CN101570612B - 一种车用低voc内饰件pp复合材料的制备方法 - Google Patents

一种车用低voc内饰件pp复合材料的制备方法 Download PDF

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CN101570612B
CN101570612B CN2009100378279A CN200910037827A CN101570612B CN 101570612 B CN101570612 B CN 101570612B CN 2009100378279 A CN2009100378279 A CN 2009100378279A CN 200910037827 A CN200910037827 A CN 200910037827A CN 101570612 B CN101570612 B CN 101570612B
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interior trim
trim parts
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CN101570612A (zh
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郝源增
余鹏
刘文志
郝建鑫
刘志
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GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD.
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GUANGZHOU JINGYING PLASTIC CO Ltd
JUSAILONG ENGINEERING PLASTICS Co Ltd CONGHUA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means 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
    • B29C48/40—Means 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion 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
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92923—Calibration, after-treatment or cooling zone

Abstract

本发明涉及汽车领域，属于一种低VOC(有机挥发物)高性能汽车内饰件专用PP复合材料及其制备方法，该专用料由下述组分质量份制备而成：聚丙烯(PP)60-80份，增强填充剂10-25份，增韧剂10-15份，无机光催化剂0.5-2份，抗氧剂0.2-0.5份，光稳定剂0.1-0.5份。本发明所得聚丙烯复合材料TVOC＜40μgC/g，23℃下的悬臂梁缺口冲击强度10-42KJ/m2，弯曲模量1000-2400MPa，230℃，2.16Kg时的熔融指数10-30g/10min，该车用低VOC内饰件PP复合材料具有低成本、稳定性好、具有自净化VOC功能。可广泛应用于汽车内饰件的生产。

Description

一种车用低VOC内饰件PP复合材料的制备方法
技术领域
本发明涉及汽车领域，具体涉及一种车用内饰件材料的制备方法。
背景技术
随着汽车行业对材料性能要求的不断严格，环保型低VOC材料已成为汽车用内饰材料开发的热点和方向之一。汽车内饰件一般为改性PP复合材料，其产生VOC的原因主要有：(1)PP树脂。常规高流动PP树脂一般通过有机过氧化物降解法生产，树脂内残留的过氧化物会反应生成醇、醛等有机挥发物；(2)加工助剂的与基体PP树脂的相容性。耐热性差、与基体树脂相容差的加工助剂会通过析出、挥发产生VOC；(3)改性PP复合材料的热稳定性。PP树脂分子链会在持续的热氧化过程中部分断链降解成小分子或低分子，由此产生VOC。
目前国内对低VOC汽车专用料研究甚少，只有个别关于低气味汽车料的报道，如，中国专利《高性能低气味汽车仪表板专用聚丙烯的制备方法》，专利申请号：200510024840.2，报道通过添加吸附剂如多孔分子筛来降低材料的低气味，但这种方式制得的产品存在吸附平衡的问题；中国专利《低散发型汽车内饰件专用料的制备方法》，专利申请号：200810023327.5，报道通过添加有机物驱除剂如异丙醇/水来降低材料的低气味，然而这种方式存在相容性、持久性问题。
因此，如何使材料具有全面持久的低VOC排放性、自洁性以及满足汽车专用料的高性能要求，将具有重要的实际应用价值，相关途径还未见报道。
发明内容
本发明的目的是针对现有技术的不足而提供一种制备容易、低成本、稳定性好、具有自净化VOC功能的车用低VOC内饰件PP复合材料的制备方法。
本发明的上述目的可以通过以下技术方案实现：
一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：包括如下步骤，
(1)将增强填充剂、增韧剂、无机光催化剂、抗氧剂、光稳定剂加入搅拌机中，在300-500转/分的转速下搅拌混合3-5分钟；
(2)加入聚丙烯树脂在300-500转/分的转速下搅拌混合3-5分钟；
(3)将上述混合物放入双螺杆挤出机中，于180-210℃下熔融挤出造粒即得成品。双螺杆挤出机螺杆转速为250-400rpm；水槽温度20-40℃；切粒机转速为600-1000rpm；
上述组分按重量百分比为：
(1)聚丙烯树脂          60-80％；
(2)增强填充剂          10-25％；
(3)增韧剂              10-15％；
(4)无机光催化剂        0.5-2％；
(5)抗氧剂              0.2-0.5％；
(6)光稳定剂            0.1-0.5％；
上述各组分配方比例总和为100％。
所述的聚丙烯树脂为均聚聚丙烯树脂和共聚聚丙烯树脂混合物，其熔体流动速率为5-40g/10min，其中均聚聚丙烯35-45％，共聚聚丙烯55-65％，配方比例总和为100％。
所述增强填充剂为超细滑石粉，其粒径为1-6μm。
所述增韧剂为聚烯烃弹性体乙烯-丙烯-辛烯共聚物、苯乙烯-丁二烯共聚物、氢化的苯乙烯-丁二烯-苯乙烯嵌段共聚物中的任一种或两种以上的混合物。
所述的无机光催化剂为铈粒子掺杂的纳米TiO2粒子，其粒径为40-50nm。
所述的抗氧剂为为酚类抗氧剂、亚磷酸酯类抗氧剂、金属钝化剂中的任一种或两种以上的混合物。
所述的光稳定剂为受阻胺类、N-烷基化类、紫外线吸收剂苯并三唑类、三嗪苄叉丙二酸酯类中的任一种或两种以上的混合物。
所述的抗氧剂为酚类抗氧化剂1010。
所述的光稳定剂为受阻胺类汽巴的TINUV770与苯并三唑类汽巴326的1∶1混合物。
本发明所述配方及工艺制得的低VOC高性能汽车内饰件专用PP复合材料采用ISO标准检测，性能如下：
密度：            1.01-1.09g/cm3
断裂伸长率：      75-150％
拉伸强度：        23-26MPa
弯曲模量：        1000-2400MPa
悬臂梁缺口冲击强度：  10-42KJ/m2
熔融指数：            10-30g/10min((230℃，2.16Kg)
TVOC：                ＜40μgC/g
其有益效果是：现有技术是通过添加除味剂或小分子驱除剂等方法控制材料的低气味，该技术方法所制得材料存在吸附平衡或持久性问题，且没有自净化VOC能力。与现有技术相比，本发明通过铈盐掺杂纳米TiO2粒子在可见光下的光催化作用，能有效分解有机小分子，降低VOC含量，提供一种具有自净化VOC功能的汽车内饰件专用PP复合材料。
具体实施方式
实施例1：
下述组分按重量百分比为：
(1)均聚聚丙烯树脂                      26％
(2)共聚聚丙烯树脂                      42％
(3)增强填充剂：超细滑石粉，粒径1-6μm  20％
(4)增韧剂：乙烯-丙烯-辛烯共聚物        10.5％
(5)无机光催化剂：铈盐掺杂纳米TiO2粒子，
                 粒径40-50nm           1％
(6)抗氧剂：1010                        0.2％
(7)光稳定剂：TINUV770/326＝1           0.3％
先将增强填充剂、增韧剂、无机光催化剂、抗氧剂、光稳定剂放入搅拌机中，在300转/分的转速下搅拌混合5分钟，随后加入均聚聚丙烯树脂和共聚聚丙烯树脂，在400转/分的转速下搅拌混合5分钟。再将上述混合物放入双螺杆挤出机中，于200℃下熔融挤出造粒得到车用低VOC内饰件PP复合材料。本实施例中，双螺杆挤出机螺杆转速为300rpm，水槽温度20-40℃，切粒机转速为800rpm。
所得车用低VOC内饰件PP复合材料经检测性能如下：
密度：                1.03g/cm3
断裂伸长率：          85％
拉伸强度：            25MPa
弯曲模量：            2045MPa
悬臂梁缺口冲击强度：  36KJ/m2
熔融指数：            22.1g/10min((230℃，2.16Kg)
TVOC：                18.1μgC/g
实施例2：
下述组分按重量百分比为：
(1)均聚聚丙烯树脂                      27％
(2)共聚聚丙烯树脂                      43％
(3)增强填充剂；超细滑石粉，粒径1-6μm  15％
(4)增韧剂：乙烯-丙烯-辛烯共聚物        13％
(5)无机光催化剂：铈盐掺杂纳米TiO2粒子，
                 粒径40-50nm           1.5％
(6)抗氧剂：1010                        0.2％
(7)光稳定剂：TINUV770/326＝1           0.3份
先将增强填充剂、增韧剂、无机光催化剂、抗氧剂、光稳定剂放入搅拌机中，在300转/分的转速下搅拌混合5分钟，随后加入聚丙烯树脂在400转/分的转速下搅拌混合5分钟。再将上述混合物经双螺杆挤出机中，于180-210℃下熔融挤出造粒得到车用低VOC内饰件PP复合材料。本实施例中，双螺杆挤出机螺杆转速为300rpm，水槽温度20-40℃，切粒机转速为800rpm。
所得车用低VOC内饰件PP复合材料经检测性能如下：
密度：                1.01g/cm3
断裂伸长率：          125％
拉伸强度：            23MPa
弯曲模量：            1968MPa
悬臂梁缺口冲击强度：  40KJ/m2
熔融指数：            18.2g/10min((230℃，2.16Kg)
TVOC：                16.2μgC/g

Claims (8)

1.一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：包括如下步骤，
(1)将增强填充剂、增韧剂、无机光催化剂、抗氧剂、光稳定剂加入搅拌机中，在300-500转/分的转速下搅拌混合3-5分钟；
(2)加入聚丙烯树脂在300-500转/分的转速下搅拌混合3-5分钟；
(3)将上述混合物放入双螺杆挤出机中，于180-210℃下熔融挤出造粒即得成品，双螺杆挤出机螺杆转速为250-400rpm；水槽温度20-40℃；切粒机转速为600-1000rpm；
上述组分按重量百分比为：
(1)聚丙烯树脂          60-80％；
(2)增强填充剂          10-25％；
(3)增韧剂              10-15％；
(4)无机光催化剂        0.5-2％；
(5)抗氧剂              0.2-0.5％；
(6)光稳定剂            0.1-0.5％；
上述的无机光催化剂为铈粒子掺杂的纳米TiO2粒子，其粒径为40-50nm；
上述各组分配方比例总和为100％。
2.根据权利要求1所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述的聚丙烯树脂为均聚聚丙烯树脂和 共聚聚丙烯树脂混合物，其熔体流动速率为5-40g/10min，其中均聚聚丙烯35-45％，共聚聚丙烯55-65％，配方比例总和为100％。
3.根据权利要求1所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述增强填充剂为超细滑石粉，其粒径为1-6μm。
4.根据权利要求1所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述增韧剂为聚烯烃弹性体乙烯-丙烯-辛烯共聚物、苯乙烯-丁二烯共聚物、氢化的苯乙烯-丁二烯-苯乙烯嵌段共聚物中的任一种或两种以上的混合物。
5.根据权利要求1所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述的抗氧剂为为酚类抗氧剂、亚磷酸酯类抗氧剂、金属钝化剂中的任一种或两种以上的混合物。
6.根据权利要求1所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述的光稳定剂为受阻胺类、N-烷基化类、紫外线吸收剂苯并三唑类、三嗪苄叉丙二酸酯类中的任一种或两种以上的混合物。
7.根据权利要求6所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述的抗氧剂为酚类抗氧化剂1010。
8.根据权利要求6所述的一种车用低VOC内饰件PP复合材料的制备方法，其特征在于：所述的光稳定剂为受阻胺类汽巴的TINUV770与苯并三唑类汽326的1∶1混合物。 
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