CN102863753B - 哑光pcabs复合物及其制备方法 - Google Patents

哑光pcabs复合物及其制备方法 Download PDF

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CN102863753B
CN102863753B CN201210339078.7A CN201210339078A CN102863753B CN 102863753 B CN102863753 B CN 102863753B CN 201210339078 A CN201210339078 A CN 201210339078A CN 102863753 B CN102863753 B CN 102863753B
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pcabs
district temperature
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styrene
dumb light
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CN102863753A (zh
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黄俊生
孟波
石明东
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Changzhou Weimao New Material Technology Co., Ltd.
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JIANGSU AGT TECHNOLOGY DEVELOPMENT CO LTD
JIANGSU AGT NEW MATERIAL TECHNOLOGY 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
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • 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
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0022Combinations of extrusion moulding with other shaping operations combined with cutting
    • 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
    • B29C48/36Means 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
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/78Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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

Abstract

本发明涉及PCABS制备技术领域,特别是一种哑光PCABS复合物及其制备方法。本发明以聚碳酸酯、ABS为基体,热塑性弹性体和环氧聚合物作为哑光剂,以高胶粉HRG181作为增韧剂,加入抗氧剂和润滑剂,得到PCABS合金材料,该材料光泽低,机械性能好;本发明所得材料能够在正常模具下模塑加工,所采用的SBS、SEBS、抗氧剂、润滑剂等组分均为价廉易得的市售产品,产品的生产成本较低,适于规模化推广。

Description

哑光PCABS复合物及其制备方法
技术领域
本发明涉及PCABS制备技术领域,特别是一种哑光PCABS复合物及其制备方法。
背景技术
PCABS复合物是一种热塑性工程塑料,由于其具有表面光泽度高的优异特点,其已被广泛应用于多个领域。哑光PCABS复合物开始开发和应用始于上世纪九十年代,现有研究成果主要有:①添加二氧化硅等无机填料:材料加工时使填料流向表面,并在表面处突起,且填料中水份等挥发形成微小气泡,使表面凹凸不平,从而产生光的漫反射;②增加模具表面的粗糙度;③添加粗大橡胶粒子或轻微交联的橡胶:材料加工时在制品表面产生部分分相和橡胶颗粒的微收缩,材料本身的不相容或由于化学交联导致的微交联化效应会在材料表面形成微粗糙效果,当入射光到达微粗糙表面时,光的反射方向发生改变形成漫反射,从而产生低光泽外观,达到哑光目的。
中国塑料2009年第6期介绍了环氧化合物或BMAT对PCABS合金的哑光效果的影响,前者利用环氧基团与PC起反应,降低PC与ABS的相容性,从而造成材料表面的光泽下降;而后者由于BMAT自身的高分子量,大分子体积,与其他成分的相容性差,从而导致材料光泽下降,但是,单一的加入环氧化合物或BMAT,都不能达到令人满意的哑光效果。
发明内容
本发明要解决的技术问题是:提供一种哑光PCABS复合物及其制备方法,该哑光PCABS复合物流动性好、光泽低、强度高、韧性好,其制备方法加工成型简单、精度高。
本发明解决其技术问题所采用的技术方案是:一种哑光PCABS复合物,按重量分数计,其组分配方如下:
聚碳酸酯(PC)                          40~80%;
丙烯腈-丁二烯-苯乙烯共聚物(ABS)       10~50%;
增韧剂                                  2~15%;
热塑性弹性体                            1~15%;
环氧聚合物                              2~15%;
抗氧剂1010                              0.1~1%;
抗氧剂168                               0.1~1%;
润滑剂                                  0.1~1%;
所述聚碳酸酯为分子量为10000~30000的双酚A型聚碳酸酯。
ABS为乳液聚合物或本体聚合物,其中苯乙烯含为量30~65%,丙烯腈含量20~35%,丁二烯含量10~50%;增韧剂为ABS高胶粉。
热塑性弹性体为苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)或苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS);环氧聚合物为美国杜邦公司的PTW或法国阿科玛公司的AX8900。
抗氧剂1010为四[β-(3,5-二特丁基4-羟基苯基)丙酸]季戊四醇酯,商品名Irganox 1010,瑞士汽巴精化公司生产;抗氧剂168为三(2,4-二叔丁基酚)亚磷酸酯,商品名Irganox 168,瑞士汽巴精化公司生产;润滑剂选用美国龙沙公司的PETS。
一种哑光PCABS复合物的制备方法,具有如下步骤:
(1)按重量百分比计,将聚碳酸酯40~80%、丙烯腈-丁二烯-苯乙烯共聚物10~50%、增韧剂2~15%、热塑性弹性体1~15%、环氧聚合物2~15%、抗氧剂10100.1~1%、抗氧剂1680.1~1%和润滑剂0.1~1%精确称量后,在90~100℃预先干燥;
(2)将上述干燥后的物料加入高速混合机中干混1~4min,然后将混合物料加入双螺杆挤出机,经双螺杆挤出机熔融挤出后冷却、干燥、切粒即得成品。
本发明的哑光PCABS复合物采用德国Krauss Maffei公司的ZE 25A×36D UTX双螺杆挤出机生产,其各段参数设定如下:一区温度230-240℃,二区温度240-250℃,三区温度240-250℃,四区温度240-250℃,五区温度240-250℃,六区温度240-250℃,七区温度240-250℃,八区温度240-250℃,九区温度240-250℃,十区温度240-250℃,机头250℃,主机转速为300转/分钟,产量约20kg/h。
本发明中加入了一些与PC和ABS不相容的SBS,SEBS,SEPS或SIS,这些材料与PC相容性差,以大粒径颗粒分布于PCABS复合物的表面,使复合物表面达到哑光效果;同时,这种弹性体与环氧聚合物并用具有协同效应,该环氧聚合物与聚碳酸酯的端基基团起反应,降低了PC与ABS的相容性,也能起到降低PCABS合金的光泽的作用。
有益效果:本发明以聚碳酸酯,ABS为基体,热塑性弹性体和环氧聚合物作为哑光剂,以高胶粉HRG181作为增韧剂,加入抗氧剂和润滑剂,得到PCABS合金材料,该材料光泽低,机械性能好;本发明所得材料能够在正常模具下模塑加工,所采用的SBS,SEBS,抗氧剂、润滑剂等组分均为价廉易得的市售产品,产品的生产成本较低,适于规模化推广。
具体实施方式
下面结合具体实施例对本发明作进一步说明。所用物料中,PC选用韩国LG公司的PC 1201-15;ABS选用上海高桥石化公司的ABS 8391;增韧剂选用韩国锦湖公司生产的ABS高胶粉HRG181;热塑性弹性体为岳阳巴陵石化的SBSYH792或SEBS YH561;
实施例一
一种哑光PCABS复合物的制备方法,具有如下步骤:
(1)按重量百分比计,将PC 49.3%、ABS 36%、增韧剂4%、SEBS 10%、10100.2%、1680.2%和PETS 0.3%精确称量后,在90~100℃预先干燥;
(2)将上述干燥后的物料加入高速混合机中干混1~4min,然后将混合物料加入双螺杆挤出机,经双螺杆挤出机熔融挤出后冷却、干燥、切粒即得成品;
所述双螺杆挤出机的各段参数设定如下:一区温度230℃,二区温度250℃,三区温度250℃,四区温度250℃,五区温度250℃,六区温度250℃,七区温度250℃,八区温度250℃,九区温度250℃,十区温度250℃,机头250℃,主机转速为300转/分钟,产量约20kg/h。
实施例二
一种哑光PCABS复合物的制备方法,其制备步骤和物料产地同实施例一,配方为:PC 64.3%、ABS 25%、增韧剂4%、SBS 6%、10100.2%、1680.2%和PETS 0.3%。
实施例三
一种哑光PCABS复合物的制备方法,其制备步骤和物料产地同实施例一,配方为:PC 49.3%、ABS 32%、增韧剂4%、SEBS 6%、PTW 4%、10100.2%、1680.2%和PETS 0.3%。
实施例四
一种哑光PCABS复合物的制备方法,其制备步骤和物料产地同实施例一,配方为:PC 64.3%、ABS 21%、增韧剂4%、SBS 6%、PTW 4%、10100.2%、1680.2%和PETS 0.3%。
对比例一
一种哑光PCABS复合物的制备方法,其制备步骤和物料产地同实施例一,配方为:PC 49.3%、ABS 42%、增韧剂8%、10100.2%、1680.2%和PETS 0.3%。
对比例二
一种哑光PCABS复合物的制备方法,其制备步骤和物料产地同实施例一,配方为:PC 60.3%、ABS 30%、增韧剂5%、PTW4%,10100.2%、1680.2%和PETS 0.3%。
按上述方法将实施例和对比例所得粒子在100℃的烘箱中干燥3~6h,然后将干燥好的粒子在注射成形机上注射制样,注射成型模温控制在35~45℃。
缺口冲击强度按ISO 179执行,试样尺寸为80×10×4mm,测试设备为台湾高铁公司的GT-7045-MDH型悬臂梁测试仪;拉伸性能测试按ISO527-2执行,试样尺寸为150×10×4mm,测试设备为台湾高铁公司的GT-TCS-2000型电子拉力机,拉伸速度为50mm/min;弯曲性能测试按ISO 178进行,试样尺寸为80×10×4mm,弯曲速度为3mm/min,跨距为64mm,测试设备为台湾高铁公司的GT-TCS-2000型电子拉力机;表面光泽按ASTM D523执行,测试设备为BYK公司的微型三角光泽仪,测试角度分别为20°、60°、85°。实施例一到四和对比例一到二的配方及性能比较见表1。
表1实施例一到四和对比例一到二的配方及性能比较
Figure BDA00002136683300061
通过表1中的实施例一,实施例二及对比例一中的配方及各项性能数据可知,热塑性弹性体SBS和SEBS能够大幅度降低哑光PCABS复合物的表面光泽,20°时的光泽度分别为2.8和3.5,从外观上看,光泽度在4以下哑光效果比较明显,同时实施例一、实施例二的机械性能也影响不大,未加SBS,SEBS的配方体系,如对比例一,20°时的光泽度为45,光泽较高。PTW的加入能够降低材料的表面光泽,如对比例二,20°时的光泽度为16,但对于哑光的要求还相差很大。实施例三和实施例四中,PCABS复合物的光泽相比实施例一和实施例二中的PCABS复合物光泽度更低,可见热塑性弹性体如SBS,SEBS与环氧聚合物PTW在表面光泽方面起协同作用,对PCABS复合物的光泽的影响效果比单纯使用热塑性弹性体要好,当然也比对比例二中单纯使用环氧聚合物PTW效果要好。
本发明制备的哑光PC/ABS合金光泽度低,机械性能好,尺寸稳定性好,且成本低,可以常温加工,适用于汽车内饰注塑件和挤出板材领域。

Claims (4)

1.一种哑光PCABS复合物,其特征是:按重量分数计,其组分配方如下: 
Figure FDA0000453331440000011
所述热塑性弹性体为SBS、SEPS或SIS;环氧聚合物为美国杜邦公司的PTW或法国阿科玛公司的AX8900。 
2.如权利要求1所述的哑光PCABS复合物,其特征是:所述PC的分子量为10000~30000的双酚A型聚碳酸酯。 
3.如权利要求1所述的哑光PCABS复合物,其特征是:所述ABS为乳液聚合物或本体聚合物,其中苯乙烯含量为30~65%,丙烯腈含量20~35%,丁二烯含量10~50%;增韧剂为ABS高胶粉。 
4.如权利要求1所述的哑光PCABS复合物的制备方法,其特征是:其具有如下步骤: 
(1)按重量百分比计,将聚碳酸酯40~80%、丙烯腈-丁二烯-苯乙烯共聚物10~50%、增韧剂2~15%、热塑性弹性体1~15%、环氧聚合物2~15%、抗氧剂1010 0.1~1%、抗氧剂168 0.1~1%和润滑剂0.1~1%精确称量后,在90~100℃预先干燥; 
(2)将上述干燥后的物料加入高速混合机中干混1~4min,然后将混合物 料加入双螺杆挤出机,经双螺杆挤出机熔融挤出后冷却、干燥、切粒即得成品; 
所述双螺杆挤出机的各段参数设定如下:一区温度230-240℃,二区温度240-250℃,三区温度240-250℃,四区温度240-250℃,五区温度240-250℃,六区温度240-250℃,七区温度240-250℃,八区温度240-250℃,九区温度240-250℃,十区温度240-250℃,机头250℃,主机转速为300转/分钟。 
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CN111040406B (zh) * 2019-11-25 2023-04-07 上海锦湖日丽塑料有限公司 一种高耐热、耐化学品性吹塑abs/pc合金材料及其制备方法
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