CN114958214A - 一种可循环利用的耐水压防水中底胶膜及其制备方法 - Google Patents
一种可循环利用的耐水压防水中底胶膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种可循环利用的耐水压防水中底胶膜及其制备方法,该胶膜包括热塑性树脂50份‑70份;醚类防水树脂10份‑20份;聚酰胺蜡1份‑8份;光引发剂0.1份‑1份;抗水解剂0.1份‑1份;乙烯基胍胺0.1份‑1份;交联剂0.1份‑1份;相容剂3份‑10份;其中,热塑性树脂含有10wt%‑70wt%的回收料。上述胶膜的酰胺基中的氧原子电负性大,易与热溶胶级热塑性树脂的氢原子形成氢键,使体系形成立体网状结构,增加粘接的能力,提高体系的耐水压防水性能,通过光引发剂的作用,在紫外光照射下,能够引入高分子的支链上,再一次使其产生交联自由基,增加胶膜的粘接性能,实现废料的可循环利用在胶膜中。
Description
技术领域
本发明涉及中底胶膜技术领域,尤其涉及一种可循环利用的耐水压防水中底胶膜及其制备方法。
背景技术
中底胶主要用于制鞋时鞋底中底板的贴合、纸板贴纸板、纸板贴EVA等物料粘接。由于中底胶承接着上下层的物料粘接,需要粘接力较强且粘接时间要短,才能避免粘接后鞋底因重力原因脱胶。
一些在生产过程中所产生的边角料或者易于回收的回收料,如流延加工边角料、外购再生回收料或鞋底使用生命周期结束后的回收料,含有大量的热塑性树脂。目前这些热塑性树脂会回收用于生产如鞋子等产品,尚未有生产工艺或者配方将其回收用于制备胶膜。
发明内容
为了克服现有技术的不足,本发明目的之一在于提供一种可循环利用的耐水压防水中底胶膜,其粘接力较强,并且在其内添加可回收利用的回收料,使其具有环保的作用。
本发明目的之二在于提供一种可循环利用的耐水压防水中底胶膜的制备方法。
本发明目的之一采用如下技术方案实现:
一种可循环利用的耐水压防水中底胶膜,包括如下重量份的组分:
热塑性树脂50份-70份;醚类防水树脂10份-20份;聚酰胺蜡1份-8份;光引发剂0.1份-1份;抗水解剂0.1份-1份;乙烯基胍胺0.1份-1份;交联剂0.1份-1份;相容剂3份-10份;其中,热塑性树脂含有10wt%-70wt%的回收料。
优选地,所述热塑性树脂为氯乙烯-乙烯共聚物树脂和/或氯乙烯-偏氯乙烯共聚树脂。热塑性树脂作为配方体系的主基材,所选的共聚树脂具有良好的防水性能。回收料为流延加工边角料、外购再生回收料或鞋底使用生命周期结束后的回收料中的一种,回收料中热塑性树脂的质量百分比为50%-80%,邵氏硬度为80A-200A,熔融指数为3-8g/10min(190℃/2.16kg)。回收料中热塑性树脂与主料的热塑性树脂的类型相同。
优选地,所述聚醚类防水树脂为聚醚酯类热塑性弹性体和/或聚酰胺类聚醚弹性体。聚醚类防水树脂选自聚醚类弹性体,具有较好的弹性及较低的硬度,能够提高物质之间的柔软性。
进一步优选地,所述聚醚类防水树脂中聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg)。
优选地,所述光引发剂为2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、1-羟基环己基苯甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2甲基-1-丙烷-1-酮中的一种或者两种以上。通过在体系中引入光引发剂,当鞋底与中底板采用溶剂分开后,可以通过紫外光等光照后,以激发体系产生自由基,使体系其他物质继续产生聚合反应,使该鞋底与中底板继续粘合,不需再增加一层胶膜,使鞋底与中底板之间产生有较厚的粘接层。
优选地,所述抗水解剂为N,N'-二(2,6-二异丙基苯基)碳二亚胺类和环氧官能团接枝丙烯腈-苯乙烯类抗水解剂。抗水解剂提高聚醚类防水树脂的水解稳定性。优选地,抗水解剂为上海朗亿的抗水解剂HyMax系列和/或南通日之升抗水解剂SAG-005。
优选地,所述交联剂为交联剂TAC。交联剂TAC即2,4,6-三烯丙氧基-1,3,5-三嗪,为三官能度反应的交联剂,能显著提高产品的强度、刚性和耐热性能。添加了交联剂TAC后,在较低的能量下,即可产生交联剂自由基,促进其他物质产生自由基,进行聚合反应。
优选地,所述热塑性树脂、醚类防水树脂、聚酰胺蜡的质量比为1:(0.1-0.3):(0.05-0.08)。进一步优选地,所述热塑性树脂、醚类防水树脂、聚酰胺蜡的质量比为1:0.2:0.05。
优选地,所述相容剂为马来酸酐接枝聚烯烃(MAH-g-poe、MAH-g-PVOH)、苯乙烯-马来酸酐共聚物(SMA)、甲基丙烯酸缩水甘油酯接枝聚烯烃共聚物(GMA-g-PVOH)中的一种或两种以上。
本发明目的之二采用如下技术方案实现:
一种可循环利用的耐水压防水中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气驱氧气,再加入乙烯基胍胺,在油浴中反应过夜,接着,将温度降至40℃以下,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜;其中,热塑性树脂含有10wt%-70wt%的回收料。
进一步地,该可循环利用的耐水压防水中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在80℃-120℃油浴中反应过夜,接着,将温度降至30℃-40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在120℃-160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜;其中,热塑性树脂含有10wt%-70wt%的回收料。
相比现有技术,本发明的有益效果在于:
本发明的可循环利用的耐水压防水中底胶膜通过热塑性树脂、醚类防水树脂、聚酰胺蜡、光引发剂、抗水解剂、乙烯基胍胺和交联剂等材料结合,由于聚酰胺蜡主要由非极性的脂肪烃部分和极性的酰胺基官能团构成,酰胺基中的氧原子电负性大,易和烃基部分的氢原子形成氢键,使其与热溶胶级热塑性树脂的氢原子形成氢键,使体系形成立体网状结构,增加粘接的能力,提高体系的耐水压防水性能,并且聚酰胺蜡在低温环境下,容易活化,以使体系具有低温活化效果,由于回收料除了含有大量的热塑性树脂外,还含有其他的添加剂,难于控制胶膜中的添加剂含量,并且热塑性树脂由于已经发生交联,难于在其他材料中分散,易于影响胶膜的质量,本发明通过添加了光引发剂、相容剂、交联剂、乙烯基胍胺等材料与其配合,使其易于分散在其他材料,且通过光引发剂的作用,乙烯基胍胺富有聚合性,在紫外光照射下,能够引入高分子的支链上,再一次使其产生交联自由基,增加胶膜的粘接性能,实现废料的可循环利用在胶膜中。
具体实施方式
下面,结合具体实施方式,对本发明做进一步描述,需要说明的是,在不相冲突的前提下,以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。以下是本发明具体的实施例,在下述实施例中所采用的原材料、设备等除特殊限定外均可以通过购买方式获得。
实施例1
一种可循环利用的耐水压防水中底胶膜,包括如下重量份的组分:
热塑性树脂50份;醚类防水树脂10份;聚酰胺蜡1份;光引发剂0.1份;抗水解剂0.1份;乙烯基胍胺0.1份;交联剂0.1份;相容剂3份。其中,热塑性树脂为氯乙烯-乙烯共聚物树脂;聚醚类防水树脂为聚醚酯类热塑性弹性体,其聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg);光引发剂为2,2-二甲氧基-2-苯基苯乙酮;抗水解剂为上海朗亿的抗水解剂HyMax系列;交联剂为交联剂TAC;所述相容剂为马来酸酐接枝聚烯烃。热塑性树脂含有15wt%的回收料。回收料中热塑性树脂的质量百分比为50%,邵氏硬度为80A,熔融指数为8g/10min(190℃/2.16kg)。
该中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在120℃油浴中反应过夜,接着,将温度降至40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜。
实施例2
一种可循环利用的耐水压防水中底胶膜,包括如下重量份的组分:
热塑性树脂60份;醚类防水树脂15份;聚酰胺蜡5份;光引发剂0.5份;抗水解剂0.5份;乙烯基胍胺0.5份;交联剂0.5份;相容剂8份。其中,热塑性树脂为氯乙烯-乙烯共聚物树脂;聚醚类防水树脂为聚醚酯类热塑性弹性体,其聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg);光引发剂为2,2-二甲氧基-2-苯基苯乙酮;抗水解剂为上海朗亿的抗水解剂HyMax系列;交联剂为交联剂TAC;所述相容剂为马来酸酐接枝聚烯烃。热塑性树脂含有35wt%的回收料。回收料中热塑性树脂的质量百分比为50%,邵氏硬度为80A,熔融指数为8g/10min(190℃/2.16kg)。
该中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在120℃油浴中反应过夜,接着,将温度降至40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜。
实施例3
一种可循环利用的耐水压防水中底胶膜,包括如下重量份的组分:
热塑性树脂70份;醚类防水树脂20份;聚酰胺蜡8份;光引发剂1份;抗水解剂1份;乙烯基胍胺1份;交联剂1份;相容剂10份其中,热塑性树脂为氯乙烯-乙烯共聚物树脂;聚醚类防水树脂为聚醚酯类热塑性弹性体,其聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg);光引发剂为2,2-二甲氧基-2-苯基苯乙酮;抗水解剂为上海朗亿的抗水解剂HyMax系列;交联剂为交联剂TAC;所述相容剂为马来酸酐接枝聚烯烃。热塑性树脂含有50wt%的回收料。回收料中热塑性树脂的质量百分比为50%,邵氏硬度为80A,熔融指数为8g/10min(190℃/2.16kg)。
该中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在120℃油浴中反应过夜,接着,将温度降至40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜。
实施例4
一种可循环利用的耐水压防水中底胶膜,包括如下重量份的组分:
热塑性树脂65份;醚类防水树脂13份;聚酰胺蜡3.3份;光引发剂0.1份;抗水解剂0.1份;乙烯基胍胺0.1份;交联剂0.1份;相容剂5份其中,热塑性树脂为氯乙烯-乙烯共聚物树脂;聚醚类防水树脂为聚醚酯类热塑性弹性体,其聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg);光引发剂为2,2-二甲氧基-2-苯基苯乙酮;抗水解剂为上海朗亿的抗水解剂HyMax系列;交联剂为交联剂TAC;所述相容剂为马来酸酐接枝聚烯烃。热塑性树脂含有35wt%的回收料。回收料中热塑性树脂的质量百分比为75%,邵氏硬度为80A,熔融指数为8g/10min(190℃/2.16kg)。
该中底胶膜的制备方法包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在120℃油浴中反应过夜,接着,将温度降至40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜。
对比例1
与实施例1不同的是,对比例1的中底胶膜包括如下重量份的组分:
热塑性树脂50份;醚类防水树脂10份;光引发剂0.1份;抗水解剂0.1份;乙烯基胍胺0.1份;交联剂0.1份,其中,热塑性树脂含有15wt%的回收料。
其他制备方法与实施例1相同。
对比例2
与实施例1不同的是,对比例1的中底胶膜包括如下重量份的组分:
热塑性树脂90份;醚类防水树脂10份,其中,热塑性树脂含有15wt%的回收料。
其他制备方法与实施例1相同。
性能测试
防水测试:GB/T16641-2019《鞋类整鞋试验方法动态防水性能》中的水槽测试方法分析。
剥离强度测试:测试材料的贴合剥离强度,材料为20cm*20cm*1.0mm,贴合在金属上,其中,常温条件为将试片置于23℃,50%RH条件下放置48h,拿出迅速进行剥离拉力测试;耐水条件为将试片浸泡在水中48h,再取出后进行剥离拉力测试;紫外光照射条件为将材料放置在波长为200nm-400nm,光强为400mW/cm2的紫外光下照射3S-5S后,贴合在金属上,然后测试其剥离拉力大小,以上结果均取平均值。
测试结果如下所示:
表1
上述实施方式仅为本发明的优选实施方式,不能以此来限定本发明保护的范围,本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (10)
1.一种可循环利用的耐水压防水中底胶膜,其特征在于,包括如下重量份的组分:
热塑性树脂50份-70份;醚类防水树脂10份-20份;聚酰胺蜡1份-8份;光引发剂0.1份-1份;抗水解剂0.1份-1份;乙烯基胍胺0.1份-1份;交联剂0.1份-1份;相容剂3份-10份;其中,热塑性树脂含有10wt%-70wt%的回收料。
2.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述热塑性树脂为氯乙烯-乙烯共聚物树脂和/或氯乙烯-偏氯乙烯共聚树脂;所述回收料中热塑性树脂的质量百分比为50%-80%,邵氏硬度为80A-200A,熔融指数为3-8g/10min(190℃/2.16kg)。
3.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述聚醚类防水树脂为聚醚酯类热塑性弹性体和/或聚酰胺类聚醚弹性体。
4.根据权利要求3所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述聚醚类防水树脂中聚醚链段的质量百分比为30%-40%,熔点为120℃-140℃,邵氏硬度为80A-100A,重均分子量为10000g/mol-50000g/mol,熔融指数为3-8g/10min(190℃/2.16kg)。
5.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述光引发剂为2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、1-羟基环己基苯甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、1-[4-(2-羟基乙氧基)苯基]-2-羟基-2甲基-1-丙烷-1-酮中的一种或者两种以上。
6.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述抗水解剂为N,N'-二(2,6-二异丙基苯基)碳二亚胺类和环氧官能团接枝丙烯腈-苯乙烯类抗水解剂。
7.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述交联剂为交联剂TAC;所述相容剂为马来酸酐接枝聚烯烃、苯乙烯-马来酸酐共聚物、甲基丙烯酸缩水甘油酯接枝聚烯烃共聚物中的一种或两种以上。
8.根据权利要求1所述的可循环利用的耐水压防水中底胶膜,其特征在于,所述热塑性树脂、醚类防水树脂、聚酰胺蜡的质量比为1:(0.1-0.3):(0.05-0.08)。
9.一种如权利要求1-8任一项所述的可循环利用的耐水压防水中底胶膜的制备方法,其特征在于,包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气驱氧气,再加入乙烯基胍胺,在油浴中反应过夜,接着,将温度降至40℃以下,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜;其中,热塑性树脂含有10wt%-70wt%的回收料。
10.根据权利要求9所述的可循环利用的耐水压防水中底胶膜的制备方法,其特征在于,包括如下制备步骤:
将热塑性树脂、醚类防水树脂、聚酰胺蜡、相容剂和抗水解剂加入到反应釜中,搅拌均匀,然后通入氮气10min-20min,驱氧气,再加入乙烯基胍胺,在80℃-120℃油浴中反应过夜,接着,将温度降至30℃-40℃,加入光引发剂和交联剂,搅拌均匀,然后投入螺杆挤出机中在120℃-160℃下熔融挤出,经延流、冷却、牵引及收卷的步骤,得到可循环利用的耐水压防水中底胶膜;其中,热塑性树脂含有10wt%-70wt%的回收料。
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