CN101302316A - 共插层型纳米聚丙烯复合材料的生产方法 - Google Patents

共插层型纳米聚丙烯复合材料的生产方法 Download PDF

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CN101302316A
CN101302316A CNA2008101227318A CN200810122731A CN101302316A CN 101302316 A CN101302316 A CN 101302316A CN A2008101227318 A CNA2008101227318 A CN A2008101227318A CN 200810122731 A CN200810122731 A CN 200810122731A CN 101302316 A CN101302316 A CN 101302316A
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CN101302316B (zh
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唐敖齐
贾国富
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Jiangsu Xinquan Automobile Accessories Co., Ltd.
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

共插层型纳米聚丙烯复合材料由以下组份组成(以wt.%表示):70-100%PP的材料和0.3-40%纳米填料,1份重量的纳米填料中含有10-90%的无机层状材料和10-90%的共插层剂。生产方法包括研磨、纳米填料混料、挤压、造粒。采用本发明,由于加入了丙烯酸酯使PP材料的极性提高到μ=0.65,有效解决了PP材料与聚氨酯粘接的问题;其次是使丙烯酸酯获得更好的分散效果,达到10-30纳米尺度,具有非常大的界面面积,化学键合使无机分散相与聚合物基体界面具有理想的粘接性能,可消除无机物与聚合物基体两物质热膨胀系数不匹配问题,充分发挥无机物内在的优异力学性能、高耐热性、阻隔性。

Description

共插层型纳米聚丙烯复合材料的生产方法
技术领域
本发明涉及以PP为原料的高新领域复合材料,尤其是加入以无机层状材料和丙烯酸酯及其他助剂复合而成的纳米填料混合形成新型复合材料——共插层型纳米聚丙烯复合材料的生产方法。
背景技术
目前国内外市场上汽车仪表板骨架普遍采用的是ABS工程材料,该材料综合性能较好,具有易加工性以及很高的抗冲击强度因而受到广泛应用,但其热变形温度低(一般在80℃),可燃、比重大且价格高,PP材料具有更强的抗冲击强度、表面刚度和韧性,其热变形温度一般在100℃,通过加入纳米填料后可以提高到115℃。
PP材料的流动性较好,熔融指数远高于ABS,在注射时压力可降低25%,大大降低了设备能耗,其成本因选用的基料不同也可以得到很好控制,鉴于以上两种材料性能对比,仪表板骨架材料采用PP材料替代ABS正是在降低成本、提高产品特性、解决汽车轻量化等的前提下提出的。传统的PP材料是非极性材料,其不易和聚氨脂发泡料粘接是汽车仪表板行业普遍存在的技术难题,
PP材料与聚氨酯粘接的问题,有两个关键因素是必须要解决的:首先是PP材料表面的极性化处理,由于PP材料为非极性材料,在常规情况下它是不能和聚氨酯融合的,其次是使丙烯酸酯获得更好的分散效果,虽然丙烯酸酯能够提高材料的极性,但由于其在常规状态下不能得到更好的分散,致使极性化处理效果不佳。
发明内容
针对以上不足,本发明的目的在于提供一种共插层型纳米聚丙烯复合材料,是以PP为原料,加入以无机层状材料和丙烯酸酯及其少量硅烷,并对成品骨架进行适当的表面处理,从而达到很好的与聚氨脂发泡材料粘接,增强材料极性的纳米复合材料。
本发明的另一个目的在于提供上述共插层型纳米聚丙烯复合材料的生产方法。
本发明的技术方案是通过以下方式实现的:共插层型纳米聚丙烯复合材料,其特征在于:由以下组份组成(以wt.%表示),70-100%的PP材料和0.3-40%的纳米填料,其中1份重量的纳米填料含有10-90%的无机层状材料和10-90%的共插层剂。
上述的纳米填料其最佳含量范围是0.5-20%。
上述的无机层状材料是钠基蒙脱土、钙基蒙脱土、镁基蒙脱土等蒙脱土类,也可以是绿脱石、锂皂石、皂石、斑脱石、伊利石、高岭土、蒙脱土与伊利石的复合物或是磷酸盐。
上述的1份重量的共插层剂含有60-80%的丙烯酸酯类和20-40%的硅烷类材料。
上述的丙烯酸酯类是丙氧基化新戊二醇二丙烯酸酯。
上述的硅烷类是长链烷基三甲氧基硅烷。
一种共插层型纳米聚丙烯复合材料的生产方法,依次包括以下步骤:
1)、研磨:将无机层状材料,用球磨机、振动磨、喷射磨等粉碎成粒径为200目-400目的颗粒;
2)、纳米填料混料:将60-80%的丙烯酸酯类和20%-40%的硅烷类混料;
3)、挤压:取10-90%的无机层状材料和10-90%的共插层剂在双螺杆挤出机内挤出、挤出机温度控制在140-170℃、得到的产物即为半成品共插层型纳米填料;
4)、造粒:将0.3-40%半成品共插层型纳米填料与70-100%PP材料投入如双螺杆挤出机中熔融挤出造粒,挤出机的温度控制在200-230℃之间。即可得到最终的纳米复合材料。
采用本发明,由于加入了丙烯酸酯使PP材料的极性提高到μ=0.65;将极性基团-丙烯酸酯以纳米尺度分散在PP基体中,从而有效解决了PP材料与聚氨酯粘接的问题;其次是使丙烯酸酯获得更好的分散效果,达到10-30纳米尺度,具有非常大的界面面积,化学键合使无机分散相与聚合物基体界面具有理想的粘接性能,可消除无机物与聚合物基体两物质热膨胀系数不匹配问题,充分发挥无机物内在的优异力学性能、高耐热性、阻隔性。
具体实施方式
本发明由下述过程组成:
1)研磨:将无机层状材料,此类材料包括钠基蒙脱土(sodiummontmorillonite)、钙基蒙脱土(calcium montmorillonite)、镁基蒙脱土(magnesium montmorillonite)等蒙脱土类(smectite),绿脱石(nontronite)、贝得石(beidelite)、富铬绿脱石(volkonskoite)、锂皂石(hectorite)、皂石(saponite)、锌皂石(sauconite)、斯皂石(stevensite)、斑脱石(bentonite)、伊利石(illite)、高岭土(kaolin)、蒙脱土与伊利石的复合物如累脱石(rectorite)等。除了以上天然矿物外,人工水热合成的蒙脱土及皂石也包括在本发明所指的无机层状材料之中。另外还包括具有层状晶体结构的磷酸盐,过渡金属氧化物及卤氧化物,如三氧化钼(MoO3)、水合五氧化二矾(V2O5·nH2O,n≥0)以及水合硫酸氢铁(HFe(SO4)2·nH2O,n≥0)等。用球磨机、振动磨、喷射磨等将其粉碎成所希望的颗粒尺寸,一般粒径应在200目-400目。
2)、纳米填料混料:60-80%丙氧基化新戊二醇二丙烯酸酯和20%-40%长链烷基三甲氧基硅烷混料;
3)、挤压:取10-90%的无机层状材料和10-90%的共插层剂在双螺杆挤出机内挤出、挤出机温度控制在160℃、得到的产物即为半成品共插层型纳米填料;
4)、造粒:将0.3-40%半成品共插层型纳米填料与70-100%PP投入如双螺杆挤出机中熔融挤出造粒,挤出机的温度控制在200-230℃之间。即可得到最终的纳米复合材料。
共插层型含量低于0.3%,纳米填料不足以产生足够的增强作用;当插层型纳米填料含量超过40%,纳米复合材料不能加工成型。在方法中,纳米填料的最佳含量范围是0.5-20%。挤出机的温度控制在200-230℃之间。
本方法使纳米填料分散相达到10-30纳米尺度,具有非常大的界面面积,化学键合使无机分散相与聚合物基体界面具有理想的粘接性能,可消除无机物与聚合物基体两物质热膨胀系数不匹配问题,充分发挥无机物内在的优异力学性能、高耐热性、阻隔性。同时将丙烯酸酯以纳米尺度分散在PP基体中,从而赋予了PP材料的可粘接性。性能试验结果对照表
试验项目 单位 ABS 普通PP   共插层型纳米聚丙烯复合材料
  密度   g/cm3   1.04   0.99   1.04
  燃烧灰份   %   -   13.5   20
  拉伸强度   Mpa   22   24.3   24.7
  断裂伸长率   %   42   200   422
  弯曲强度   Mpa   47   32.2   34
  弯曲模量   Mpa   1700   1690   2062
  悬臂梁缺口冲击强度   KJ/m2   9.2   10.9   109
  热变形温度   ℃   85   100   116
  粘接力   N   3   0   3

Claims (7)

1、共插层型纳米聚丙烯复合材料,其特征在于:由以下组份组成(以wt.%表示):70-100%的PP材料和0.3-40%的纳米填料,其中1份重量的纳米填料中含有10-90%的无机层状材料和10-90%的共插层剂。
2、根据权利要求1所述的共插层型纳米聚丙烯复合材料,其特征在于:所述的纳米填料其最佳含量范围是0.5-20%。
3、根据权利要求1所述的共插层型纳米聚丙烯复合材料,其特征在于;所述的无机层状材料是钠基蒙脱土、钙基蒙脱土、镁基蒙脱土蒙脱土类,也可以是绿脱石、锂皂石、皂石、斑脱石、伊利石、高岭土、蒙脱土与伊利石的复合物或是磷酸盐。
4、根据权利要求1所述的共插层型纳米聚丙烯复合材料,其特征在于:所述的1份重量的共插层剂是60-80%的丙烯酸酯类和20%-40%的硅烷类。
5、根据权利要求4所述的共插层型纳米聚丙烯复合材料,其特征在于:所述的丙烯酸酯类是丙氧基化新戊二醇二丙烯酸酯。
6、根据权利要求4所述的共插层型纳米聚丙烯复合材料,其特征在于:所述的硅烷类是长链烷基三甲氧基硅烷。
7、一种共插层型纳米聚丙烯复合材料的生产方法,依次包括以下步骤(以wt.%表示):
1)、研磨:将无机层状材料,用球磨机、振动磨、喷射磨等粉碎成粒径为200目-400目的颗粒;
2)、纳米填料混料:将60-80%的丙烯酸酯类和20%-40%的硅烷类混料;
3)、挤压:取10-90%的无机层状材料和10-90%的共插层剂在双螺杆挤出机内挤出、挤出机温度控制在140-170℃、得到的产物即为半成品共插层型纳米填料;
4)、造粒:将0.3-40%半成品共插层型纳米填料与70-100%PP投入如双螺杆挤出机中熔融挤出造粒,挤出机的温度控制在200-230℃之间。即可得到最终的纳米复合材料。
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CN105733308A (zh) * 2016-01-27 2016-07-06 哈尔滨理工大学 聚硅烷-二硫化钼夹层复合材料的制备方法

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CN1123613C (zh) * 1998-12-03 2003-10-08 中国石化齐鲁石油化工公司 高分子热熔粘合剂及其制造方法
CN1209408C (zh) * 2002-04-23 2005-07-06 上海交通大学 在紫外光照射下可发出蓝绿光的聚丙烯复合材料
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CN104558768B (zh) * 2014-12-23 2017-05-31 贾纬民 一种环保减量清洁生态型发泡材料的制备方法及制备的发泡材料和终端成品
CN105733308A (zh) * 2016-01-27 2016-07-06 哈尔滨理工大学 聚硅烷-二硫化钼夹层复合材料的制备方法
CN105733308B (zh) * 2016-01-27 2017-12-29 哈尔滨理工大学 聚硅烷‑二硫化钼夹层复合材料的制备方法

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