CN101679725A - 阻燃性和形状保持性增强的聚酯 - Google Patents
阻燃性和形状保持性增强的聚酯 Download PDFInfo
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Abstract
本发明公开了一种赋予聚酯优良的阻燃性和形状保持性的组合物。基于100重量%的组合物,所述组合物包含:(i)55重量%~75重量%的硅酸钠溶液,(ii)0.5重量%~7重量%的羧甲基纤维素,(iii)0.7重量%~10重量%的聚氨酯树脂,(iv)0.7重量%~10重量%的丙烯酸树脂混合物和(v)剩余重量百分比的水,其中,(i)硅酸钠溶液包含摩尔比为1∶2.1~1∶2.9的Na2O和SiO2,(iii)聚氨酯树脂由70重量%~80重量%的亚甲基二苯基异氰酸酯和20重量%~30重量%的甲基聚乙二醇组成,和(iv)丙烯酸树脂混合物由36重量%~40重量%的丙烯酸丁酯单体、10重量%~13重量%的甲基丙烯酸甲酯、1重量%~2重量%的乳化剂、3重量%~5重量%的丙烯酸以及剩余重量百分比的水组成。本发明还公开了制备所述组合物的方法以及将所述组合物应用于聚酯树脂的方法。应用了所述组合物的聚酯树脂适于用作汽车NVH部件,尤其是发动机舱的吸音绝热部件。
Description
技术领域
本发明涉及一种赋予聚酯阻燃性和形状保持性的组合物、将所述组合物应用于聚酯树脂的方法以及应用了所述组合物的聚酯树脂。
背景技术
驾驶舒适度是驾驶者在汽车行驶时所体验的感觉之一,决定驾驶舒适度的NVH性能近来在汽车行业中备受关注。然而,汽车材料的选择受到环境问题的限制。因此,需要开发既没有环境问题又显示出改善的NVH性能的材料。
本发明中使用的术语“NVH”是由三个影响汽车驾驶者的驾驶舒适度的因素,即“噪声(Noise)”、“振动(Vibration)”和“声振粗糙度(Harshness)”的首字母组成的首字母缩写词。因此,NVH部件包括所有降低三个因素的水平并因此使汽车驾驶者感到最佳驾驶舒适度的汽车部件。这三个因素定义如下:
(1)噪声:行驶的汽车产生的外部或内部令人不舒适的声音
(2)振动:行驶的汽车周期性振动的现象
(3)声振粗糙度:在不平的道路上行驶时与道路表面碰撞所产生的振动或噪音。
目前通过使用热压或冷压将吸音绝热材料压入模具中来模塑用于交通工具如汽车的NVH部件。作为材料,通常使用EVR板、聚氨酯泡沫、玻璃棉、树脂毡和聚酯等。特别是,由于如发动机舱等高热部件要求显示出某种程度的阻燃性,因此其由玻璃棉制成。然而,玻璃棉导致与粉尘散布以及废物处理相关的环境污染,因此其使用受到限制。
聚酯对人类无害并且磨损不产生粉尘,因此对环境友好。此外,聚酯的优势在于其优良的绝热性能和优异的吸音性能。然而,聚酯具有这样的缺陷:阻燃性差,模塑中和模塑后因高弹性导致形状不稳定。
在此情况下,有必要使用增塑剂以稳定地保持最终产品的形状。目前使用的保持形状的增塑剂具有以下问题:它们含有铅、六价铬(Cr)、二间苯二甲酸酯(DOP)、PVC、酚醛树脂、脲醛树脂或者P.P.(聚丙烯),所有这些物质都因其为有毒材料或者在燃烧过程中放出有毒气体而受到管控。
发明内容
技术问题
本发明的目的之一是提供一种赋予聚酯阻燃性和形状保持性的组合物以及制备所述组合物的方法。
本发明的另一个目的是提供将所述组合物应用于聚酯树脂的方法和应用了所述组合物的聚酯树脂,所述聚酯树脂显示出改善的阻燃性和形状保持性,同时保持了其固有的性能,如对人类无害、环境友好和优良的绝热和吸音性能。
本发明的再一个目的是提供由所述聚酯树脂制备的NVH部件,所述NVH部件能够改善汽车的驾驶舒适度而不产生任何环境问题。
技术方案
根据实现上述目的的本发明的一个方面,提供能够赋予聚酯优异的阻燃性和形状保持性的组合物。基于100重量%的组合物,所述组合物包含下列组成成分:(i)55重量%~75重量%的硅酸钠溶液,(ii)0.5重量%~7重量%的羧甲基纤维素,(iii)0.7重量%~10重量%的聚氨酯树脂,(iv)0.7重量%~10重量%的丙烯酸树脂混合物和(v)剩余重量百分比的水,其中,(i)硅酸钠溶液包含摩尔比为1∶2.1~1∶2.9的Na2O和SiO2,(iii)聚氨酯树脂由70重量%~80重量%的亚甲基二苯基异氰酸酯和20重量%~30重量%的甲基聚乙二醇组成,且(iv)丙烯酸树脂混合物由36重量%~40重量%的丙烯酸丁酯单体、10重量%~13重量%的甲基丙烯酸甲酯、1重量%~2重量%的乳化剂、3重量%~5重量%的丙烯酸以及剩余重量百分比的水组成。
组合物中所含的硅酸钠溶液是赋予本领域中长时间广泛使用的聚酯以优异的阻燃性的组成组分。由于氧化钠(Na2O)与二氧化硅(SiO2)在高温环境下的反应,硅酸钠溶液导致形成碳化硅膜。燃烧时,消耗碳化硅膜,同时产生二氧化碳和一氧化碳气体,因此起到改善绝热性能的作用。
构成硅酸钠溶液的Na2O和SiO2优选以摩尔比1∶2.1~1∶2.9使用。所述摩尔比是指SiO2与Na2O的摩尔比,并通过以SiO2/Na2O的重量比乘以常数1.032计算。使用包含所述摩尔比的Na2O和SiO2的硅酸钠溶液的原因是:所述摩尔比的组合物易于应用于聚酯并脱水,并且具有较高的干燥效率,因此改进制备效率,并导致在合成聚酯纤维的表面上形成均匀的阻燃膜。
硅酸钠溶液的含量影响最终聚酯产品的重量和阻燃性。因此,基于组合物的总重量,硅酸钠溶液的用量优选为55重量%~75重量%。如果硅酸钠溶液的含量低于55重量%,则不能充分地赋予阻燃性。同时,如果硅酸钠溶液的含量超过75重量%,则组合物的粘度增加,因而导致难以进行实现阻燃的应用和干燥工序,并导致制备效率下降。
组合物中的羧甲基纤维素降低硅酸钠溶液的粘度,因此使得组合物能很好地渗透入阻燃材料中,并改善组合物的储存稳定性。
基于组合物的总重量,羧甲基纤维素的用量为0.5重量%~7重量%。如果羧甲基纤维素的含量低于0.5重量%,则组合物的粘度不能降至理想的水平。因此,羧甲基纤维素不能充分发挥其使得组合物易于应用于聚酯树脂、使聚酯树脂能够良好地干燥并增加储存稳定性的作用。同时,如果羧甲基纤维素的含量超过7重量%,则其它组分,特别是硅酸钠溶液的含量降低,因此不能充分实现阻燃性。
组合物的聚氨酯树脂和丙烯酸树脂是热固性树脂,将热固性树脂定义为这样的聚合物材料:一旦它们因热固化成型为永久的形状,就不能在固化后重新成型为另一种形状。这些热固性树脂抑制了聚酯树脂的热塑性,由此使得形状得以保持。
可以在本发明中使用的聚氨酯树脂是70重量%~80重量%的异氰酸酯类化合物(如甲苯二异氰酸酯(TDI)或者亚甲基二苯基异氰酸酯(MDI))和20重量%~30重量%甲基聚乙二醇的混合物。作为异氰酸酯类化合物,优选的是使用低毒的亚甲基二苯基异氰酸酯。
丙烯酸树脂混合物由36重量%~40重量%的丙烯酸丁酯单体、10重量%~13重量%的甲基丙烯酸甲酯、1重量%~2重量%的乳化剂、3重量%~5重量%的丙烯酸和剩余重量百分比的水组成。
基于组合物的总重量,聚氨酯树脂和丙烯酸树脂混合物的用量均为0.7重量%~10重量%。如果每种组分的含量低于0.7重量%,则不能充分地赋予聚酯树脂以形状保持性,而且模塑的聚酯树脂的强度较低。同时,如果每种组分的含量超过10重量%,则材料的重量增加并且吸音性能劣化。
除了所述组分外,基于100重量%的组合物,所述组合物还包含剩余重量百分比的水。
本发明涉及制备所述组合物的方法。所述方法包括:(a)混合硅酸钠溶液和聚氨酯树脂;(b)混合丙烯酸树脂混合物和水;(c)在搅拌的同时缓慢将在步骤(b)中得到的混合物加入在步骤(a)中得到的混合物中;和(d)向在步骤(c)中得到的反应混合物中加入羧甲基纤维素。
如果将硅酸钠溶液直接与水混合,则出现部分凝结,因此不能形成均匀的混合物。由于此原因,将聚氨酯树脂和丙烯酸树脂混合物用作介质。更具体而言,在缓慢搅拌的同时向硅酸钠溶液和聚氨酯树脂的混合物中加入丙烯酸树脂混合物和水的混合物,由此可以制备均匀的反应混合物,并且最终的组合物可显示出优异的储存稳定性。
此外,本发明涉及将所述组合物应用于聚酯树脂的方法。优选使用浸渍法以使组合物能够完全应用于全部的聚酯树脂。通过浸渍、脱水和干燥工序实现所述浸渍。使用高压喷嘴进行浸渍工序。通过辊压、抽真空和振动进行脱水工序,并通过高温固化和低温干燥进行干燥工序。
如果对其中浸渍有组合物的聚酯树脂进行加热,则组合物的粘度和比重下降。结果,组合物沉在底部。因此,在初始干燥步骤中,向聚酯树脂引入160℃或更高温度的热气压(3kg/cm2~7kg/cm2),由此快速固化聚酯树脂,同时防止组合物沉在底部。在高温固化的过程中,将聚酯树脂干燥至大约70%的干燥率,在110℃~130℃的低温脱水,并进行用于保持形态的冷却。
此外,本发明还涉及应用了所述组合物的聚酯树脂。应用了所述组合物的聚酯树脂的形状没有特别限制,但是优选使用具有双密度结构的层压聚酯树脂。这种聚酯树脂由于双密度而具有强粘附性并使得能够更稳定地保持模塑产品的形状。
双密度层压聚酯树脂可以通过将纤维成型为网状、层压所述纤维并针刺层压物以使纤维相互编织而制备。将成型为网状的另一纤维热结合至经编织的纤维,从而将纤维成型为片状。为了使片的厚度达到理想的水平,可以使用仅在其上表面使网状纤维相互编织的半穿刺。
可以根据其用途很好地控制构成双密度聚酯板的两层的密度范围。例如,可以使用其中高密度(≥70kg/m3)聚酯与低密度(≥10kg/m3)聚酯结合的双密度聚酯板,这样基于应用了树脂组合物的聚酯树脂的密度,可将板的总体平均密度调整为15kg/m3~50kg/m3。
应用了组合物的聚酯树脂可以用作汽车NVH部件用材料。如图1所示,NVH部件的实例包括但不限于绝缘罩、内部/外部挡板、防护垫(fender seal)、顶部衬垫、尾箱盖、尾箱板、轮罩、制动底板(back plate)、后底板、前底板和集成垫(integrated carpet)。应用了组合物的聚酯树脂适于用作用于要求耐热性和绝热性的发动机舱的吸音绝热材料。
有益效果
本发明的组合物能够赋予聚酯优异的阻燃性和形状保持性。应用了所述组合物的聚酯显示出改善的阻燃性和形状保持性,同时保留了其固有的性能,即对人体无害、环境友好以及优良的绝热和吸音性能。因此,本发明的聚酯可用于生产能够改善汽车驾驶舒适度而不导致任何环境问题的NVH部件。
附图说明
通过下述结合附图的详细说明会更清楚地理解本发明的上述和其它目的、特征以及其它优点,附图中:
图1显示了可由应用了本发明的组合物的聚酯树脂制成的汽车NVH部件的实例。
具体实施方式
通过下述实施例将更好地理解本发明。不应将这些实施例理解为限制本发明的范围。
实施例
实施例1
(1)组合物的制备
通过将2号硅酸钠液体和3号硅酸钠液体(均商购获得)混合来制备硅酸钠溶液,使得摩尔比(即SiO2/Na2O的重量比×1.032)被调整为2.5。此处使用的2号硅酸钠液体在20℃包含52重量%~54重量%的Be′、14重量%~15重量%的Na2O、34重量%~35重量%的SiO2、0.05重量%以下的Fe2O3和0.2重量%以下的水不溶性固体。此处使用的3号硅酸钠液体在20℃包含40重量%~42重量%的Be′、9重量%~10重量%的Na2O、28重量%~30重量%的SiO2、0.03重量%以下的Fe2O3和0.2重量%以下的水不溶性固体。
基于100重量%,向硅酸钠溶液中添加:5重量%的羧甲基纤维素;5重量%的聚氨酯树脂(基于100重量%的聚氨酯树脂,其由70重量%的亚甲基二苯基异氰酸酯(MDI)和30重量%的甲基聚乙二醇组成);5重量%的丙烯酸树脂混合物(基于丙烯酸树脂混合物的重量,其由36重量%的丙烯酸丁酯单体、10重量%的甲基丙烯酸甲酯、1重量%的乳化剂、3重量%的丙烯酸和剩余重量百分比的水组成);和剩余重量百分比的水,由此制备赋予聚酯阻燃性和形状保持性的组合物。
(2)聚酯板的制备和组合物(1)向聚酯板的应用
使低密度(15.5kg/m3)聚酯层和高密度(47kg/m3)聚酯层彼此结合。将层压物浸入在第(1)部分中制备的组合物中,然后干燥,以制备包括厚度为27nm的低密度(32.5kg/m3)聚酯层和厚度为3nm的高密度(74kg/m3)聚酯层的双密度聚酯板(总厚度:30nm;总体平均密度:37kg/m3)。
(3)阻燃性测试
KS F 2271测试
在韩国的火灾保险商实验室(Fire Insurers Laboratories),根据用于测试建筑物结构和内部材料的阻燃性的KS F 2271测试法测试第(2)部分中制备的聚酯板的阻燃性。结果如下表1所示。由表1所示数据可以确定,基于KS F 2271测试标准,第(2)部分中制备的聚酯板显示出高于二级的阻燃性。
表1
UL94 V-0测试
如果所测试的材料满足下述标准,则将其归类为UL94V-0级别:i)对样品施用燃烧器火焰10秒然后移开时,燃烧时间(直至所施用的样品火焰熄灭的时间)不超过10秒;ii)对一组五个样品重复测试10次时,总燃烧时间不超过50秒;iii)没有燃烧物滴落,该滴落物可能引起下方(即与任意测试样品距离大约30cm)的棉花燃烧。只要五个样品中的至少一个不满足上述要求之一,则对另外五个样品重复相同的测试。在此情况下,总燃烧时间应当在51秒~55秒内。
对第(2)部分中制备的聚酯板进行上述测试。结果,可以确定该聚酯板满足UL 94V-0标准。
实施例2
干燥第(2)部分中制备的聚酯板,并在160℃~220℃使用装有模具的热压机将其压在非织造织物和铝(Al)箔上15秒~45秒。
应用了本发明的组合物的聚酯树脂显示出改善的阻燃性。可以确定,由该聚酯树脂制备的NVH部件显示出优良的形状保持性。
通常用作NVH部件用材料的玻璃棉与本发明的聚酯树脂的性能比较简要示于表2中。
表2
权利要求书(按照条约第19条的修改)
1.一种赋予聚酯优良的阻燃性和形状保持性的组合物,基于100重量%的所述组合物,所述组合物包含:
(i)55重量%~75重量%的硅酸钠溶液;
(ii)0.5重量%~7重量%的羧甲基纤维素;
(iii)0.7重量%~10重量%的聚氨酯树脂;
(iv)0.7重量%~10重量%的丙烯酸树脂混合物;和
(v)剩余重量百分比的水,
其中,(i)所述硅酸钠溶液包含摩尔比为1∶2.1~1∶2.9的Na2O和SiO2,(iii)所述聚氨酯树脂由70重量%~80重量%的亚甲基二苯基异氰酸酯和20重量%~30重量%的甲基聚乙二醇组成,且(iv)所述丙烯酸树脂混合物由36重量%~40重量%的丙烯酸丁酯单体、10重量%~13重量%的甲基丙烯酸甲酯、1重量%~2重量%的乳化剂、3重量%~5重量%的丙烯酸以及剩余重量百分比的水组成。
2.制备权利要求1所述的组合物的方法,所述方法包括:
(a)混合所述硅酸钠溶液和所述聚氨酯树脂;
(b)混合所述丙烯酸树脂混合物和水;
(c)在搅拌的同时缓慢将在步骤(b)中得到的混合物添加至在步骤(a)中得到的混合物中;和
(d)向在步骤(c)中得到的反应混合物中加入羧甲基纤维素。
3.一种处理聚酯树脂以赋予所述聚酯树脂阻燃性和形状保持性的方法,所述方法包括将所述聚酯树脂浸渍至权利要求1所述的组合物中,然后脱水和干燥。
4.如权利要求3所述的方法,其中,使用高压喷嘴进行所述浸渍,通过辊压、抽真空和振动进行所述脱水,并通过高温固化和低温干燥进行所述干燥。
5.如权利要求3所述的方法,其中,所述聚酯树脂的形状为双密度聚酯板。
6.经权利要求3~5中任一项所述的方法处理的聚酯树脂,所述聚酯树脂具有阻燃性和形状保持性。
7.一种汽车用NVH部件,所述NVH部件通过压铸权利要求6所述的聚酯树脂制备而成。
Claims (7)
1.一种赋予聚酯优良的阻燃性和形状保持性的组合物,基于100重量%的所述组合物,所述组合物包含:
(i)55重量%~75重量%的硅酸钠溶液;
(ii)0.5重量%~7重量%的羧甲基纤维素;
(iii)0.7重量%~10重量%的聚氨酯树脂;
(iv)0.7重量%~10重量%的丙烯酸树脂混合物;和
(v)剩余重量百分比的水,
其中,(i)所述硅酸钠溶液包含摩尔比为1∶2.1~1∶2.9的Na2O和SiO2,(iii)所述聚氨酯树脂由70重量%~80重量%的亚甲基二苯基异氰酸酯和20重量%~30重量%的甲基聚乙二醇组成,且(iv)所述丙烯酸树脂混合物由36重量%~40重量%的丙烯酸丁酯单体、10重量%~13重量%的甲基丙烯酸甲酯、1重量%~2重量%的乳化剂、3重量%~5重量%的丙烯酸以及剩余重量百分比的水组成。
2.制备权利要求1所述的组合物的方法,所述方法包括:
(a)混合所述硅酸钠溶液和所述聚氨酯树脂;
(b)混合所述丙烯酸树脂混合物和水;
(c)在搅拌的同时缓慢将在步骤(b)中得到的混合物添加至在步骤(a)中得到的混合物中;和
(d)向在步骤(c)中得到的反应混合物中加入羧甲基纤维素。
3.一种处理聚酯树脂以赋予所述聚酯树脂阻燃性和形状保持性的方法,所述方法包括将所述聚酯树脂浸渍至权利要求1所述的组合物中,然后脱水和干燥。
4.如权利要求3所述的方法,其中,使用高压喷嘴进行所述浸渍,通过辊压、抽真空和振动进行所述脱水,并通过高温固化和低温干燥进行所述干燥。
5.如权利要求3所述的方法,其中,所述聚酯树脂的形状为双密度聚酯板。
6.经权利要求3~6中任一项所述的方法处理的聚酯树脂,所述聚酯树脂具有阻燃性和形状保持性。
7.一种汽车用NVH部件,所述NVH部件通过压铸权利要求6所述的聚酯树脂制备而成。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104119649A (zh) * | 2014-06-30 | 2014-10-29 | 惠州市昌亿新材料有限公司 | 一种玻纤/pbt复合材料的耐高温阻燃剂及由其制备的玻纤/pbt复合材料 |
CN104119649B (zh) * | 2014-06-30 | 2016-09-28 | 惠州市集和光电科技有限公司 | 一种玻纤/pbt复合材料的耐高温阻燃剂及由其制备的玻纤/pbt复合材料 |
CN104927675A (zh) * | 2015-06-24 | 2015-09-23 | 瓮安县瑞丰贸易有限公司 | 一种水玻璃胶粘剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US8142689B2 (en) | 2012-03-27 |
CN101679725B (zh) | 2012-06-13 |
US20100152335A1 (en) | 2010-06-17 |
EP2142598A1 (en) | 2010-01-13 |
JP2010525136A (ja) | 2010-07-22 |
JP5121924B2 (ja) | 2013-01-16 |
RU2426760C1 (ru) | 2011-08-20 |
EP2142598A4 (en) | 2012-11-28 |
RU2009143077A (ru) | 2011-06-10 |
WO2008133365A1 (en) | 2008-11-06 |
KR100852710B1 (ko) | 2008-08-19 |
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