CN108676303A - 一种轻质隔音丙烯酸树脂 - Google Patents
一种轻质隔音丙烯酸树脂 Download PDFInfo
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Abstract
本发明涉及增强树脂技术领域,具体涉及一种轻质隔音丙烯酸树脂,所述轻质隔音丙烯酸树脂包括相互独立包装的组分A、组分B和组分C,其中:所述组份A包括:第一聚合物乳液、第一部分扩链剂、发泡剂;所述组份B包括:第二聚合物乳液、可溶性金属盐、第二部分扩链剂;所述组份C包括:丙烯酸树脂、有机溶剂。本发明通过在丙烯酸树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强丙烯酸树脂的作用。
Description
技术领域
本发明涉及增强树脂技术领域,具体涉及一种轻质隔音丙烯酸树脂。
背景技术
近年来,汽车轻量化已经成为当下汽车领域发展的重点方向,轻量化技术不仅能够有效的解决其环境污染的问题,实现节能减排的目标,还很大程度上降低了汽车制造的成本,相比于现在的所使用的汽车而言具有很大的经济效益。
目前,汽车轻量化的方法主要包括采用轻质材料和降低门板的截面。降低门板的截面也就是降低门板的厚度,虽然能够降低汽车的整体重量,但是也会导致汽车门板的强度降低,在碰撞时,会产生严重形变,降低了汽车的安全性。采用轻质材料是指采用质量轻、强度大的材料替代目前车门的的钢制材料,目前,常用的轻质材料有铝合金型材、高强度复合树脂和碳纤维材料。其中,高强度树脂凭借自身比重小、隔音隔热、耐腐蚀、吸收冲击能量、比强度高、成本低、易加工、装饰效果好等诸多优点,已然成为汽车轻量化中轻质材料的发展趋势。
丙烯酸酯树脂是一类通用合成聚合物。由于其独特的优点:耐候性能好,抗溶剂解聚,拥有良好的粘结性能、电绝缘性能等,因此,丙烯酸树脂基复合树脂在汽车内饰领域占有重要的地位。然而,丙烯酸酯聚合物热稳定性差,易燃的缺点使其在使用过程中受到限制,很大程度上限制了高性能材料的开发。
发明内容
本发明的目的是为了克服现有技术存在的问题,提供一种轻质隔音丙烯酸树脂,该轻质隔音丙烯酸树脂具有强度高、韧性好、质量轻的特点,在汽车发动机盖板上具有广阔的应用前景。
为了实现上述目的,本发明提供一种轻质隔音丙烯酸树脂,所述轻质隔音丙烯酸树脂包括相互独立包装的组分A、组分B和组分C;以丙烯酸树脂100重量份为基准,其中:所述组份A包括:第一聚合物乳液10~30重量份、第一部分扩链剂5~25重量份、发泡剂0.6~10重量份;所述组份B包括:第二聚合物乳液5~30重量份、可溶性金属盐1~6重量份、第二部分扩链剂5~15重量份;所述组份C包括:丙烯酸树脂40~120重量份、有机溶剂200~400重量份。
通过上述技术方案,本发明通过在丙烯酸树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强丙烯酸树脂的作用。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
为了提高丙烯酸树脂的强度和韧性,降低丙烯酸树脂的质量,本发明提供一种轻质隔音丙烯酸树脂,包括丙烯酸树脂和分散在丙烯酸树脂内部的复合纤维,所述复合纤维包括具有大孔的内芯和含有介孔的外壁。
本发明中,通过在丙烯酸树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强丙烯酸树脂的作用。
为了进一步优化复合纤维的韧性,优选情况下,所述内芯中大孔的孔径范围为50~100nm,所述外壁上介孔的孔径范围为10~45nm。
为了进一步优化复合纤维的韧性,优选情况下,所述内芯的直径为0.5~2μm,所述外壁的厚度为50~150nm。
本发明中,丙烯酸树脂与复合纤维的配比是影响丙烯酸树脂性能的重要因素,优选情况下,所述丙烯酸树脂与所述复合纤维的质量比为1:(0.1~0.25)。
根据本发明,优选情况下,所述内芯选自多孔聚丙烯腈纤维、多孔聚己内酯纤维、多孔聚氨酯纤维、多孔氟化聚氨酯纤维、多孔聚砜纤维、多孔聚醚砜纤维、多孔聚偏氟乙烯-六氟丙烯纤维、多孔聚偏氟乙烯-四氟乙烯-全氟甲基乙烯基醚纤维、多孔聚偏氟乙烯-三氟氯乙烯纤维中的至少一种。
在本发明的另一个优选实施方式中,所述轻质隔音丙烯酸树脂包括相互独立包装的组分A、组分B和组分C;以丙烯酸树脂100重量份为基准,其中:所述组份A包括:第一聚合物乳液10~30重量份、第一部分扩链剂5~25重量份、发泡剂0.6~10重量份;所述组份B包括:第二聚合物乳液5~30重量份、可溶性金属盐1~6重量份、第二部分扩链剂5~15重量份;所述组份C包括:丙烯酸树脂40~120重量份、有机溶剂200~400重量份。
为了优化丙烯酸树脂的强度和韧性,优选情况下,以丙烯酸树脂100重量份为基准,其中:所述组份A包括:第一聚合物乳液20~24重量份、第一部分扩链剂15~18重量份、发泡剂2~6重量份;所述组份B包括:第二聚合物乳液10~12重量份、可溶性金属盐2~4重量份、第二部分扩链剂5~6重量份;所述组份C包括:丙烯酸树脂100重量份、有机溶剂240~360重量份。
根据本发明,本发明中通过将发泡剂与第一聚合物乳液混合,并进行静电纺丝,生成含有发泡剂的聚合物纤维,发泡剂经高温分解后,在聚合物纤维内部形成孔隙,因此,发泡剂是形成聚合物内部空隙的重要成分之一,优选情况下,所述发泡剂选自4,4-氧代双苯磺酰肼、偶氮二甲酰胺、N,N’-二亚硝基五次甲基四胺中的至少一种。
根据本发明,优选情况下,所述第一聚合物乳液和第二聚合物乳液各自独立的选自聚丙烯腈乳液、聚己内酯乳液、聚氨酯乳液、氟化聚氨酯乳液、聚砜乳液、聚醚砜乳液、聚偏氟乙烯-六氟丙烯乳液、聚偏氟乙烯-四氟乙烯-全氟甲基乙烯基醚乳液、聚偏氟乙烯-三氟氯乙烯乳液中的至少一种。
根据本发明,优选情况下,所述第一聚合物乳液的固含量为25~72%。根据本发明,优选情况下,所述第二聚合物乳液的固含量为18~60%。
根据本发明,本发明对酸性溶液的种类没有特殊的要求,可以为盐酸、硫酸、硝酸等中的至少一种。
根据本发明,将聚合物纤维在含有可溶性金属盐和扩链剂的第二聚合物乳液中反应,可以在聚合物纤维的表面生成含有金属离子的聚合物外壁,聚合物外壁中的金属离子能够在酸性溶液中发生迁移,从聚合物外壁上迁移至溶液中,从而在聚合物外壁上形成微孔结构。可溶性金属盐是形成外壁上介孔结构的重要因素,优选情况下,所述可溶性金属盐选自钠盐、钾盐、可溶性铜盐、可溶性锌盐、可溶性铁盐、可溶性镍盐、可溶性钴盐和可溶性锰盐中的至少一种,更具体的,所述可溶性金属盐选自氯化钠、硫酸钠、硝酸钠、氯化钾、硫酸钾、硝酸钾、氯化铁、硫酸铜、硝酸锌、氯化锌、氯化铁、硫酸镍、硝酸镍、醋酸镍、氯化镍、硫酸钴、硝酸钴、醋酸钴、氯化钴、硫酸锰、硝酸锰、醋酸锰、氯化锰中的至少一种。
根据本发明,优选情况下,所述扩链剂选自脂肪族二醇、芳香族二醇中的至少一种。其中所述脂肪族二醇选自乙二醇、1,3-丁二醇、1,10-葵二醇、1,4-环己二醇、1,8-辛二醇、新戊二醇、2-甲基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇和3-甲基-1,5-戊二醇中的至少一种;其中所述芳香族二醇选自对苯二酚双羟乙基醚和/或间苯二酚双羟乙基醚。
根据本发明,其中对有机溶剂的种类没有特殊的要求,只要能够溶解丙烯酸树脂即可,优选情况下,所述有机溶剂选自丙酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基乙酰胺、二氯甲烷、磷酸三乙酯、三氯甲烷、甲苯、乙醇、醋酸、乙酸乙酯、甲酸、氯仿、四氢呋喃、液体石蜡和二甲基亚砜中的至少一种。
本发明还提供一种轻质隔音丙烯酸树脂的制备方法,包括以下步骤:
(1)将第一部分聚合物乳液、第一部分扩链剂和发泡剂混合均匀后进行纺丝,得到聚合物纤维;
(2)将聚合物纤维、第二部分扩链剂和可溶性金属盐置于第二部分聚合物乳液中,在60~100℃下反应15~60min,然后在酸性溶液中浸泡,然后在150~200℃下处理15~30min,得到复合纤维;
(3)将丙烯酸树脂、复合纤维在有机溶剂中混合均匀后,在80~120℃下回流3~5h,得到轻质隔音丙烯酸树脂。
本发明中,将聚合物乳液与发泡剂进行混合后进行纺丝,及得到含有发泡剂的聚合物纤维,再将聚合物纤维与可溶性金属盐在聚合物乳液中进行聚合反应,在聚合物纤维表面生成含有金属离子的外壁,得到复合纤维A,再将其置于酸性溶液中浸泡,将金属离子置换到溶液中,形成含有介孔结构的外壁,得到复合纤维B,将复合纤维B在高温下热处理,使发泡剂分解,在内芯中形成大孔,即得到复合纤维。
通过在丙烯酸树脂中加入具有多重孔结构的复合纤维,多孔结构一方面可以降低体系的质量,另一方面还可以阻挡声音的传播,起到隔音的作用。此外,由于该复合纤维由内芯和外壁双重结构构成,具有较高的强度和高韧性,起到增强丙烯酸树脂的作用。本发明在丙烯酸树脂的合成过程中加入复合纤维,能够提高丙烯酸树脂与复合纤维间的结合力,从而提高复合纤维在丙烯酸树脂中的稳定性。
根据本发明,优选情况下,所述纺丝的工艺为:电源电压10~60KV,纺丝环境条件为温度15~35℃,相对湿度25~90%;多针头喷丝单元针头间距2~30cm,喷丝单元针头数量为6~90个。
根据本发明,本发明通过将复合纤维A在酸性溶液中浸泡,将金属离子置换到溶液中,从而形成含有介孔结构的外壁,优选情况下,在步骤(2)中,所述酸性溶液的pH值为1~5。为了提高金属离子的洗脱效率,进一步优选的,在浸泡过程中,每隔30min换一次浸泡液,至浸泡液的pH值不在发生变化。
以下将通过实施例对本发明进行详细描述。以下实施例中,采用排水法测试各样品的密度。按照GB/T1447-2005的方法测试各样品的拉伸性能。按照GB/T1449-2005的方法测各样品的试弯曲性能。按照GB/T1040.1-2006的方法测试各样品的断裂伸长率。按照GB/T1451-2005的方法测试各样品的冲击韧性。按照GB/T18696.2-2002的方法测试各样品的吸声系数。测试样品是直径为7.8cm,厚度为1.2cm的圆片,测试频率范围为100~2500Hz。
实施例1
A、将24g固含量为50%的聚己内酯乳液、15g乙二醇、6g 4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到聚己内酯纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取22g聚己内酯纤维、5g乙二醇和3g硝酸锌置于12g固含量为32%的聚己内酯乳液中,在80℃下反应45min,得到复合纤维A,然后将复合纤维A在pH为3的盐酸溶液中浸泡2h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在180℃下处理15min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为80nm;外壁上介孔的孔径范围为15nm;内芯的直径为1μm;所述外壁的厚度为60nm。
C、将200g丙烯酸2-乙基己酯和复合纤维C在300gN-甲基吡咯烷酮中混合均匀后,在100℃下回流3.5h,得到轻质隔音丙烯酸树脂。
实施例2
A、将20g固含量为38%的氟化聚氨酯乳液、18g 1,3-丁二醇和2g 4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到氟化聚氨酯纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取18g氟化聚氨酯纤维、6g 1,3-丁二醇和2g醋酸钴置于10g固含量为45%的氟化聚氨酯乳液中,在80℃下反应30min,得到复合纤维A,然后将复合纤维A在pH为2的盐酸溶液中浸泡1.5h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在150℃下处理30min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为60nm;外壁上介孔的孔径范围为20nm;内芯的直径为1.5μm;所述外壁的厚度为100nm。
C、将200g甲基丙烯酸甲酯和复合纤维C在240gN-甲基吡咯烷酮中混合均匀后,在110℃下回流3.5h,得到轻质隔音丙烯酸树脂。
实施例3
A、将10g固含量为63%的聚偏氟乙烯-三氟氯乙烯乳液、20g新戊二醇和2g偶氮二甲酰胺混合均匀后进行纺丝,得到聚偏氟乙烯-三氟氯乙烯纤维,纺丝工艺为:电源电压30KV,纺丝环境条件为温度25℃,相对湿度60%;多针头喷丝单元针头间距15cm,喷丝单元针头数量为45个;
B、取9g聚偏氟乙烯-三氟氯乙烯纤维、4g新戊二醇和4g硫酸锰置于30g固含量为26%的聚偏氟乙烯-三氟氯乙烯乳液中,在75℃下反应45min,得到复合纤维A,然后将复合纤维A在pH为4.2的盐酸溶液中浸泡2h,其中每10min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在200℃下处理25min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为80nm;外壁上介孔的孔径范围为30nm;内芯的直径为0.8μm;所述外壁的厚度为120nm。
C、将200g甲基丙烯酸乙酯和复合纤维C在360g二甲基乙酰胺中混合均匀后,在100℃下回流4h,得到轻质隔音丙烯酸树脂。
实施例4
A、将30g固含量为25%的聚醚砜乳液、25g 2-甲基-1,3-丙二醇和10g偶氮二甲酰胺混合均匀后进行纺丝,得到聚醚砜纤维,纺丝工艺为:电源电压60KV,纺丝环境条件为温度35℃,相对湿度90%;多针头喷丝单元针头间距30cm,喷丝单元针头数量为90个;
B、取28g聚醚砜纤维、5g 2-甲基-1,3-丙二醇和6g硫酸钾置于20g固含量为18%的聚醚砜乳液中,在100℃下反应15min,得到复合纤维A,然后将复合纤维A在pH为1的盐酸溶液中浸泡1h,其中每10min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在200℃下处理30min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为50nm;外壁上介孔的孔径范围为10nm;内芯的直径为0.5μm;所述外壁的厚度为50nm。
C、将200g丙烯酸丁酯和复合纤维C在200g二甲基乙酰胺中混合均匀后,在120℃下回流3h,得到轻质隔音丙烯酸树脂。
实施例5
A、将15g固含量为72%的聚己内酯乳液、5g 1,8-辛二醇和0.6g 4,4-氧代双苯磺酰肼混合均匀后进行纺丝,得到聚己内酯纤维,纺丝工艺为:电源电压10KV,纺丝环境条件为温度15℃,相对湿度25%;多针头喷丝单元针头间距2cm,喷丝单元针头数量为6个;
B、取13g聚己内酯纤维、5g 1,8-辛二醇和1g氯化钠置于5g固含量60%的聚己内酯乳液中,在60℃下反应60min,得到复合纤维A,然后将复合纤维A在pH为5的盐酸溶液中浸泡3h,其中每15min更换一次盐酸溶液,得到复合纤维B,将复合纤维B在150℃下处理20min,得到复合纤维C;
所述复合纤维C由具有大孔的内芯和含有介孔的外壁组成,其中内芯中大孔的孔径范围为100nm;外壁上介孔的孔径范围为45nm;内芯的直径为2μm;所述外壁的厚度为150nm。
C、将200g丙烯酸2-乙基己酯和复合纤维C在400g乙酸乙酯中混合均匀后,在80℃下回流5h,得到轻质隔音丙烯酸树脂。
对比例1
按照实施例1的方法,不同的是,在轻质隔音丙烯酸树脂的制备中不添加发泡剂。
对比例2
按照实施例1的方法,不同的是,在轻质隔音丙烯酸树脂的制备中不含有步骤B。
对比例3
按照实施例1的方法,不同的是,在轻质隔音丙烯酸树脂的制备中不添加可溶性金属盐。
对比例4
直接在丙烯酸树脂中添加聚己内酯纤维,得到复合丙烯酸树脂。
表1实施例1~5和对比例1~4中各阻燃高强度轻质树脂的的性能表
以上详细描述了本发明的优选实施方式,但是,本发明并不限于此。在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,包括各个技术特征以任何其它的合适方式进行组合,这些简单变型和组合同样应当视为本发明所公开的内容,均属于本发明的保护范围。
Claims (9)
1.一种轻质隔音丙烯酸树脂,其特征在于,所述轻质隔音丙烯酸树脂包括相互独立包装的组分A、组分B和组分C;以丙烯酸树脂100重量份为基准,其中:
所述组份A包括:第一聚合物乳液10~30重量份、第一部分扩链剂5~25重量份、发泡剂0.6~10重量份;
所述组份B包括:第二聚合物乳液5~30重量份、可溶性金属盐1~6重量份、第二部分扩链剂5~15重量份;
所述组份C包括:丙烯酸树脂40~120重量份、有机溶剂200~400重量份。
2.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,以丙烯酸树脂100重量份为基准,其中:
所述组份A包括:第一聚合物乳液20~24重量份、第一部分扩链剂15~18重量份、发泡剂2~6重量份;
所述组份B包括:第二聚合物乳液10~12重量份、可溶性金属盐2~4重量份、第二部分扩链剂5~6重量份;
所述组份C包括:丙烯酸树脂100重量份、有机溶剂240~360重量份。
3.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述发泡剂选自4,4-氧代双苯磺酰肼、偶氮二甲酰胺、N,N’-二亚硝基五次甲基四胺中的至少一种。
4.根据权利要求3所述的轻质隔音丙烯酸树脂,其中,所述第一聚合物乳液和第二聚合物乳液各自独立的选自聚丙烯腈乳液、聚己内酯乳液、聚氨酯乳液、氟化聚氨酯乳液、聚砜乳液、聚醚砜乳液、聚偏氟乙烯-六氟丙烯乳液、聚偏氟乙烯-四氟乙烯-全氟甲基乙烯基醚乳液、聚偏氟乙烯-三氟氯乙烯乳液中的至少一种。
5.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述第一聚合物乳液的固含量为25~72%;和/或
所述第二聚合物乳液的固含量为18~60%。
6.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述可溶性金属盐选自钠盐、钾盐、可溶性铜盐、可溶性锌盐、可溶性铁盐、可溶性镍盐、可溶性钴盐和可溶性锰盐中的至少一种。
7.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述丙烯酸树脂选自丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸乙酯、丙烯酸乙酯中的至少一种。
8.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述扩链剂选自所述扩链剂选自脂肪族二醇和/或芳香族二醇。
9.根据权利要求1所述的轻质隔音丙烯酸树脂,其中,所述有机溶剂选自丙酮、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基乙酰胺、二氯甲烷、磷酸三乙酯、三氯甲烷、甲苯、乙醇、醋酸、乙酸乙酯、甲酸、氯仿、四氢呋喃、液体石蜡和二甲基亚砜中的至少一种。
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CN103897287A (zh) * | 2012-12-27 | 2014-07-02 | 浙江艾迪雅科技股份有限公司 | 多模无机填料及高分子复合阻尼材料以及其制作方法 |
CN107760182A (zh) * | 2017-10-30 | 2018-03-06 | 汪涛 | 一种吸音涂料组合物 |
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CN1944500A (zh) * | 2006-09-28 | 2007-04-11 | 湘潭大学 | 纤维增强发泡聚合物材料及其制备方法 |
CN103897287A (zh) * | 2012-12-27 | 2014-07-02 | 浙江艾迪雅科技股份有限公司 | 多模无机填料及高分子复合阻尼材料以及其制作方法 |
CN107760182A (zh) * | 2017-10-30 | 2018-03-06 | 汪涛 | 一种吸音涂料组合物 |
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