abstract
本发明涉及一种热塑性聚氨酯弹性体发泡材料组合物及发泡材料。所述组合物,按重量份计,包括如下组份:热塑性聚氨酯弹性体25‑98份、含碳碳双键的不饱和化合物2‑75份、发泡剂0.1‑25份、交联剂0.1‑15份;其中,所述热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量份和为100份。所述组合物经混合、模压或射出发泡后即可制得热塑性聚氨酯弹性体发泡材料。该发泡材料具有耐磨性好,高回弹,止滑性能优良等优点。
Description
技术领域
本发明涉及一种发泡材料,尤其涉及一种热塑性聚氨酯弹性体发泡材料及制备其的组合物,属于轻量化材料技术领域。
背景技术
乙烯-醋酸乙烯酯共聚物(EVA)发泡材料因其质轻,柔软,穿着舒适而作为发泡鞋材、包装等材料广泛使用,但高发泡倍率的乙烯-醋酸乙烯酯共聚物具有压缩永久形变较大、回弹性较差、不耐磨等缺点。热塑性聚氨酯弹性体兼具橡胶的弹性和塑料的加工性能,其发泡材料具有强度高、弹性好、耐磨、耐寒、耐油、耐老化等优点。但普通的热塑性聚氨酯弹性体材料因为分子上缺乏交联点而无法直接应用于乙烯醋酸乙烯酯的交联发泡体系。
CN107614615A公开了一种通过向TPU分子链上引入交联位置,来将TPU用于乙烯醋酸乙烯酯(EVA)的交联发泡体系。此方法工艺路线较为复杂。
CN102604306A公开了一种EVA/TPU组合物采用交联发泡工艺来制备热塑性聚氨酯组合物发泡材料的方法。但此EVA/TPU组合物中TPU添加量较小,仅为1-5份,无法将热塑性聚氨酯材料的性能优势体现在最终的发泡材料中。
CN107151373A公开了一种烯烃类聚合物/TPU组合物发泡材料,其通过增容剂的作用,使烯烃类聚合物/TPU形成互穿网络结构,然后在采用交联发泡工艺来制备烯烃类聚合物/TPU组合物发泡材料。此种方法容易造成烯烃类聚合物和TPU的两相分布不均匀,从而影响最终发泡制品的性能。
尽管现有的改善TPU材料交联发泡性能的方法已经获得了一定的效果,但在发泡材料的压缩永久形变、回弹性能等方面还存在改善的空间。
发明内容
本发明针对现有发泡材料存在的不足,提供一种热塑性聚氨酯弹性体发泡材料组合物及制备的发泡材料。所述发泡材料具有耐磨、压缩永久形变低、回弹及止滑性优良等优点,制备工艺简单,成本低。
为解决以上技术问题,本发明提供以下技术方案:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组份:
热塑性聚氨酯弹性体25-98份;
含碳碳双键的不饱和化合物2-75份;
发泡剂0.1-25份;
交联剂0.1-15份;
其中,所述热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量份和为100份。
作为一种优选的方案,一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组份:
热塑性聚氨酯弹性体50-95份;
含碳碳双键的不饱和化合物5-50份;
发泡剂1-15份;
交联剂0.2-8份;
其中,所述热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量份和为100份。
作为另一种优选的方案,一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组份:
热塑性聚氨酯弹性体70-90份;
含碳碳双键的不饱和化合物10-30份;
发泡剂2-8份;
交联剂0.5-3份;
其中,所述热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量份和为100份。
本发明所述的含碳碳双键的不饱和化合物是指分子链上含有碳碳双键,在引发剂的作用下可交联的物质。
本发明所述的含碳碳双键的不饱和物质可以是含碳碳双键的不饱和小分子,包含二乙烯基苯、丁二烯、戊二烯、辛二烯、异戊二烯、三烯丙基异氰脲酸酯、三烯丙基三聚氰酸酯、三羟甲基丙烷丙烯酸酯等中的一种或多种。
本发明所述的含碳碳双键的不饱和物质也可以是含碳碳双键的不饱和低聚物,包含低聚物聚丁二烯、低聚物聚戊二烯、低聚物聚异戊二烯、低聚物聚二乙烯基苯等中的一种或多种。
本发明所述的含碳碳双键的不饱和低聚物,可以进一步包含酸酐基团-COOCO-、羧基-COOH、羟基-OH、仲氨基-NH-、伯氨基-NH2、异氰酸酯基-NCO、环氧基、脲基-NHCONH-等极性侧基,这样其在和热塑性聚氨酯弹性体混合的过程中会有更好的相容性。优选的,含极性侧基的不饱和低聚物可以是马来酸酐接枝低聚物聚丁二烯、马来酸酐接枝低聚物聚异戊二烯、羟基改性低聚物聚丁二烯、羟基改性低聚物聚异戊二烯等。
本发明所述的含碳碳双键的不饱和低聚物,其数均分子量优选为500-15000g/mol,更优选为1500-10000g/mol。
本发明所述的含碳碳双键的不饱和化合物还可以是含碳碳双键的不饱和聚和物,包含聚丁二烯、聚戊二烯、聚异戊二烯、聚二乙烯基苯,聚乙炔,天然橡胶,不饱和聚酯,不饱和聚酰胺等中的一种或多种。上述聚和物可进一步包含极性侧基,如酸酐基团-COOCO-、羧基-COOH、羟基-OH、仲氨基-NH-、伯氨基-NH2、异氰酸酯基-NCO、环氧基、脲基-NHCONH-等。所述的含极性侧基的不饱聚合物可以是马来酸酐接枝聚丁二烯、马来酸酐接枝聚异戊二烯、羟基改性低聚丁二烯、羟基改性聚异戊二烯等。
本发明所述的含碳碳双键的不饱和聚合物,其数均分子量Mn优选30000-500000g/mol,优选50000-300000g/mol。
本发明所述的含碳碳双键的不饱和化合物,可以采用单独一种或将几种含碳碳双键的不饱和化合物混合使用。
本发明所述热塑性聚氨酯弹性体为聚酯型热塑性聚氨酯弹性体、聚醚型热塑性聚氨酯弹性体、聚己内酯型热塑性聚氨酯弹性体、聚碳酸酯型热塑性聚氨酯弹性体中的一种或多种;其邵氏硬度为40A-80D,优选45A-98A,再优选60A-85A。
本发明所述的热塑性聚氨酯弹性体,由至少一种多异氰酸酯、至少一种多元醇和至少一种扩链剂反应制备。
本发明所述热塑性聚氨酯弹性体的制备中使用的多异氰酸酯选自芳香族多异氰酸酯和脂肪族多异氰酸酯中的一种或多种;所述多异氰酸酯包括但不限于4,4'-二苯基甲烷二异氰酸酯(4,4'-MDI)、2,4'-二苯基甲烷二异氰酸酯(2,4'-MDI)、2,2'-二苯基甲烷二异氰酸酯(2,2'-MDI)、苯二亚甲基二异氰酸酯(XDI)、1,5-萘二异氰酸酯(NDI)、对苯二异氰酸酯(PPDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、1,4-环己基二异氰酸酯(CHDI)、六亚甲基二异氰酸酯(HDI)、癸烷-1,10-二异氰酸酯和二环己基甲烷-4,4'-二异氰酸酯(H12MDI)中的一种或多种,优选4,4'-二苯基甲烷二异氰酸酯。
本发明所述热塑性聚氨酯弹性体的制备中使用的多元醇选自聚酯多元醇、聚醚多元醇、聚内酯多元醇和聚碳酸酯多元醇中的一种或多种,优选聚酯多元醇和/或聚醚多元醇。
本发明所述聚酯多元醇可通过二元醇与二元羧酸、二元羧酸酸酐或二元羧酸酯进行酯化或酯交换反应制备得到。所述聚酯多元醇的数均分子量(Mn)为500-10000,优选为700-5000,更优选为750-4000;酸值为0-1.0mgKOH/g,优选为0.1-0.5mgKOH/g。
本发明所述聚内酯多元醇优选为聚己内酯多元醇,是由ε-己内酯单体和起始剂在催化剂引发作用下制备而成。所述聚己内酯多元醇的数均分子量(Mn)优选为500-3000,更优选为1000-2000。
本发明所述聚碳酸酯多元醇可采用有光气法、二氧化碳调节共聚法、环状碳酸酯开环聚合法或酯交换法合成获得。
本发明所述聚碳酸酯多元醇的数均分子量(Mn)为500-4000,优选为1000-3000。
本发明所述聚醚多元醇是由起始剂与含有2至6个碳原子的环氧化合物反应,制备得到的聚醚多元醇。
本发明所述聚醚多元醇的数均分子量(Mn)为500至10000,优选为700-4000。
本发明所述热塑性聚氨酯弹性体的制备中使用的扩链剂选自具有2至10个碳原子的二醇中的一种或多种,优选乙二醇、二乙二醇、丙二醇、二丙二醇、1,4-丁二醇、1,6-己二醇、1,3-丁二醇、1,5-戊二醇、1,4-环己二醇、氢醌二(羟乙基)醚、新戊二醇、甘油单烯丙基醚、三羟甲基丙烷单烯丙基醚、甘油单丙烯酸酯中的一种或多种。
本发明所述扩链剂的用量为基于多异氰酸酯与多元醇总质量的3%-25%,优选为5%-20%。
本发明所述发泡剂包含放热型发泡剂或吸热型发泡剂中的一种或多种,优选的,所述发泡剂包含偶氮二甲酰胺、偶氮二异丁腈、偶氮二甲酸钡、N-亚硝基化合物(发泡剂H)、N-硝基脲、4,4’-氧代双苯磺酰肼、对甲苯磺酰肼、碳酸氢钠和碳酸氢铵中的一种或多种。一般的,可以单独使用放热性发泡剂,也可以将放热性发泡剂和吸热型发泡剂复合使用。
本发明所述的交联剂可以是过氧化物,合适的例子包括但不限于过氧化二异丙苯、双叔丁基过氧化二异丙基苯、过氧化苯甲酰、过氧化月桂酰、过氧化二叔丁基、过氧化苯甲酸叔丁酯、过氧化甲乙酮、过氧化环己酮、过硫酸钾、过硫酸钠、过硫酸铵等中的一种或多种,优选过氧化二异丙苯、双叔丁基过氧二异丙苯、过氧化环己酮中的一种或多种。
作为一个优选的方案,本发明所述的发泡材料用组合物,可以进一步包含同时含有异氰酸酯基和乙烯基的笼型倍半硅氧烷(记为POSS-NCO-VINYL)。
本发明所述的POSS-NCO-VINYL的用量为0.1-5wt%,优选1-3wt%,基于热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量和计。
一种制备本发明所述的POSS-NCO-VINYL的方法,包括以下步骤:
1)式I的水解未完全的T7型含有七个乙烯基团的POSS与式II的含有氨基的三官能硅烷通过水解聚合反应制备式III的同时含有氨基和乙烯基的POSS(记为POSS-AMINO-VINYL);
2)将同时含有氨基和乙烯基的POSS(POSS-AMINO-VINYL)与多异氰酸酯反应得到同时含有异氰酸酯基和乙烯基的POSS(POSS-NCO-VINYL)。
本发明所述式I中,R1为含有乙烯基的取代基,包括但不限于乙烯基、烯丙基、对乙烯基苯基,优选对乙烯基苯基。
本发明所述式II中,R2为含有氨基的取代基,包括但不限于2-氨基乙基、3-氨基丙基、4-氨基丁基、对氨基苯基,优选对氨基苯基;X为卤素或烷氧基,包括但不限于氯、溴、碘、甲氧基、乙氧基,优选氯、甲氧基、乙氧基。优选的式II的化合物为对氨基苯基三氯硅烷、对氨基苯基三甲氧基硅烷。
本发明所述的制备POSS-NCO-VINYL的方法中,所述多异氰酸酯包含4,4'-二苯基甲烷二异氰酸酯(4,4'-MDI)、2,4'-二苯基甲烷二异氰酸酯(2,4'-MDI)、2,2'-二苯基甲烷二异氰酸酯(2,2'-MDI)、苯二亚甲基二异氰酸酯(XDI)、1,5-萘二异氰酸酯(NDI)、对苯二异氰酸酯(PPDI)、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、1,4-环己基二异氰酸酯(CHDI)、六亚甲基二异氰酸酯(HDI)、癸烷-1,10-二异氰酸酯和二环己基甲烷-4,4'-二异氰酸酯(H12MDI)中的一种或多种。本发明所述式I化合物与式II化合物的摩尔比为1:(1-5),优选1:(1-3)本发明所述步骤1)的反应温度为-20℃~40℃,优选-10℃~30℃;反应时间为1-8h,优选2-6h。
本发明所述的步骤1)的反应是在三乙胺或氢氧化四烷基铵等碱性物质的存在下进行的,所述的碱性物质可以和反应生成的酸性物质相结合,促进反应的进行。
优选的,本发明所述步骤1)反应结束后,还包括提纯的步骤,所述提纯的步骤包括但不限于蒸馏、水洗、干燥等。
本发明所述步骤2)中,多异氰酸酯与POSS-AMINO-VINYL的比例为1:(0.5-3),优选1:(1-2)。
优选的,本发明所述步骤2)反应结束后,还包括提纯的步骤,所述提纯的步骤包括但不限于蒸馏、干燥等。
令人意想不到的是,POSS-NCO-VINYL的引入可以极大的提升发泡材料的止滑性能,克服了传统发泡材料止滑性能差的缺点。POSS-NCO-VINYL中的乙烯基和异氰酸根基可以改善POSS的分散效果,防止POSS在发泡材料基体中发生团聚。同时POSS-NCO-VINYL中的乙烯基和异氰酸酯基可以分别和含碳碳双键的不饱和化合物及热塑性聚氨酯发生反应,促进发泡过程中热塑性聚氨酯的交联。
本发明所述的发泡材料用组合物,还可以进一步包含改善加工性能的润滑剂、促进发泡剂分解的活性剂、增塑剂、耐磨剂、抗UV助剂、色粉、有机或无机填料等本领域公知的助剂。
本发明所述的润滑剂可以改善混炼或挤出混合过程中的加工效果,使得混合更加容易。本发明中所述的润滑剂可以使用常用于橡胶加工过程中的润滑剂,包括加工油、液体石蜡、聚乙烯蜡、脂肪油、脂肪酸等。
本发明所述的促进发泡剂分解的活性剂用于调节发泡剂的分解温度,使得发泡过程中发泡剂的分解温度和交联剂的交联温度更好的匹配,从而获得更好的发泡效果。本发明所述的活性剂包括氧化铅、氧化镁、氧化钙、氧化锌、醋酸锌、硝酸锌、碳酸钙、碳酸锌、碳酸钾、己二酸、水杨酸、丁二酸、柠檬酸、马来酸、硼砂等。
本发明所述的增塑剂可以降低热塑性聚氨酯的加工温度,从而解决部分热塑性聚氨酯无法混炼加工的问题。本发明所述的增塑剂包括邻苯二甲酸酯类增塑剂、脂肪族酯类增塑剂、磷酸酯类增塑剂、环氧基增塑剂等中的一种或多种。
本发明所述的有机或无机填料可以对发泡材料进行补强,同时还可以节约成本。本发明所述的有机或无机填料包括滑石粉、超细碳酸钙、高岭土、硅藻土、玻璃纤维、碳纤维、碳纳米管、石墨烯、炭黑、金属粉末等中的一种或多种。
一种制备热塑性聚氨酯弹性体发泡材料的方法,包含如下步骤:
a)按照比例,将热塑性聚氨酯弹性体、含碳碳双键的不饱和化合物、发泡剂、交联剂、任选的助剂,通过混炼或熔融挤出的方式混合均匀,制得可发泡组合物;
b)将步骤1)所得可发泡组合物采用交联发泡的工艺发泡,冷却定型,得到热塑性聚氨酯弹性体发泡材料。
本发明所述的步骤a)中,如果采用混炼的方式混合,可以先将所述热塑性聚氨酯弹性体、含碳碳双键的不饱和化合物投入开炼机或密炼机中,在80-130℃下混炼8-30min,然后再投入发泡剂、交联剂和任选的助剂,继续在80-130℃下混炼8-30min,得到可发泡组合物。或者,将所有组分一次性投入开炼机或密炼机中,在80-130℃下混炼8-30min,得到可发泡组合物。
本发明所述的步骤a)中,如果采用熔融挤出的方式混合,可将热塑性聚氨酯弹性体、含碳碳双键的不饱和化合物、发泡剂、交联剂、任选的助剂混合之后投入挤出机中,在80-180℃下熔融挤出得到可发泡组合物。
对于使用含碳碳双键的不饱和小分子和/或含碳碳双键的不饱和低聚物的情况来说,可以将热塑性聚氨酯弹性体与含碳碳双键的不饱和小分子和/或含碳碳双键的不饱和低聚物进行混合,也可以在热塑性聚氨酯弹性体的合成过程中,将含碳碳双键的不饱和小分子或含碳碳双键的不饱和低聚物混合到多元醇中,直接用于热塑性聚氨酯弹性体的合成,从而得到混有含碳碳双键的不饱和物的热塑性聚氨酯弹性体,然后与发泡剂、交联剂、任选的助剂,通过混炼或熔融挤出的方式混合均匀,制得可发泡组合物。
具体的,本发明所述的步骤b),包括以下步骤:将可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为140-220℃,发泡时间为1-50分钟,压力10-30MPa,冷却出模,得到热塑性聚氨酯弹性体发泡材料;或者,将可发泡组合物投入到射出发泡成型机中,采用射出发泡的工艺,得到热塑性聚氨酯弹性体发泡材料。
本发明所述的热塑性聚氨酯弹性体发泡材料具有优异的耐磨性能,其在不添加耐磨助剂的情况下即可获得优于普通TPU和EVA发泡材料的回弹性能。
本发明所述的热塑性聚氨酯弹性体发泡材料,其压缩永久形变在20%以下,回弹性能在60%以上;当引入POSS-NCO-VINYL,止滑系数在0.6以上。
与现有技术相比,本发明提供的热塑性聚氨酯弹性体发泡材料及其制备方法的有益效果如下:工艺比较简单,成本较低,获得的发泡材料具有耐磨、压缩永久形变低、回弹及止滑性优良等优点。
本发明采用在热塑性聚氨酯弹性体中引入含碳碳双键的不饱和化合物,改善了热塑性聚氨酯弹性体本身缺少交联点而无法进行交联发泡的缺点;当引入POSS-NCO-VINYL,聚氨酯的交联效果得到改善,同时获得优异的止滑效果。得到的热塑性聚氨酯弹性体发泡材料具有低压缩永久形变、高回弹、高止滑等性能。
本发明的热塑性聚氨酯弹性体适合用于鞋材、家居、保险杠等领域。
本发明的热塑性聚氨酯弹性体发泡材料组合物,可直接采用现有的EVA发泡设备进行热塑性聚氨酯弹性体发泡材料的制备,适合工业化生产。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所用实例只用于解释本发明,并非用于限定本发明的范围。
制备POSS-NCO-VINYL
1)将22.24g(0.02mol)式I所示七聚笼状倍半硅氧烷(R1为对乙烯基苯基)溶解于100g四氢呋喃中,向其中加入6.06g(0.06mol)三乙胺,用冰盐浴冷却调节体系温度为0℃左右,滴加4.53g(0.02mol)对氨基苯基三氯硅烷(式II化合物),用冰盐浴维持体系温度为0℃左右搅拌反应4h,反应结束,升温至40℃减压回收溶剂并蒸除残留低沸物,产物经水洗,真空干燥,得20g式III所示的POSS-AMINO-VINYL(R1为对乙烯基苯基、R2为对氨基苯基)。
2)将6.145g(0.005mol)POSS-AMINO-VINYL溶解于甲苯中,加入1.25g(0.005mol)4,4’-二苯基甲烷二异氰酸酯,搅拌反应30min,反应结束后在40℃减压蒸馏回收溶剂,然后真空干燥得到POSS-NCO-VINYL。
实施例1:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-8175RV万华化学)95份;
三羟甲基丙烷三丙烯酸酯(长兴化学)5份;
过氧化二异丙苯0.8份;
偶氮二甲酰胺2份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将热塑性聚氨酯弹性体、三羟甲基丙烷丙烯酸酯、过氧化二异丙苯、偶氮二甲酰胺、硬脂酸、氧化锌投入密炼机中,混炼15min,温度为115℃,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料。
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例2:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1180万华化学)90份;
液态低聚物聚丁二烯(N4-9000昕特玛公司)10份;
双叔丁基过氧化二异丙苯0.5份;
偶氮二甲酰胺3.5份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将热塑性聚氨酯弹性体、液态低聚物聚丁二烯、双叔丁基过氧化二异丙苯、偶氮二甲酰胺、硬脂酸和氧化锌置于密炼机中混炼,混炼时间15min,温度115℃,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例3:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1170IC万华化学)85份;
液态低聚物聚异戊二烯(IR-565林氏化学)15份;
双叔丁基过氧化二异丙苯1份;
对甲苯磺酰肼5份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将热塑性聚氨酯弹性体、液态低聚物聚异戊二烯、双叔丁基过氧化二异丙苯、对甲苯磺酰肼、硬脂酸和氧化锌置于密炼机中混炼,混炼时间15min,温度115℃,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例4:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1180万华化学)75份;
马来酸酐接枝液态低聚物聚丁二烯(Lithene ultra N4-B-10MA昕特玛公司)25份;
过氧化二异丙苯1.5份;
偶氮二甲酰胺4.5份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将热塑性聚氨酯弹性体、液态低聚物聚丁二烯马来酸酐接枝共聚物、硬脂酸、氧化锌、偶氮二甲酰胺、过氧化二异丙苯一起投入开炼机中,混炼15min,温度120℃,直至混炼均匀,得到可发泡组合物。
2)将所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例5:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-7180万华化学)25份;
聚丁二烯(JSB RB830合成橡胶株式会社)75份;
过氧化环己酮3份;
偶氮二甲酸钡8份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将热塑性聚氨酯弹性体、聚丁二烯、硬脂酸、氧化锌,直接通过双螺杆挤出机混合均匀,得到发泡基料,然后将所得发泡基料和偶氮二甲酸钡、过氧化环己酮一起投入开炼机中,混炼20min,至混炼均匀,得到可发泡组合物。
3)将所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为185℃,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例6:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1180万华化学)90份;
液态低聚物聚丁二烯(Lithene ultra N4-9000昕特玛公司)10份;
双叔丁基过氧化二异丙苯0.5份;
偶氮二甲酰胺3.5份;
POSS-NCO-VINYL 1份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将上述所有组分置于密炼机中混炼,混炼时间15min,温度120℃,制备可发泡组合物。
3)将步骤2)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
实施例7:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1170IC万华化学)85份;
低聚物聚异戊二烯(IR-565濮阳林氏化学)15份;
对甲苯磺酰肼5份;
POSS-NCO-VINYL 2份;
双叔丁基过氧化二异丙苯1份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将上述组分投入密炼机中混炼,混炼时间15min,温度120℃,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
对比例1:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计包括如下组分:
热塑性聚氨酯弹性体(WHT-1170IC万华化学)100份;
对甲苯磺酰肼5份;
POSS-NCO-VINYL 2份;
双叔丁基过氧化二异丙苯1份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将上述组分投入密炼机中,在115℃下混炼15min,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为175℃,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
结果:未得到发泡材料
对比例2:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1180万华化学)90份;
液态低聚物聚丁二烯(Lithene ultra N4-9000昕特玛公司10份;
双叔丁基过氧化二异丙苯0.5份;
偶氮二甲酰胺3.5份;
氢基-POSS 1份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将上述组分置于密炼机中混炼,混炼时间15min,温度120℃,制备可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
对比例3:
一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组分:
热塑性聚氨酯弹性体(WHT-1170IC万华化学)85份;
低聚物聚异戊二烯(IR-565濮阳林氏化学)15份;
对甲苯磺酰肼5份;
八乙烯基POSS(POSS-VINYL)2份;
双叔丁基过氧化二异丙苯1份;
硬脂酸1份;
氧化锌2份。
本实例中的热塑性聚氨酯弹性体发泡材料,通过如下方法制备:
1)将所有组分投入密炼机中,在115℃下混炼15min,得到可发泡组合物。
2)将步骤1)所得的可发泡组合物置于平板硫化机中进行模压发泡,发泡温度为170℃,发泡压力30MPa,发泡时间为20分钟,冷却出模,得到热塑性聚氨酯弹性体发泡材料;
通过上述方法制备的热塑性聚氨酯弹性体发泡材料在常温下冷却24h进行性能测试。
上述实施例及对比例所得样品的测试结果如下表1:
表1样品测试结果
综上所述,本发明所制备的热塑性聚氨酯弹性体发泡材料在发泡倍率、强度、回弹性、压缩永久形变、耐磨性方面都有优异的表现,且制备工艺简单,设备投资成本较低,适合大规模工业化生产。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种热塑性聚氨酯弹性体发泡材料组合物,按重量份计,包括如下组份:
热塑性聚氨酯弹性体25-98份,优选50-95份,更优选70-90份;
含碳碳双键的不饱和化合物2-75份,优选5-50份,更优选10-30份;
发泡剂0.1-25份,优选1-15份,更优选2-8份;
交联剂0.1-15份,优选0.2-8份,更优选0.5-3份;
其中,所述热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量份和为100份。
2.根据权利要求1所述的组合物,其特征在于,所述的含碳碳双键的不饱和物质选自含碳碳双键的不饱和小分子、含碳碳双键的不饱和低聚物、含碳碳双键的不饱和聚和物中的一种或多种。
3.根据权利要求2所述的组合物,其特征在于,所述含碳碳双键的不饱和小分子包含二乙烯基苯、丁二烯、戊二烯、辛二烯、异戊二烯、三烯丙基异氰脲酸酯、三烯丙基三聚氰酸酯、三羟甲基丙烷丙烯酸酯中的一种或多种。
4.根据权利要求2所述的组合物,其特征在于,所述含碳碳双键的不饱和低聚物,选自含有或不含极性基团的低聚物聚丁二烯、低聚物聚戊二烯、低聚物聚异戊二烯、低聚物聚二乙烯基苯中的一种或多种;所述极性基团选自酸酐基团、羧基、羟基、仲氨基、伯氨基、异氰酸酯基、环氧基、脲基;所述含碳碳双键的不饱和低聚物的数均分子量为500-15000g/mol,优选为1500-10000g/mol。
5.根据权利要求2所述的组合物,其特征在于,所述含碳碳双键的不饱和聚和物,选自含有或不含极性基团的聚丁二烯、聚戊二烯、聚异戊二烯、聚二乙烯基苯、聚乙炔、天然橡胶、不饱和聚酯、不饱和聚酰胺中的一种或多种;所述极性基团选自酸酐基团、羧基、羟基、仲氨基、伯氨基、异氰酸酯基、环氧基、脲基。
6.根据权利要求1所述的组合物,其特征在于,所述热塑性聚氨酯弹性体为聚酯型热塑性聚氨酯弹性体、聚醚型热塑性聚氨酯弹性体、聚己内酯型热塑性聚氨酯弹性体、聚碳酸酯型热塑性聚氨酯弹性体中的一种或多种;邵氏硬度为40A-80D,优选45A-98A,更优选60A-85A。
7.根据权利要求1所述的组合物,其特征在于,所述的组合物还包含含有异氰酸酯基和乙烯基的笼型倍半硅氧烷。
8.根据权利要求7所述的组合物,其特征在于,所述的含有异氰酸酯基和乙烯基的笼型倍半硅氧烷的用量为0.1-5wt%,优选1-3wt%,基于热塑性聚氨酯弹性体和含碳碳双键的不饱和化合物的重量和计。
9.根据权利要求7所述的组合物,其特征在于,所述的含有异氰酸酯基和乙烯基的笼型倍半硅氧烷,其制备方法,包括以下步骤:
1)式I的水解未完全的T7型含有七个乙烯基团的笼型倍半硅氧烷与式II的含有氨基的三官能硅烷通过水解聚合反应制备式III的同时含有氨基和乙烯基的笼型倍半硅氧烷;
2)将同时含有氨基和乙烯基的笼型倍半硅氧烷与多异氰酸酯反应得到同时含有异氰酸酯基和乙烯基的笼型倍半硅氧烷;
其中,R1为含有乙烯基的取代基,选自乙烯基、烯丙基、对乙烯基苯基,优选对乙烯基苯基;
R2为含有氨基的取代基,选自2-氨基乙基、3-氨基丙基、4-氨基丁基、对氨基苯基,优选对氨基苯基;
X为卤素或烷氧基,选自氯、溴、碘、甲氧基、乙氧基,优选氯、甲氧基、乙氧基。
10.根据权利要求1-9任一项所述组合物制备的热塑性聚氨酯弹性体发泡材料。
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CN115028984A (zh) * | 2022-06-07 | 2022-09-09 | 江西铂易鸿电子有限公司 | 一种阻燃性性能好的导电泡棉材料及其制备方法 |
CN115028984B (zh) * | 2022-06-07 | 2023-08-18 | 江西铂易鸿电子有限公司 | 一种阻燃性性能好的导电泡棉材料及其制备方法 |
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