CN116496517A - 一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料及其制备方法 - Google Patents
一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料及其制备方法 Download PDFInfo
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- CN116496517A CN116496517A CN202310044524.XA CN202310044524A CN116496517A CN 116496517 A CN116496517 A CN 116496517A CN 202310044524 A CN202310044524 A CN 202310044524A CN 116496517 A CN116496517 A CN 116496517A
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Abstract
本发明公开了一种纳米纤维‑颗粒复合增强的高模量聚氨酯复合材料及其制备方法。这种纳米纤维‑颗粒复合增强的高模量聚氨酯复合材料是由树脂、固化剂和纳米增强材料组成的聚氨酯组合料和改性增强纤维按照先超声在混合加工的步骤制备得到的。本发明通过引入改性纳米纤维和颗粒形成的纳米复合网络增强结构在聚氨酯树脂与增强纤维间形成多尺度的拓扑结构,通过改性纳米纤维与纳米颗粒之间的相互作用力,在纳米颗粒结合于纳米纤维附近,并通过较高的毛细管力和分子间作用力使纳米纤维互相缠结和纳米颗粒形成具有极高内聚力的纳米复合网络结构,并进一步在复合材料中形成具有超稳定性的多相系统。相比较传统的单独纳米材料,纳米复合网络结构在稳定性和界面附着能力有明显增强。作为连接宏观增强纤维和树脂基体的枢纽,这种复合结构的引入可以大大提升材料的力学性能。并且该高模量聚氨酯复合材料制备技术作用机理清晰、生产工艺简单、性能优秀,适用于大规模生产,对于高性能复合材料构件的制备具有重要意义。
Description
技术领域
本发明属于高分子复合材料领域,具体涉及一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料及其制备方法。
背景技术
聚氨酯是由多元醇和多异氰酸酯聚合反应制得的一种聚合物材料,通过不同的原料可以得到不同的结构和性能,可制备为从液体到固体、从软质到硬质的涂料、粘合剂、塑料、纤维、橡胶等各类制品。聚氨酯硬化体有着优异的韧性、抗冲击性、耐磨性、抗撕裂性。聚氨酯加工成型工艺简单,注射、浇筑等工艺均可得到较好的成型效果,因此其应用十分广泛且应用范围增长迅速。
聚氨酯复合材料是使用聚氨酯树脂为基体,以玻璃纤维、碳纤维、玄武岩纤维等作为增强材料,通过缠绕、拉挤、注射成型等工艺制成的纤维增强型树脂复合材料。与传统树脂相比,聚氨酯与增强材料的结合更好,因此抗冲击性能、力学性能和耐候性优异。聚氨酯树脂中不含苯乙烯等挥发物,完全满足国家对“加强绿色产品应用研发加强绿色产品应用研发,推广轻量化、低功耗技术工艺”的相关要求。聚氨酯用于拉挤成型具有黏度低、成型速度更快的工艺优势。聚氨酯复合材料具有密度低、拉伸性、抗冲击性好、耐久性佳、材料可设计性强等特点,被广泛的应用于窗框、电线杆、浴缸、汽车大型部件等制品的生产制造中。
在通常情况下聚氨酯材料的刚性较低,在面对需要有较高模量和强度的使用场景则难以完全满足,如在电网电杆或是铁路接触网支柱等领域应用时,在相同载荷下的目前聚氨酯复合材料杆体的挠度值比相近尺寸的水泥杆体和钢结构杆体大很多,约为水泥杆体的4倍左右。这也使得传统聚氨酯复合材料杆体在受到较大横向力时会出现明显弯曲现象,难以满足在相关领域的使用要求。
基于上述原因,具有高强度和高模量并保持较好韧性的聚氨酯复合材料的开发成为相关研究人员的研究方向,也是未来聚氨酯复合材料的主要发展方向之一。专利CN201110330929公开了一种高刚性聚氨酯的制备方法,通过引入三官能度的聚合物多元醇使聚氨酯分子之间产生化学交联而提升其抗热性能和刚性。专利CN109294215B公开了一种高强度高模量聚氨酯组合料,通过引入聚苯醚微球粒子提升材料的强度与模量,材料力学性能较高,制备工艺简单。专利CN115012220A公开了一种高强度聚氨酯复合材料的制备方法,通过使用表面上浆接枝的聚酰亚胺纤维作为增强材料,制备得到了高强度聚氨酯复合材料,并具有优异的阻燃性能、耐温性能和耐紫外性能。
由于聚氨酯复合材料为较为复杂的多相体系,现有技术对于体系内的微相分布研究和利用不够充分,因此通过适合尺度的微观纳米材料对于体系相分布和相界面进行改性,可以有效提升聚氨酯复合材料的整体性能,得到力学性能和耐久性能更佳的材料,对于行业提升具有重要意义。
发明内容
本发明的目的在于解决上述问题,提供一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料及其制备方法。
本发明所述的一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料是由聚氨酯组合料和增强纤维经由相应复合生产工艺流程制备得到的聚氨酯复合材料;其中所述聚氨酯组合料和增强纤维的质量比为1:(2.5~4);其中所述聚氨酯组合料是由A组分树脂、B组分固化剂和C组分增强材料按照质量比为1:(0.82~1.18):(0.05~0.13)形成的组合料;其中所述增强纤维为通过表面处理剂对于增强纤维进行表面处理得到的表面改性纤维。
该聚氨酯复合材料中所述的聚氨酯组合料中A组分树脂由多元醇、扩链剂、增溶剂和催化剂组成,其中扩链剂、增溶剂和催化剂的含量分别为5-14%、0.8-1.5%和0.3-1.5%,以A组分的总质量计;所述多元醇为饱和脂肪族聚酯多元醇、不饱和脂肪族聚酯多元醇、聚己内酯多元醇、聚芳香酯多元醇、聚混酸酯多元醇或聚醚多元醇中的至少一种;所述扩链剂为乙二醇、丁二醇、1,6-乙二醇、1,4-二(2-羟基乙氧基)苯、甘油、三羟甲基丙烷、季戊四醇、4,4'-亚甲基二(2-氯苯胺)、二甲硫基甲苯二胺、二乙基甲苯二胺中的至少一种;所述相容剂为有机硅表面活性剂、有机锌表面活性剂中的至少一种;其中所述催化剂为热敏延迟性催化剂。
该聚氨酯复合材料中所述聚氨酯组合料中A组分官能度为2-6,羟值为60~480 mgKOH/g。
该聚氨酯复合材料中所述聚氨酯组合料中B组分固化剂由甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体和六亚甲基二异氰酸酯缩二脲中的至少一种组成。
该聚氨酯复合材料中所述聚氨酯组合料中C组分增强材料由纳米纤维和纳米颗粒组成的;所述纳米纤维为纤维素纳米晶体、纤维素纳米纤丝、细菌纤维素、静电纺丝纤维素纳米纤丝、聚酰胺纳米纤维、聚乳酸纳米纤维、聚乙烯吡咯烷酮纳米纤维、聚对苯二甲酸乙二醇酯纳米纤维、纳米玻璃纤维中的至少一种;所述纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒、聚脲纳米颗粒、聚氨酯纳米颗粒、钙矾石纳米颗粒、碳化硅纳米颗粒中的至少一种。
该聚氨酯复合材料中所述聚氨酯组合料C组分中改性纳米纤维为使用多胺类试剂进行表面改性得到的;所述改性纳米纤维的直径在10nm-120nm的范围内,长径比在3-30范围内;所述改性纳米颗粒的直径在30nm-200nm的范围内;纳米纤维和纳米颗粒的质量比为1:(0.7~1.2)。
该聚氨酯复合材料中所述增强纤维为常规纤维经过有机硅类表面改性剂进行改性所得;所述常规纤维为连续玻璃纤维、玻璃纤维毡、竹纤维、碳纤维或聚合物纤维中的至少一种。
该聚氨酯复合材料的制备方法包括以下步骤:
(1)在40~60℃下将聚氨酯组合料中A组分树脂与C组分增强材料经过高速搅拌混合并同时进行超声处理2~10min;
(2)将处理后的混合物在30min内与B组分固化剂混合均匀,并使用相应的复合生产工艺将组合料与增强纤维进行复合制备复合材料,常温熟化8-12h即可得到高模量聚氨酯复合材料。
该制备方法步骤(2)中所述复合生产工艺为拉挤成型、缠绕成型、注射成型、反应注射成型或注射压缩成型中的至少一种。
本发明一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料及其制备方法的积极效果是:
与现有的聚氨酯复合材料相比较,本发明通过引入改性纳米纤维和颗粒形成的纳米复合网络结构在聚氨酯树脂与增强纤维间形成多尺度的拓扑结构,通过纳米纤维与颗粒之间的相互作用力,在纳米纤维结合于纳米颗粒附近,并通过较高的毛细管力和分子间作用力使纳米纤维互相缠结和纳米颗粒形成具有极高内聚力的纳米复合网络结构进一步在复合材料中形成具有超稳定性的多相系统。相比较传统的单独纳米材料其形成的纳米复合网络结构在稳定性和界面附着能力有明显增强,作为连接宏观增强纤维和树脂基体的枢纽,这种结构的引入可以大大提升了材料的力学性能。
由于宏观增强纤维和纳米增强材料均经过相应的表面处理,纳米增强材料会以多尺度的拓扑结构的形式分布在树脂与宏观纤维界面及树脂内部和表面,极大增强宏观纤维和树脂基体的作用力。当材料受到外力作用时可以有效保护基体不受损伤,并减少相应的载荷银纹和剪切带的产生和扩展;在载荷较大时纳米材料可以通过改变银纹及微裂纹的扩展方向,增加材料的极限载荷范围。而在外加载荷超出体系承受范围时,断裂带和破坏应力在这种具有较高内聚力的特殊微纳米增强结构中的传播需要耗散大量的能量,因此有效限制了材料破坏的发展,从强度和韧性上均全方面增强了聚氨酯复合材料的力学性能。
可以看出本发明提供的一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料作用机理清晰、生产工艺简单、性能优秀,适用于大规模生产,对于高性能复合材料构件的制备具有重要意义。
实施方式
下面结合具体实施例对本发明做进一步详细的描述。
实施例1:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A1树脂:460g聚四亚甲基醚多元醇,6g有机硅表面活性剂,30g1,4-二(2-羟基乙氧基)苯和2.5g热敏延迟性催化剂。B1固化剂:411g甲苯二异氰酸酯。C1增强组分:21.2g改性纤维素纳米晶体和18.8g二氧化硅纳米颗粒。
(2)在45℃下将聚氨酯组合料中A1组分树脂与C1组分增强材料经过高速搅拌混合并同时进行超声处理5min。
(3)将处理后的混合物在30min内与B1组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3300g改性连续玻璃纤维进行复合制备聚氨酯复合材料,常温熟化10h即可得到高模量聚氨酯复合材料。
实施例2:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A2树脂:432g聚己二酸酯多元醇,6.3g有机锌表面活性剂,45g4,4'-亚甲基二(2-氯苯胺)和1.5g热敏延迟性催化剂。B2固化剂:446g异佛尔酮二异氰酸酯。C2增强组分:24.8g改性纤维素纳米纤丝和20.2g聚脲纳米颗粒。
(2)在40℃下将聚氨酯组合料中A2组分树脂与C2组分增强材料经过高速搅拌混合并同时进行超声处理5min。
(3)将处理后的混合物在30min内与B2组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3500g改性玻璃纤维毡进行复合制备聚氨酯复合材料,常温熟化8h即可得到高模量聚氨酯复合材料。
实施例3:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A3树脂:448g聚己内酯多元醇,5.1g有机硅表面活性剂,55g 三羟甲基丙烷和3g热敏延迟性催化剂。B3固化剂:430g二苯基甲烷二异氰酸酯。C3增强组分:28g改性聚酰胺纳米纤维和23.2g二氧化钛纳米颗粒。
(2)在40℃下将聚氨酯组合料中A3组分树脂与C3组分增强材料经过高速搅拌混合并同时进行超声处理6min。
(3)将处理后的混合物在30min内与B3组分固化剂混合均匀,并使用缠绕成型生产工艺将组合料与3770g改性聚合物纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到高模量聚氨酯复合材料。
实施例4:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A4树脂:470g聚氧化丙烯多元醇,7g有机锌表面活性剂,42g 二甲硫基甲苯二胺和3.5g热敏延迟性催化剂。B4固化剂:438g二环己基甲烷二异氰酸酯。C4增强组分:15.4g改性聚乙烯吡咯烷酮纳米纤维和16.6g聚氨酯纳米颗粒。
(2)在55℃下将聚氨酯组合料中A4组分树脂与C4组分增强材料经过高速搅拌混合并同时进行超声处理5min。
(3)将处理后的混合物在30min内与B4组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3800g改性碳纤维进行复合制备聚氨酯复合材料,常温熟化8h即可得到高模量聚氨酯复合材料。
实施例5:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A5树脂:445g聚邻苯二甲酸二乙二醇酯多元醇,4.5g有机硅表面活性剂,28g季戊四醇和2.9g热敏延迟性催化剂。B5固化剂:422g六亚甲基二异氰酸酯。C5增强组分:26.4g改性聚对苯二甲酸乙二醇酯纳米纤维和26.4g碳化硅纳米颗粒。
(2)在50℃下将聚氨酯组合料中A5组分树脂与C5组分增强材料经过高速搅拌混合并同时进行超声处理8min。
(3)将处理后的混合物在30min内与B5组分固化剂混合均匀,并使用注射成型生产工艺将组合料与3600g改性玻璃纤维毡进行复合制备聚氨酯复合材料,常温熟化8h即可得到高模量聚氨酯复合材料。
实施例6:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A6树脂:448g二聚酸聚酯多元醇,5.5g有机锌表面活性剂,50.8g二乙基甲苯二胺和4g热敏延迟性催化剂。B6固化剂:220g苯二亚甲基二异氰酸酯和310g甲苯二异氰酸酯三聚体。C6增强组分:33.2g改性纳米玻璃纤维和22.8g钙矾石纳米颗粒。
(2)在45℃下将聚氨酯组合料中A6组分树脂与C6组分增强材料经过高速搅拌混合并同时进行超声处理10min。
(3)将处理后的混合物在30min内与B6组分固化剂混合均匀,并使用缠绕成型生产工艺将组合料与4100g改性碳纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到高模量聚氨酯复合材料。
实施例7:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A7树脂:302g聚四亚甲基醚二醇,205g聚氧化丙烯多元醇,4.6g有机锌表面活性剂,38.4g三羟甲基丙烷和3.3g热敏延迟性催化剂。B7固化剂:233g对苯二异氰酸酯和344g六亚甲基二异氰酸酯三聚体。C7增强组分:29.7g改性纤维素纳米纤丝和25.3g二氧化硅纳米颗粒。
(2)在50℃下将聚氨酯组合料中A7组分树脂与C7组分增强材料经过高速搅拌混合并同时进行超声处理8min。
(3)将处理后的混合物在30min内与B7组分固化剂混合均匀,并使用注射成型生产工艺将组合料与3900g改性连续玻璃纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到高模量聚氨酯复合材料。
实施例8:一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其制备过程如下
(1)聚氨酯组合料:A8树脂:310g聚氧化丙烯多元醇,167g聚己内酯多元醇,4.2g有机硅表面活性剂,36g三异丙醇胺和3g热敏延迟性催化剂。B8固化剂:430g环己烷二亚甲基二异氰酸酯。C8增强组分:34.5g改性聚酰胺纳米纤维和30.5g聚脲纳米颗粒。
(2)在45℃下将聚氨酯组合料中A8组分树脂与C8组分增强材料经过高速搅拌混合并同时进行超声处理10min。
(3)将处理后的混合物在30min内与B8组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与4060g改性竹纤维进行复合制备聚氨酯复合材料,常温熟化8h即可得到高模量聚氨酯复合材料。
对比例1:无纳米材料增强的聚氨酯复合材料
(1)将A1组分树脂与B1组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3300g改性连续玻璃纤维进行复合制备聚氨酯复合材料,常温熟化10h即可得到无纳米材料增强的聚氨酯复合材料。
对比例2:未改性纳米纤维和增强纤维的聚氨酯复合材料
(1)聚氨酯组合料:A3树脂和B3固化剂同上。C9增强组分:28g未改性聚酰胺纳米纤维和23.2g二氧化钛纳米颗粒。
(2)在40℃下将聚氨酯组合料中A3组分树脂与C9组分增强材料经过高速搅拌混合并同时进行超声处理6min。
(3)将处理后的混合物在30min内与B3组分固化剂混合均匀,并使用缠绕成型生产工艺将组合料与3770g未改性聚合物纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到未改性纳米纤维和增强纤维的聚氨酯复合材料。
对比例3:纯纳米纤维增强的聚氨酯复合材料
(1)聚氨酯组合料:A4树脂和B4固化剂同上。C10增强组分:32g改性聚乙烯吡咯烷酮纳米纤维。
(2)在55℃下将聚氨酯组合料中A4组分树脂与C10组分增强材料经过高速搅拌混合并同时进行超声处理5min。
(3)将处理后的混合物在30min内与B4组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3800g改性碳纤维进行复合制备聚氨酯复合材料,常温熟化8h即可得到纯纳米纤维增强的聚氨酯复合材料。
对比例4:纯纳米颗粒增强的聚氨酯复合材料
(1)聚氨酯组合料:A4树脂和B4固化剂同上。C11增强组分:32g聚氨酯纳米颗粒。
(2)在55℃下将聚氨酯组合料中A4组分树脂与C11组分增强材料经过高速搅拌混合并同时进行超声处理5min。
(3)将处理后的混合物在30min内与B4组分固化剂混合均匀,并使用拉挤成型生产工艺将组合料与3800g改性碳纤维进行复合制备聚氨酯复合材料,常温熟化8h即可得到纯纳米颗粒增强的聚氨酯复合材料。
对比例5:纳米纤维颗粒复合增强的聚氨酯复合材料
(1)聚氨酯组合料:A7树脂和B7固化剂同上。C12增强组分:44g改性纤维素纳米纤丝和11g二氧化硅纳米颗粒。
(2)在50℃下将聚氨酯组合料中A7组分树脂与C12组分增强材料经过高速搅拌混合并同时进行超声处理8min。
(3)将处理后的混合物在30min内与B7组分固化剂混合均匀,并使用注射成型生产工艺将组合料与3900g改性连续玻璃纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到高模量聚氨酯复合材料。
对比例6:纳米纤维颗粒复合增强的聚氨酯复合材料
(1)聚氨酯组合料:A7树脂和B7固化剂同上。C13增强组分:11g改性纤维素纳米纤丝和44g二氧化硅纳米颗粒。
(2)在50℃下将聚氨酯组合料中A7组分树脂与C13组分增强材料经过高速搅拌混合并同时进行超声处理8min。
(3)将处理后的混合物在30min内与B7组分固化剂混合均匀,并使用注射成型生产工艺将组合料与3900g改性连续玻璃纤维进行复合制备聚氨酯复合材料,常温熟化9h即可得到高模量聚氨酯复合材料。
效果说明:
使用本发明中实施例1-8中制备的纳米纤维-颗粒复合增强的高模量聚氨酯复合材料与对比例1-6制备的聚氨酯复合材料进行性能测试对比。
按照GB/T 2567-2008《树脂浇筑体性能试验方法》和GB/T 9640-2008《软质和硬质泡沫聚合材料加速老化试验方法》进行力学性能和耐久性能测试。其中紫外老化测试按GB/T 16422.3-2014 模拟产品的自然紫外老化效果,采用2型(UVB-313)灯(方法C),暴露循环1000h;盐雾老化按GB/T 10125-2012规定的中性盐雾试验(NSS)方法,老化1000h;湿热老化:按GB/T 2573-2008规定的湿热试验方法,老化720h。
将相关测试结果整理至表1:
表1 聚氨酯复合材料性能测试结果
样品 | 纵向拉伸强度(MPa) | 纵向拉伸弹性模量(GPa) | 纵向弯曲强度(MPa) | 纵向弯曲弹性模量(GPa) | 纵向压缩强度(MPa) | 紫外老化拉伸强度保留率 (%) | 盐雾老化拉伸强度保留率(%) | 湿热老化拉伸强度保留率(%) |
实施例1 | 982 | 45.8 | 1426 | 51.2 | 692 | 96.3 | 95.2 | 94.3 |
实施例2 | 1060 | 48.2 | 1538 | 54.3 | 746 | 95.4 | 94.5 | 92.2 |
实施例3 | 996 | 46.9 | 1457 | 52.5 | 721 | 97.6 | 96.3 | 93.7 |
实施例4 | 973 | 44.8 | 1420 | 50.6 | 695 | 94.5 | 94.4 | 94.6 |
实施例5 | 1010 | 47.6 | 1573 | 56.3 | 773 | 97.0 | 95.8 | 95.3 |
实施例6 | 986 | 46.1 | 1480 | 53.1 | 729 | 95.6 | 93.6 | 91.8 |
实施例7 | 1053 | 47.9 | 1551 | 55.7 | 765 | 96.4 | 93.5 | 92.9 |
实施例8 | 1005 | 47.1 | 1496 | 53.6 | 736 | 95.5 | 94.7 | 93.4 |
对比例1 | 588 | 23.1 | 886 | 31.8 | 432 | 91.5 | 88.3 | 85.7 |
对比例2 | 775 | 30.5 | 1154 | 41.4 | 562 | 92.2 | 87.5 | 86.6 |
对比例3 | 682 | 26.8 | 964 | 34.6 | 470 | 89.7 | 89.2 | 84.3 |
对比例4 | 653 | 25.7 | 955 | 32.3 | 439 | 91.8 | 91.1 | 89.2 |
对比例5 | 735 | 28.9 | 999 | 35.9 | 488 | 88.7 | 89.7 | 86.4 |
对比例6 | 786 | 31.0 | 1054 | 37.9 | 516 | 92.5 | 90.6 | 90.1 |
从表1的数据可以看出,实施例所制备的聚氨酯复合材料的力学性能和耐久性性能十分优异,具有较高的各向强度和模量,尤其是弯曲强度和模量较高,这对于聚氨酯复合材料在实际应用中的构件挠度和变形控制有很大的意义。
而对比例1中由于缺少纳米材料作为体系中的增强材料,断裂应力及微裂纹的传递及界面滑移容易,其力学性能较实施例有明显降低。而对比例2使用未表面改性的纳米材料与增强纤维,由于未改性材料的界面作用显著降低,因此不论是纳米材料的复合网络构建及与增强纤维的界面分布均产生较大变化,导致强度有一定的降低。对比例3和对比例4仅使用一种纳米材料作为微观增强材料,由于单一纳米材料形成的增强体系较纳米纤维-颗粒形成的复合网络结构其内聚力有明显下降,因此增强效果也有所降低。对比例5和对比例6则可以看出,纳米纤维和颗粒的比例必须在一定的范围内才可以在较短的时间内在超声的条件下形成增强的复合网络结构形式,当两种材料比例在推荐配比之外时,则增强效果明显降低。从耐久性数据可以看出,对于紫外、盐雾和湿热老化而言,其主要性能是由于树脂本身带来的,所以对比例和实施例的区别并没有很明显,但纳米增强体系的引入由于对于复合材料整体性能的提升,依旧带来了一定的耐久性能提升。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,任何未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
1.一种纳米纤维-颗粒复合增强的高模量聚氨酯复合材料,其特征在于,其是由聚氨酯组合料和增强纤维经由相应复合生产工艺流程制备得到的聚氨酯复合材料;其中所述聚氨酯组合料和增强纤维的质量比为1:(2.5~4);其中所述聚氨酯组合料是由A组分树脂、B组分固化剂和C组分增强材料按照质量比为1:(0.82~1.08):(0.05~0.13)形成的组合料;其中所述增强纤维为通过表面处理剂对于增强纤维进行表面处理得到的表面改性纤维。
2.根据权利要求1中所述的一种聚氨酯复合材料,其特征在于所述的聚氨酯组合料中A组分树脂由多元醇、扩链剂、增溶剂和催化剂组成,其中扩链剂、增溶剂和催化剂的含量分别为5-14%、0.8-1.5%和0.1-1.5%,以A组分的总质量计;其中所述多元醇为饱和脂肪族聚酯多元醇、不饱和脂肪族聚酯多元醇、聚己内酯多元醇、聚芳香酯多元醇、聚混酸酯多元醇或聚醚多元醇中的至少一种;其中所述扩链剂为乙二醇、丁二醇、1,6-乙二醇、1,4-二(2-羟基乙氧基)苯、甘油、三羟甲基丙烷、季戊四醇、4,4'-亚甲基二(2-氯苯胺)、二甲硫基甲苯二胺、二乙基甲苯二胺或三异丙醇胺中的至少一种;其中所述相容剂为有机硅表面活性剂、有机锌表面活性剂中的至少一种;其中所述催化剂为热敏延迟性催化剂。
3.根据权利要求2中所述的一种聚氨酯复合材料,其特征在于所述的聚氨酯组合料中A组分官能度为2-6,羟值为60~480 mgKOH/g。
4.根据权利要求1中所述的一种聚氨酯复合材料,其特征在于所述的聚氨酯组合料中B组分固化剂由甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯、环己烷二亚甲基二异氰酸酯、对苯二异氰酸酯、苯二亚甲基二异氰酸酯、甲苯二异氰酸酯三聚体、六亚甲基二异氰酸酯三聚体和六亚甲基二异氰酸酯缩二脲中的至少一种组成。
5.根据权利要求1中所述的一种聚氨酯复合材料,其特征在于所述的聚氨酯组合料中C组分增强材料由改性纳米纤维和纳米颗粒组成的;其中所述改性纳米纤维为改性纤维素纳米晶体、改性纤维素纳米纤丝、改性细菌纤维素、改性静电纺丝纤维素纳米纤丝、改性聚酰胺纳米纤维、改性聚乳酸纳米纤维、改性聚乙烯吡咯烷酮纳米纤维、改性聚对苯二甲酸乙二醇酯纳米纤维、改性纳米玻璃纤维中的至少一种;所述纳米颗粒为二氧化硅纳米颗粒、二氧化钛纳米颗粒、聚脲纳米颗粒、聚氨酯纳米颗粒、钙矾石纳米颗粒、碳化硅纳米颗粒中的至少一种。
6.根据权利要求5中所述的一种聚氨酯复合材料,其特征在于所述聚氨酯组合料C组分中改性纳米纤维为纳米纤维使用多胺类试剂进行表面改性得到的;所述改性纳米纤维的直径在10nm-120nm的范围内,长径比在3-30范围内;所述纳米颗粒的直径在30nm-200nm的范围内;改性纳米纤维和纳米颗粒的质量比为1:(0.7~1.2)。
7.根据权利要求1中所述的一种聚氨酯复合材料,其特征在于所述增强纤维为常规纤维经过有机硅类表面改性剂进行改性所得;所述常规纤维为改性连续玻璃纤维、改性玻璃纤维毡、改性竹纤维、改性碳纤维或改性聚合物纤维中的至少一种。
8.根据权利要求1中所述的一种聚氨酯复合材料的制备方法,其特征在于包括以下步骤:
(1)在40~60℃下将聚氨酯组合料中A组分树脂与C组分增强材料经过高速搅拌混合并同时进行超声处理2~10min;
(2)将处理后的混合物在30min内与B组分固化剂混合均匀,并使用相应的复合生产工艺将组合料与增强纤维进行复合制备复合材料,常温熟化8-12h即可得到高模量聚氨酯复合材料。
9.根据权利要求8中所述的一种聚氨酯复合材料的制备方法,其中所述复合生产工艺为拉挤成型、缠绕成型、注射成型、反应注射成型或注射压缩成型中的至少一种。
10.根据权利要求1中所述一种聚氨酯复合材料作为栏杆、枕木、支柱、桥架、墙体及建筑物的应用。
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