CN106117765B - 一种复合鞋底及其制备方法 - Google Patents
一种复合鞋底及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种复合鞋底及其制备方法。所述复合鞋底由EVA注塑中底、橡胶外底和注塑足弓支撑架依次复合而成;EVA注塑中底由高回弹耐老化EVA发泡材料制成,高回弹耐老化EVA发泡材料按照包括如下步骤的方法制备:1)利用硅烷偶联剂对木质纤维素粉体进行改性,得到改性木质纤维素粉体;2)将部分氢化苯乙烯丁二烯聚合物、乙烯‑醋酸乙烯共聚物和改性木质纤维素粉体混合后进行混炼;3)将发泡剂、架桥剂、活性剂和氧化锌加入混炼的体系中进行混炼;4)经步骤2)和步骤3)密炼后的物料进行造粒,然后进行射出发泡,经冷却成型即得。本发明复合鞋底具有良好的弹性、弹性恢复性、防滑性、耐磨性,满足的运动及休闲类鞋靴的穿着舒适性需要。
Description
技术领域
本发明涉及一种复合鞋底及其制备方法。
背景技术
乙烯醋酸乙酯共聚物(简称EVA)发泡材料的传统工艺是将EVA原料塑炼造粒后,通过密炼、开炼、出片、发泡等工序。由于EVA具有良好的可塑性、弹性、可加工性,因此,一般运动鞋的鞋底的发泡中底均有EVA发泡材料制成。目前绝大多数运动鞋的中底采用EVA发泡材料。
传统工艺生产的EVA发泡材料与橡胶的粘合大底,虽然具有相对好的可塑性和弹性,但是其抗撕裂性能较差,同时回弹性不高。因此,需要提供一种改性的EVA发泡材料与改性橡胶的粘合底来改善其抗撕裂性能、回弹、耐磨和防滑性能。
发明内容
本发明的目的是提供一种梯度功能的复合鞋底及其制备方法。
本发明提供的复合鞋底,由EVA注塑中底、橡胶外底和注塑足弓支撑架依次复合而成;
所述EVA注塑中底由高回弹耐老化EVA发泡材料制成,所述高回弹耐老化EVA发泡材料按照包括如下步骤的方法制备得到:
1)利用硅烷偶联剂对木质纤维素粉体进行改性,得到改性木质纤维素粉体;
2)将部分氢化苯乙烯丁二烯聚合物、乙烯-醋酸乙烯共聚物和所述改性木质纤维素粉体混合后进行混炼;
3)将发泡剂、架桥剂、活性剂和氧化锌加入所述混炼的体系中进行混炼;
4)经步骤2)和步骤3)密炼后的物料进行造粒,然后进行射出发泡,经冷却成型即得所述高回弹耐老化EVA发泡材料。
上述的复合鞋底中,所述硅烷偶联剂可为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基-三甲氧基硅烷、γ-甲基丙烯酰氧基丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-甲基-三甲氧基硅烷、γ-氯丙基-三甲氧基硅烷、γ-巯丙基-三甲氧基硅烷和γ-氨丙基-三甲氧基硅烷中至少一种;
所述硅烷偶联剂的用量为所述木质纤维素粉体质量的0.1~1.5%。
所述硅烷偶联剂的用量可为所述木质纤维素粉体质量的0.1~1.5%,如1%;
进行所述改性时,将所述硅烷偶联剂喷淋到所述木质纤维素粉体,实现对所述木质纤维素粉体的表面改性。
上述的复合鞋底中,所述木质纤维素粉体可为汉麻杆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子至少一种;
所述木质纤维素粉体的粒径为200目~1000目;
所述部分氢化苯乙烯丁二烯聚合物的数均分子量为12000~50000;
所述乙烯-醋酸乙烯共聚物的数均分子量为400~4000,所述乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量为20~40%;
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种;
所述架桥剂选自过氧化二异丙苯、硫磺和二叔丁基过氧化物中的至少一种;
所述活性剂选自硬脂酸、碳酸镁和氧化钙中的至少一种。
上述的复合鞋底中,所述乙烯-醋酸乙烯共聚物、所述部分氢化苯乙烯丁二烯聚合物、所述改性木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比可为50:50:20~80:3.0~5.0:0.4~1.0:1.0~3.0:0.5~2.5,具体可为50:50:40~70:3.5~4.5:0.6~0.8:2~2.5:1~1.5、50:50:50:4.0:0.6:2:1、50:50:50:4.5:0.6:2:1、50:50:50:4.0:0.8:2:1、50:50:50:4.0:0.6:2.5:1、50:50:50:4.0:0.6:2:1.5、50:50:50:3.5:0.6:2:1.5或50:50:50:4.5:0.6:2.5:1。
上述的复合鞋底中,所述高回弹耐老化EVA发泡材料的制备方法中,步骤2)中,所述混炼的温度可为80~90℃,如90℃,每5℃进行除尘翻料;
所述混炼的时间可为7.5~12min,如12min;
步骤3)中,所述混炼的温度可为90℃~110℃,如100℃;
所述混炼的时间可为6~8min,如6min。
步骤4)中,所述射出发泡的条件如下:模具的上模温度为177~183℃,模具的下模温度为177~183℃。
上述的复合鞋底中,所述橡胶外底由耐磨止滑橡胶制成,所述耐磨止滑橡胶按照包括如下步骤的方法制备得到:
1)利用所述硅烷偶联剂对短纤维进行改性,得到改性短纤维;
所述短纤维为碳纤维、玻璃纤维和玄武岩纤维中至少一种;
所述短纤维的直径为10~100μm,长度为1~10mm;
所述硅烷偶联剂的用量为所述短纤维质量的0.1%~1.5%;
2)称取天然橡胶、顺丁二烯橡胶、丁腈橡胶和所述改性短纤维作为粗坯;将部分所述粗坯进行混炼;
3)向余量的所述粗坯中加入氧化镁、硅烷、硬脂酸、促进剂和活性剂,然后加入至步骤2)所述混炼后的物料中进行混炼;所述促进剂和所述活性剂依次加入至所述粗坯中;
4)步骤3)所述混炼后的物料进行硫化成型,得到所述耐磨止滑橡胶。
上述的制备方法中,步骤2)和步骤3)中所述粗坯的量没有具体的要求,可根据具体的情况进行调整。
上述的复合鞋底中,所述促进剂可为硫磺;所述活性剂可为ZnO、聚乙烯醇和聚乙烯中至少一种;
利用所述硅烷偶联剂对所述短纤维进行预处理,以对所述短纤维的表面新型改性,从而使短纤维与橡胶的界面的结合更加紧密,形成一个良好的粘结界面;
所述硅烷偶联剂的用量可为所述短纤维质量的1%。
上述的复合鞋底中,所述天然橡胶、所述顺丁二烯橡胶、所述丁腈橡胶、所述硬脂酸、所述氧化镁、所述改性短纤维、所述硅烷、所述活性剂与所述促进剂的质量比可为400:400:200:15:40~50:100~250:20~40:93~103:6.4~9,具体可为400:400:200:15:40:100:20:93:6.4、400:400:200:15:45:150:30:103:9、400:400:200:15:45:180:30:103:9、400:400:200:15:45:210:30:103:9或400:400:200:15:45:250:40:103:9。
上述的复合鞋底中,所述耐磨止滑橡胶的制备方法中步骤2)中所述混炼的温度为95℃~105℃,时间为68~112s,如90s;
步骤3)中所述混炼的温度为120℃~130℃,时间为88~132s,如120s。
步骤4)中所述硫化成型的温度可为145~155℃,硫化的时间可为5~10min。
上述的复合鞋底中,所述注塑足弓支撑架由热塑性聚氨酯注塑制成。
本发明还进一步提供了上述复合鞋底的制备方法,包括如下步骤:
将所述所述EVA注塑中底、橡胶外底和所述注塑足弓支撑架依次通过纤维素粉体改性聚氨酯胶粘剂胶浆复合即得;
所述纤维素粉体改性聚氨酯胶粘剂由下述质量份数比的组分组成:
二苯基甲烷二异氰酸酯150~200,
异佛尔酮二异氰酸酯20~50,
聚酯二元醇200~400,
扩链剂30~60,
纤维素粉体1~10,和
溶剂2000~4000。
上述的制备方法中,所述胶浆复合的温度可为50℃~60℃,具体可为50℃或60℃,压力为2~3MPa,具体可为2MPa或3MPa。
上述的制备方法中,所述聚酯二元醇选自聚己内酯二元醇、1,4-丁二醇-己二酸共聚二元醇、1,4-丁二醇-1,6己二醇-己二酸共聚二元醇、新戊二醇-己二酸共聚二醇、甲基丙二醇-己二酸共聚二醇和甲基丙二醇-新戊二醇-己二酸共聚二醇中至少一种;
所述聚酯二元醇的数均分子量为1000~3000;
所述扩链剂选自新戊二醇、甲基丙二醇、1,4-丁二醇和1,6-己二醇中至少一种;
所述溶剂选自丁酮、乙酸乙酯和丙酮中至少一种;
所述纤维素粉体改性聚氨酯胶粘剂在25℃时的粘度为1000~3500mPa.s。
所述纤维素粉体改性聚氨酯胶粘剂按照包括如下步骤的方法制备:
(1)所述苯基甲烷二异氰酸酯、所述聚酯二元醇和所述纤维素粉体改性聚氨酯胶粘剂进行反应;向所述反应的反应产物中加入所述异佛尔酮二异氰酸酯,经预聚反应得到预聚体;
(2)向所述预聚体中加入所述扩链剂进行扩链反应;然后向所述扩链反应的反应体系中加入所述溶剂即得到所述聚氨酯胶粘剂。
上述纤维素粉体改性聚氨酯胶粘剂的制备方法中,步骤(1)中,所述反应的温度可为80~90℃,时间可为0.75~1.25小时,如在85℃下反应1小时。
上述的上述纤维素粉体改性聚氨酯胶粘剂的制备方法中,步骤(1)中,所述预聚反应的温度可为85~95℃,时间可为2.75~3.25小时,如在90℃下反应3小时。
上述的上述纤维素粉体改性聚氨酯胶粘剂的制备方法中,步骤(2)中,所述扩链反应的温度可为50~80℃,时间可为2~5小时,如在50℃下反应4小时。
本发明具有如下有益效果:所制成的复合鞋底具有良好的弹性、弹性恢复性、防滑性、耐磨性,满足的运动及休闲类鞋靴的穿着舒适性需要,同时,具有良好的抗撕裂性能和防老化开胶性能,满足了穿着的耐用性需要。
附图说明
图1为本发明实施例1中制备的加入改性麻杆粉的发泡体的电镜照片。
图2为未加入改性麻杆粉得到的EVA的电镜照片。
图3为本发明实施例1制备的耐磨止滑橡胶的电镜照片(玄武岩纤维与橡胶的黏结形态为镶嵌式)。
图4为本发明实施例1制备的耐磨止滑橡胶的电镜照片(玄武岩纤维与橡胶的黏结形态为电焊式)。
图5为图3所示玄武岩纤维与橡胶的电焊式粘结边缘的电镜照片。
图6为本发明实施例1制备的耐磨止滑橡胶的电镜照片(玄武岩纤维与橡胶的黏结形态为完全黏合式)。
图7为本发明制备的复合鞋底内侧的示意图。
图8为本发明制备的复合鞋底外侧的示意图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1、制备复合鞋底及其性能测试
一、制备纤维素粉体改性聚氨酯胶粘剂
(1)将120质量份的二苯基甲烷二异氰酸酯、5质量份的汉麻杆芯粉(粒径为20微米)、60质量份的1,4-丁二醇-己二酸共聚二元醇(分子量为1500)、330质量份的1,4-丁二醇-1,6己二醇-己二酸共聚二元醇(分子量为2000)加入反应釜中,升温至85℃进行聚合反应1小时;然后向该反应体系中加入30质量份的异佛尔酮二异氰酸酯,于90℃进行预聚反应3小时得到预聚体。
(2)向上步得到的预聚体中加入10.5质量份的新戊二醇和20质量份1,4丁二醇作为扩链剂,在50℃下进行扩链反应,当反应4小时,该反应体系的粘度和温度均不再上升,加入500质量份乙酸乙酯、1500质量份丁酮和375质量份丙酮溶剂调节粘度至约2000mPa.s,即得到鞋用纤维素粉体改性聚氨酯胶粘剂。
本实施例制备的鞋用纤维素粉体改性聚氨酯胶粘剂为无色透明液体,固含量为19.5%。
二、制备EVA注塑中底
将50重量份的粒径为500目的木质纤维素粉体用5重量份的硅烷偶联剂进行均匀的喷淋,储存、烘干制成均匀的改性木质纤维素粉体。
将50重量份的商品名为EVA7470、数均分子量为1800的乙烯-醋酸乙烯共聚物(其中醋酸乙烯(VA)的质量百分含量为26%)、50重量份的商品名为GT-01、数均分子量为20000的部分氢化苯乙烯丁二烯聚合物和50重量份的粒径为500目的改性木质纤维素粉体投入密炼机中混炼,混炼过程中,开炼机温度不超过70℃,混炼温度为90℃,混炼时间为0.2小时。
同时将4重量份的商品名为AC3000的发泡剂偶氮二甲酰胺、0.6重量份的架桥剂过氧化二异丙苯(DCP)、2重量份的活性剂硬脂酸和1重量份的氧化锌投入另一密炼机中混炼,混炼过程中,开炼机温度不超过70℃,混炼温度为100℃,混炼时间为0.1小时。
投入造粒机中间造粒:设定造粒机温度:第一段95℃,第二段95℃,第三段95℃,第四段90℃,主机转速35转,入料机转速30转,切刀转速15转,每批次的料进入搅拌桶搅拌均匀,时间20分钟。
输入至射出发泡成型机中进行射出发泡成型,模具温度:上模177~183℃;下模177~183℃。
经冷却成型得到发泡材料,恒温箱温度:85±5℃、75±5℃、65±5℃;恒温时间:30℃±5分钟;恒温机轮速:125±10转。
图1为本实施例制备的发泡体(加入改性麻杆粉)的电镜照片,与未加入改性麻杆粉的EVA的电镜照片(图2)相比,可以看出,麻杆粉加入后在EVA内形成皱褶,类似弹簧机理,有利于EVA受压缩后恢复弹性。
经测定,本实施例制备的木质纤维素粉体发泡体的物性如表1中所示。
表1中,各指标的测试方法如下:
视密度:HG/T 2872-2009,测试片带皮;
拉伸强度:GB/T 10654-2001,测试片带皮,标线距离为50mm,取两个垂直方向测试结果的平均值;
拉断伸长率:GB/T 10654-2001,测试片带皮,标线距离为50mm,取两个垂直方向测试结果的平均值;
直角形撕裂强度:GB/T 10808-2006,测试片带皮,测试速度50mm/min;
回弹性:GB/T 10652-2001,测试片带皮;
加湿老化后鞋底周圈剥离强度:GB/T 3903.7-2005,附录E.5.1,70℃、120h、95%RH。
表1、本实施例制备的木质纤维素粉体发泡体的物性
由表1中的数据可得知,本发明提供的改性木质纤维素粉体发泡体具有轻质、耐久、避震、高弹和抗撕裂性能,适用于制备各种竞技类和休闲类的鞋中底,具有重要的应用价值。
三、制备橡胶外底
采用表2中的配方进行制备本发明耐磨止滑橡胶,制备过程如下:
(1)制备预处理短纤维
喷淋乙烯基三乙氧基硅烷对玄武岩(直径为10~100μm,长度为1~10mm)进行预处理,偶联剂的用量为玄武岩质量的1%,储存、烘干制成均匀的预处理短纤维。
(2)混炼
1)先将部份粗坯(天然橡胶、丁二烯橡胶、丁腈橡胶和预处理短纤维)混炼温度为100±5℃,完毕后平铺于料盘中,时间为90s;
2)向另一部份粗坯(天然橡胶、丁二烯橡胶、丁腈橡胶和预处理短纤维)中加入氧化镁、硅烷、硬脂酸、硫磺和ZnO,硫磺和ZnO依次加入,然后加入步骤1)的物料中进行混炼温度为125±5℃,时间为120s:
混炼过程中,启动翻料机,在此过程中加入不超过13.5kg/手回收料混炼,然后将轮台距调至0.9~1.1mm,打薄三次,时间约720秒,接着轮距调至8-10mm,束筒送入14"轮台出片,时间60~120秒;出片对照一般物料方式,依照PFC设定厚度标准出片,片料送入待检区。
(3)硫化成型
将所有原料按配比经上述方法混炼后放入硫化机硫化成型,硫化温度145℃,硫化时间8分钟。
上述制备过程中,需要注意如下问题:
A、打料前轮台温度50℃以下,打料中控制在80℃以下;
B、料出片时不过水,采取凉料方式进行冷却作业;
C、片料经过检验后方可进行下一制程。
成型生产规范:
1)机台温度标准为:100℃~200℃;
2)机台压力标准:140kg/cm2~150kg/cm2。
表2实施1-5和对比例1中的原料配方(质量比)
实施1制备的橡胶的电镜照片如图3、图4、图5和图6所示,其中图3(a)的放大倍数为5000,图3(b)的放大倍数为15000,由图3可以看出,玄武岩纤维与橡胶间仍有缝隙,属于不完全黏合,该黏合形态为镶嵌式。
其中图4(a)的放大倍数为6000,图4(b)的放大倍数为17000,由图4可以看出,玄武岩纤维与橡胶间仍有缝隙,属于不完全黏合,该黏合形态为电焊式。
图4所示玄武岩纤维与橡胶的电焊式粘结边缘的电镜照片如图5所示,其中图5(a)的放大倍数为5000,图5(b)的放大倍数为15000。
图6(a)的放大倍数为100,图6(b)的放大倍数为1000,图6(b)是图4(a)的局部放大,由图4可以看出,玄武岩纤维与橡胶间没有缝隙,属于完全黏合。
经测定,实施1~6所制备的耐磨止滑橡胶的物性表现如表3和表4中所示。
表3实施1-6制备的耐磨止滑橡胶的理化性能
表4实施例1-6制备的耐磨止滑橡胶的密度、止滑性能和磨耗体积
对比表3和表4中的数据可知,本发明高耐磨高止滑橡胶具有绝佳的耐磨止滑性能,最高也在0.15以下,能经受长时间的磨耗,干止滑在1.0以上,湿止滑在0.80以上;而不加短纤维的耐磨和干湿止滑在数据上均下降很多;由该高耐磨高止滑橡胶制备的鞋大底能适用于网球鞋大底及其它对耐磨止滑性能要求较高的鞋大底。
本发明通过普通橡胶主体胶料,加入预处理短纤维,经混炼、热压及脱模,制备的高耐磨高止滑橡胶比普通的橡胶要具有更佳的耐磨止滑功能。
综上所述,本发明的高耐磨高止滑橡胶具有绝佳的耐磨止滑性能,由其制成的鞋大底耐磨止滑性好,可适用于用作耐磨止滑性能要求较高的鞋外底。不仅可以整体作为大底使用,也可以作为部分耐磨位置与普通橡胶共同使用。
四、制备复合鞋底
在将上述制备的EVA注塑中底和橡胶大底复合之前,要对EVA注塑中底表面和橡胶表面进行处理。
EVA注塑中底打磨经过:打粗(由于发泡出来的EVA表面带有一些整理剂使表面光滑不易贴合,因此打粗的目的是使表面粗糙,利于底和胶水的黏着)—磨边—消前消后(根据设计的弧度进行修整)。
橡胶外底经过丁酮、乙酸甲酯和乙酸乙酯溶剂预清洗处理,再经过:加热烤干(55℃,红外线3min)—边缘锤压—定型(至少8s)—品检。
将经处理过的EVA注塑中底与橡胶外底采用上述制备的汉麻改性聚氨酯胶粘剂进行胶浆复合,温度为50℃,压力为3MPa,再将注塑足弓支撑架(由热塑性聚氨酯注塑制成)与橡胶外底进行胶浆复合,温度为60℃,压力为2MPa,即得到复合鞋底。
本实施例制备的复合鞋底的外观示意图如图7和图8所示,其中图7为复合鞋底内侧的示意图,图8为复合鞋底外侧的示意图。
本实施例制备的复合鞋底的物理性能如表5中所示。
表5复合鞋底的物理性能
由表5中的数据可得知,所制成的复合鞋底具有良好的弹性、弹性恢复性、防滑性、耐磨性,满足的运动及休闲类鞋靴的穿着舒适性需要,同时,具有良好的抗撕裂性能和防老化开胶性能,满足了穿着的耐用性需要。
Claims (8)
1.一种复合鞋底,由EVA注塑中底、橡胶外底和注塑足弓支撑架依次复合而成;
所述EVA注塑中底由高回弹耐老化EVA发泡材料制成,所述高回弹耐老化EVA发泡材料按照包括如下步骤的方法制备得到:
1)利用硅烷偶联剂对木质纤维素粉体进行改性,得到改性木质纤维素粉体;
所述硅烷偶联剂为乙烯基三氯硅烷、乙烯基三乙氧基硅烷、乙烯基三(β-甲氧乙氧基)硅烷、γ-缩水甘油丙基-三甲氧基硅烷、γ-甲基丙烯酰氧基丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基-甲基-三甲氧基硅烷、γ-氯丙基-三甲氧基硅烷、γ-巯丙基-三甲氧基硅烷和γ-氨丙基-三甲氧基硅烷中至少一种;
所述硅烷偶联剂的用量为所述木质纤维素粉体质量的0.1~1.5%;
所述木质纤维素粉体为汉麻杆芯、黄麻杆芯、亚麻杆芯、剑麻杆芯、苎麻杆芯和竹子至少一种;
2)将部分氢化苯乙烯丁二烯聚合物、乙烯-醋酸乙烯共聚物和所述改性木质纤维素粉体混合后进行混炼;
3)将发泡剂、架桥剂、活性剂和氧化锌加入所述混炼的体系中进行混炼;
4)经步骤2)和步骤3)密炼后的物料进行造粒,然后进行射出发泡,经冷却成型即得所述高回弹耐老化EVA发泡材料;
所述复合鞋底中,所述乙烯-醋酸乙烯共聚物、所述部分氢化苯乙烯丁二烯聚合物、所述改性木质纤维素粉体、所述发泡剂、所述架桥剂、所述活性剂和所述氧化锌的质量比为50:50:40~70:3.5~4.5:0.6~0.8:2~2.5:1~1.5;
所述复合鞋底是由包括如下步骤的方法制备得到的:将所述EVA注塑中底、橡胶外底和所述注塑足弓支撑架依次通过纤维素粉体改性聚氨酯胶粘剂胶浆复合即得;
所述纤维素粉体改性聚氨酯胶粘剂由下述质量份数比的组分组成:
二苯基甲烷二异氰酸酯150~200,
异佛尔酮二异氰酸酯20~50,
聚酯二元醇200~400,
扩链剂30~60,
纤维素粉体1~10,和
溶剂2000~4000。
2.根据权利要求1所述的复合鞋底,其特征在于:所述木质纤维素粉体的粒径为200目~1000目;
所述部分氢化苯乙烯丁二烯聚合物的数均分子量为12000~50000;
所述乙烯-醋酸乙烯共聚物的数均分子量为400~4000,所述乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量为20~40%;
所述发泡剂选自偶氮二甲酰胺、对甲苯磺酰肼和偶氮二甲硫胺中的至少一种;
所述架桥剂选自过氧化二异丙苯、硫磺和二叔丁基过氧化物中的至少一种;
所述活性剂选自硬脂酸、碳酸镁和氧化钙中的至少一种。
3.根据权利要求1或2所述的复合鞋底,其特征在于:所述橡胶外底由耐磨止滑橡胶制成,所述耐磨止滑橡胶按照包括如下步骤的方法制备得到:
1)利用硅烷偶联剂对短纤维进行改性,得到改性短纤维;
所述短纤维为碳纤维、玻璃纤维和玄武岩纤维中至少一种;
所述短纤维的直径为10~100μm,长度为1~10mm;
所述硅烷偶联剂的用量为所述短纤维质量的0.1%~1.5%;
2)称取天然橡胶、顺丁二烯橡胶、丁腈橡胶和所述改性短纤维作为粗坯;将部分所述粗坯进行混炼;
3)向余量的所述粗坯中加入氧化镁、硅烷、硬脂酸、促进剂和活性剂,然后加入至步骤2)所述混炼后的物料中进行混炼;所述促进剂和所述活性剂依次加入至所述粗坯中;
4)步骤3)所述混炼后的物料进行硫化成型,得到所述耐磨止滑橡胶。
4.根据权利要求3所述的复合鞋底,其特征在于:所述促进剂为硫磺;所述活性剂为ZnO、聚乙烯醇和聚乙烯中至少一种。
5.根据权利要求1或2所述的复合鞋底,其特征在于:所述注塑足弓支撑架由热塑性聚氨酯注塑制成。
6.权利要求1-5中任一项所述复合鞋底的制备方法,包括如下步骤:将所述EVA注塑中底、橡胶外底和所述注塑足弓支撑架依次通过纤维素粉体改性聚氨酯胶粘剂胶浆复合即得;
所述纤维素粉体改性聚氨酯胶粘剂由下述质量份数比的组分组成:
二苯基甲烷二异氰酸酯150~200,
异佛尔酮二异氰酸酯20~50,
聚酯二元醇200~400,
扩链剂30~60,
纤维素粉体1~10,和
溶剂2000~4000。
7.根据权利要求6所述的制备方法,其特征在于:所述聚酯二元醇选自聚己内酯二元醇、1,4-丁二醇-己二酸共聚二元醇、1,4-丁二醇-1,6-己二醇-己二酸共聚二元醇、新戊二醇-己二酸共聚二醇、甲基丙二醇-己二酸共聚二醇和甲基丙二醇-新戊二醇-己二酸共聚二醇中至少一种;
所述聚酯二元醇的数均分子量为1000~3000;
所述扩链剂选自新戊二醇、甲基丙二醇、1,4-丁二醇和1,6-己二醇中至少一种;
所述溶剂选自丁酮、乙酸乙酯和丙酮中至少一种;
所述纤维素粉体改性聚氨酯胶粘剂在25℃时的粘度为1000~3500mPa.s。
8.根据权利要求6或7所述的制备方法,其特征在于:所述纤维素粉体改性聚氨酯胶粘剂按照包括如下步骤的方法制备:
(1)所述二苯基甲烷二异氰酸酯、所述聚酯二元醇和所述纤维素粉体改性聚氨酯胶粘剂进行反应;向所述反应的反应产物中加入所述异佛尔酮二异氰酸酯,经预聚反应得到预聚体;
(2)向所述预聚体中加入所述扩链剂进行扩链反应;然后向所述扩链反应的反应体系中加入所述溶剂即得到所述聚氨酯胶粘剂。
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