CN102807710B - 一种玻璃纤维增强聚丙烯复合材料及其制备方法 - Google Patents

一种玻璃纤维增强聚丙烯复合材料及其制备方法 Download PDF

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CN102807710B
CN102807710B CN201210290291.3A CN201210290291A CN102807710B CN 102807710 B CN102807710 B CN 102807710B CN 201210290291 A CN201210290291 A CN 201210290291A CN 102807710 B CN102807710 B CN 102807710B
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栾福进
张振华
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Ecovacs Robotics Suzhou Co Ltd
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    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
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    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
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    • B29C2948/92819Location or phase of control
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Abstract

本发明涉及玻璃纤维增强聚丙烯复合材料及其制备方法,玻璃纤维增强聚丙烯材料的原料组成为:共聚聚丙烯Ⅰ20%~40%;共聚聚丙烯Ⅱ20%~40%;相容剂5%~25%;偶联剂0.2%~1%;玻璃纤维1%~30%;绢云母1%~20%;抗氧剂0.1%~0.4%,共聚聚丙烯Ⅰ为冲击强度大于80J/m的高抗冲型共聚聚丙烯,共聚聚丙烯Ⅱ为弯曲模量大于1200MPa的高刚性型共聚聚丙烯;玻璃纤维的直径为8~17微米;绢云母的粒径介于800目~1250目之间。本发明产品能够在保持高耐热性和高刚度的前提下,达到非常低的翘曲度甚至是无翘曲。

Description

一种玻璃纤维增强聚丙烯复合材料及其制备方法
技术领域
本发明涉及一种玻璃纤维增强聚丙烯复合材料及其制备方法。
背景技术
一般玻璃纤维增强聚丙烯复合材料具有较高的刚性、耐热性,但是一方面,由于玻璃纤维在聚丙烯树脂中分布的长度远远大于玻璃纤维的直径,因此在较薄的产品部件中,玻璃纤维的取向极易导致产品翘曲;另一方面,聚丙烯是结晶性聚合物,聚丙烯球晶的大小以及结晶周期都直接影响玻璃纤维增强聚丙烯产品的翘曲程度。
专利CN1479765A公开了一种低翘曲聚丙烯树脂组合物,其组合物的基体树脂采用全同立构聚丙烯均聚物,加入不饱和羧酸或其衍生物改性聚丙烯,无机填料采用云母,其中玻纤与云母的比例为1∶0.5~8(重量比)。由于基体树脂采用均聚聚丙烯,因此,此专利技术不能消除聚丙烯高结晶所产生的翘曲,也没有论述有效防止翘曲的云母类型,最终没有完全杜绝翘曲现象,只是一种低翘曲的聚丙烯组合物。
专利CN1315465A公开了一种低收缩防翘曲玻璃纤维增强聚丙烯,其包括以下组份及含量(重量份):共聚聚丙烯200~700;苯乙烯类树脂100~300;相容剂50~200;玻璃纤维1~300;偶联剂1~10;交联剂1~10;抗氧剂1~3;分子量调节剂1~10;其它助剂0~3;无机填料1~300。该专利采用共聚聚丙烯作为基体树脂,用玻璃纤维增强,为了防止成品翘曲,在复合体系中加入苯乙烯类非结晶树脂,使材料的收缩率稳定在0.5%以下,其中加入的无机填料则进一步降低了成型收缩率。该专利虽然降低了成型收缩率,但是由于苯乙烯类树脂以相当的比例存在,其耐热性和耐腐蚀性能均低于聚丙烯,如此,聚丙烯组合物的耐热性能与一般的玻璃纤维增强聚丙烯相比有较大程度的降低,并且苯乙烯类树脂的价格大于聚丙烯的价格,也提高了产品的成本。此外,该专利中还使用了分子量调节剂和交联剂,这些成分的存在使聚合物分子产生交联,同时加速了聚丙烯的降解。
CN1315465A中的苯乙烯与聚丙烯共混产生的是海岛结构的合金,苯乙烯类树脂不耐油,在有润滑油接触的地方,虽然苯乙烯类树脂含量不高,但也会急剧降低材料的使用寿命,耐热性的影响不如耐腐蚀性的影响大;同时苯乙烯类树脂的价格大于聚丙烯的价格,也提高了产品的成本;总的来说两个技术的改性原理是不相同的。
发明内容
本发明所要解决的技术问题是克服现有技术的不足,提供一种改进的玻璃纤维增强聚丙烯复合材料,其在保持高耐热性和高刚度的前提下,可以达到非常低的翘曲度甚至是无翘曲。
本发明同时还要提供一种玻璃纤维增强聚丙烯复合材料的制备方法。
为解决上述技术问题,本发明采取的一种技术方案是:
一种玻璃纤维增强聚丙烯复合材料,以重量百分含量计,所述玻璃纤维增强聚丙烯复合材料的原料包括如下组分:
共聚聚丙烯I     20%~40%;
共聚聚丙烯II    20%~40%;
相容剂          5%~25%;
偶联剂          0.2%~1%;
玻璃纤维        1%~30%;
绢云母          1%~20%;
抗氧剂          0.1%~0.4%,
其中,共聚聚丙烯I为冲击强度大于80J/m的高抗冲型共聚聚丙烯,共聚聚丙烯II为弯曲模量大于1200Mpa的高刚性共聚聚丙烯;所述的玻璃纤维的直径为8~17微米;所述的绢云母的粒径介于800目~1250目之间。
优选地,共聚聚丙烯I与共聚聚丙烯II的冲击强度之差大于等于10J/m,熔融指数之差小于等于20g/10min;
根据本发明的一个优选方面,所述的相容剂至少包括有均聚聚丙烯接枝马来酸酐和选择性地包括有半晶型POE接枝马来酸酐。进一步优选地,均聚聚丙烯接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为5wt%~20wt%,半晶型POE接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为0~5wt%。
根据本发明的进一步优选方案:所述玻璃纤维增强聚丙烯复合材料的原料包括如下组分:
共聚聚丙烯I    25%~35%;
共聚聚丙烯II    25%~35%;
相容剂          5%~15%;
偶联剂          0.2%~0.5%;
玻璃纤维        5%~20%;
绢云母          5%~20%;
抗氧剂          0.1%~0.3%。
在该实施方案中,所述的相容剂也优选至少包括有均聚聚丙烯接枝马来酸酐和选择性地包括有半晶型POE接枝马来酸酐。进一步优选地,均聚聚丙烯接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为5wt%~10wt%,半晶型POE接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为0~5wt%。
根据本发明,所述的偶联剂可以为钛酸酯偶联剂、硅烷偶联剂等,其中,优选钛酸酯偶联剂。
所述的玻璃纤维可以为各种类型,但优选无碱玻璃纤维,更优选是无捻粗纱玻璃纤维。根据一个优选方面,玻璃纤维的直径为12~17微米。
根据本发明,绢云母为片状的无机矿物,绢云母的片状结构可以降低甚至消除聚合物的翘曲现象。优选地,本发明所用绢云母的粒度至少有2种,且2种粒度的绢云母的重量比为1∶0.5~2。至少两种粒度的绢云母的使用可使聚丙烯的结晶速度加快,减小聚丙烯球晶的尺寸,可使聚丙烯长时间尺寸稳定不发生形变。在一个具体的实施方式中,所述的绢云母的粒度有2种,且2种绢云母的粒度差优选大于等于50目,更优选大于等于100目。
根据本发明的又一优选方面,所述抗氧剂为抗氧剂1010和抗氧剂168的复配体系,二者重量比例为1.5~2.5∶1,最优选为2∶1。
本发明采取的又一技术方案是:一种上述的玻璃纤维增强聚丙烯复合材料的制备方法,该方法采用带有加纤口的双螺杆挤出机,所述方法包含如下步骤:
a、将除了玻璃纤维之外的组分按照配方比例,在混合机中混合后,加入带有加纤口的双螺杆挤出机,将玻璃纤维从双螺杆挤出机的加纤口加入;
b、全部组分在双螺杆挤出机中挤出造粒,得到玻璃纤维增强聚丙烯复合材料,其中:双螺杆挤出机的温度设定为:一区210~220℃;二区215~220℃;三区215~220℃;区215~220℃;五区215~220℃;六区215~220℃;七区215~220℃;八区200~205℃;九区190~200℃;机头215~220℃;螺杆转速为380~410转/分钟;喂料速度为45~50Hz。
进一步地,所述的双螺杆挤出机加纤口至机头之间的螺杆组合至少包括45°/5/32三个,30°/7/48三个,45°/5/32L一个。
根据一个具体方面,所述双螺杆挤出机为带有加纤口的36机。
由于以上技术方案的实施,本发明与现有技术相比具有如下优点:
本发明从影响聚丙烯翘曲的两个方面着手,一方面,采用两种不同的共聚聚丙烯作为基体树脂,在相容剂的作用下,可以获得晶粒尺寸细小而且均匀化的聚丙烯晶粒,在不对玻璃纤维产生内应力的同时,提高了拉伸强度;另一方面,片状结构的绢云母的使用有助于防止产品弯曲变形。因此,本发明的玻璃纤维增强聚丙烯即使是在产品较薄的情况下,也可以达到非常低的翘曲,甚至可以无翘曲,适于制作精密度要求较高的部件。此外,本发明没有加入影响聚丙烯耐热性的成分,改进的聚丙烯依旧保持了原本所具有的高耐热性能。
具体实施方式
实施例1
本实施例提供一种玻璃纤维增强聚丙烯复合材料,其原料组成及用量参见表1,其中:共聚聚丙烯I采用PP AR564(购自sumitomo),共聚聚丙烯II采用PP M1600(购自韩国现代)。玻璃纤维的直径为8~17微米(型号ERS200-13-T635B,购自泰山玻璃纤维有限公司)。
相容剂:均聚聚丙烯接枝马来酸酐(PP-g-MAH)(购自埃克森美孚化工),半晶型POE接枝马来酸酐(POE-g-MAH)(购自埃克森美孚化工)。
玻璃纤维增强聚丙烯复合材料的制备方法如下:按照表1中的组分数量称量物料,经混合机混合,加入双螺杆挤出机,玻璃纤维从加纤口加入,挤出造粒,制得玻璃纤维增强聚丙烯复合材料,其中:
a)双螺杆挤出机的机型采用36机,双螺杆挤出机加纤口至机头之间的螺杆组合:45°/5/32三个,30°/7/48三个,45°/5/32L一个;
b)双螺杆挤出机的温度设定为:一区210~220℃,二区215~220℃,三区215~220℃,四区215~220℃,五区215~220℃,六区215~220℃,七区215~220℃,八区200~205℃,九区190~200℃,机头215~220℃;
c)螺杆转速:380~410转/分钟;喂料速度45~50Hz;
按照标准注塑成标准样条进行物理性能测试;将玻璃纤维增强聚丙烯注塑成ZW0901卷线器(直径145mm,壁厚度2.4mm)用于翘曲测试,结果参见表1。
实施例2~3
实施例2~3分别提供了根据本发明的玻璃纤维增强聚丙烯复合材料,其主要原料组成参见表1,同时还添加有重量为表中所列原料总重量约0.1%的润滑剂。按照与实施例1相同的方法制备获得玻璃纤维增强聚丙烯复合材料。所得复合材料的性能数据参见表1。
对比例1
本对比例提供一种玻璃纤维增强聚丙烯,其原料配方中不含聚丙烯II和相容剂,具体组成参见表1。
对比例2
本对比例提供一种玻璃纤维增强聚丙烯,其原料配方中不含相容剂,具体组成参见表1。
表1
注:表中配方组分为质量分数。
从表1中数据可以看出,实施例1~3及对比例1~2的玻璃纤维增强聚丙烯复合材料与普通玻璃纤维增强聚丙烯相比,翘曲性能大幅改善,且耐热性没有降低。特别是,根据本发明的玻璃纤维增强聚丙烯纤维的耐翘曲性效果最好,可以达到无翘曲。
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,且本发明不限于上述的实施例,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围。

Claims (11)

1. 一种玻璃纤维增强聚丙烯复合材料,其特征在于:以重量百分含量计,所述玻璃纤维增强聚丙烯复合材料的原料由如下组分组成:
     共聚聚丙烯Ⅰ         20% ~ 40%;
     共聚聚丙烯Ⅱ         20% ~ 40%;
     相容剂               5% ~ 25%;
     偶联剂               0.2% ~ 1%;
     玻璃纤维             1% ~ 30%;
     绢云母               1% ~ 20%;
     抗氧剂               0.1% ~ 0.4%,
其中,共聚聚丙烯Ⅰ为冲击强度大于80J/m的高抗冲型共聚聚丙烯,共聚聚丙烯Ⅱ为弯曲模量大于1200MPa的高刚性共聚聚丙烯,共聚聚丙烯Ⅰ与共聚聚丙烯Ⅱ的冲击强度之差大于等于10J/m,熔融指数之差小于等于20g/10min;所述的玻璃纤维的直径为8~17微米;所述的绢云母的粒径介于800目~1250目之间,所述的绢云母的粒度至少有2种,且2种粒度的绢云母的重量比为1:0.5~2、粒度差大于等于50目。
2. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述的相容剂至少包括有均聚聚丙烯接枝马来酸酐和选择性地包括有半晶型POE接枝马来酸酐,所述均聚聚丙烯接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为5wt%~20wt%,所述半晶型POE接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为0~5wt%。
3. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述玻璃纤维增强聚丙烯复合材料由如下组分组成:
     共聚聚丙烯Ⅰ         25% ~ 35%;
     共聚聚丙烯Ⅱ         25% ~ 35%;
     相容剂               5% ~ 15%;
     偶联剂               0.2% ~ 0.5%;
     玻璃纤维             5% ~ 20%;
     绢云母               5% ~ 20%;
     抗氧剂               0.1% ~ 0.3%。
4. 根据权利要求3所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述的相容剂至少包括有均聚聚丙烯接枝马来酸酐和选择性地包括有半晶型POE接枝马来酸酐,所述均聚聚丙烯接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为5wt%~10wt%,所述半晶型POE接枝马来酸酐在所述玻璃纤维增强聚丙烯复合材料中的含量为0~5wt%。
5. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述的偶联剂为钛酸酯偶联剂。
6. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述的玻璃纤维为无碱玻璃纤维。
7. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述抗氧剂为抗氧剂1010和抗氧剂168的复配体系,二者重量比例为1.5~2.5:1。
8. 根据权利要求1所述的玻璃纤维增强聚丙烯复合材料,其特征在于:所述的玻璃纤维的直径为12~17微米。
9. 权利要求1至8中任一项权利要求所述的玻璃纤维增强聚丙烯复合材料的制备方法,其特征在于:包含如下步骤:
a、将除了玻璃纤维之外的组分按照配方比例,在混合机中混合后,加入带有加纤口的双螺杆挤出机,将玻璃纤维从双螺杆挤出机的加纤口加入;
b、全部组分在双螺杆挤出机中挤出造粒,得到玻璃纤维增强聚丙烯复合材料,其中:双螺杆挤出机的温度设定为:一区210 ~ 220℃;二区215~220℃;三区215~220℃;四区215~220℃;五区215~220℃;六区215~220℃;七区215~220℃;八区200~205℃;九区190~200℃;机头215~220℃;螺杆转速为380~410转/分钟;喂料速度为45~50Hz。
10. 根据权利要求9所述的玻璃纤维增强聚丙烯复合材料的制备方法,其特征在于:所述的双螺杆挤出机加纤口至机头之间的螺杆组合至少包括45°/5/32三个,30°/7/48三个,45°/5/32L一个。
11. 根据权利要求9或10所述的玻璃纤维增强聚丙烯复合材料的制备方法,其特征在于:所述双螺杆挤出机为带有加纤口的36机。
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