CN102234394B - 一种硫酸钙晶须改性聚丙烯复合材料及其制备方法 - Google Patents

一种硫酸钙晶须改性聚丙烯复合材料及其制备方法 Download PDF

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CN102234394B
CN102234394B CN2011100958695A CN201110095869A CN102234394B CN 102234394 B CN102234394 B CN 102234394B CN 2011100958695 A CN2011100958695 A CN 2011100958695A CN 201110095869 A CN201110095869 A CN 201110095869A CN 102234394 B CN102234394 B CN 102234394B
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刘珍如
刘立文
付桃梅
杨志强
宁勇
鲁纪鸣
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Hunan Fu Xiang new type building material 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
    • B29C48/03Extrusion 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
    • B29C48/92Measuring, 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
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    • B29C2948/9259Angular velocity
    • 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
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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
    • 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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Abstract

一种硫酸钙晶须改性聚丙烯复合材料及其制备方法,该硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:PP100份,硫酸钙晶须10~40份,SBS10~20份,EVA10~20份,DVB0.1~0.3份,苯甲酰肼0.5~2份,钛酸酯偶联剂1~3份。其制备方法是,将硫酸钙晶须和钛酸酯偶联剂于高速混合机中混合5~12min;再将所述其余原料与改性硫酸钙晶须在高速混合机中混合5~10min;然后再将所得混合物于双螺杆中挤出造粒。本发明之硫酸钙晶须改性聚丙烯复合材料冲击强度高和韧性好,特别适于制作各种需求高强度的电器外壳。

Description

一种硫酸钙晶须改性聚丙烯复合材料及其制备方法
技术领域
本发明涉及一种聚丙烯复合材料及其制备方法,尤其是涉及一种硫酸钙晶须改性聚丙烯复合材料及其制备方法。
背景技术
聚丙烯( PP) 是世界上使用最广泛的通用塑料之一。其具有密度小、耐化学腐蚀性好、耐虫蛀、价位低、综合物理力学性能优异等优点。但是,目前市场上的聚丙烯成型收缩率大、脆性高、缺口冲击强度低,特别是在低温时尤为严重,这就大大限制了聚丙烯的进一步推广应用。因此,国内外对PP的增强增韧改性进行了广泛而深入的研究。
发明内容
本发明要解决的技术问题是,克服现有聚丙烯材料的不足,提供一种结晶速率快、冲击强度高和韧性好的硫酸钙晶须改性聚丙烯复合材料及其制备方法。
本发明解决所述技术问题所采用的技术方案是:
本发明之硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:聚丙烯(PP) 100份,硫酸钙晶须 10~40份,苯乙烯-丁二烯嵌段共聚物(SBS) 10~20份,乙烯-醋酸乙烯共聚物(EVA)10~20份,二乙烯基苯 (DVB) 0.1~0.3份,苯甲酰肼0.5~2份,钛酸酯偶联剂1~3份。
优选的重量配比为:聚丙烯(PP )100份,硫酸钙晶须 20份,苯乙烯-丁二烯嵌段共聚物(SBS)10份,乙烯-醋酸乙烯共聚物(EVA)15份,二乙烯基苯(DVB) 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
本发明之硫酸钙晶须改性聚丙烯复合材料的制备方法,包括如下步骤:
(1)将硫酸钙晶须和钛酸酯偶联剂,加入到高速混合机中混合5~12min(优选10min),得到改性硫酸钙晶须;改性硫酸钙晶须长径比10~30,平均直径0.5~4                                               
Figure 2011100958695100002DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于55~65℃(优选60℃)下混合5~10min(优选7min);得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度范围180~230℃(优选200℃),螺杆转速100~150转/分钟(优选120转/分钟)。
硫酸钙晶须,又称石膏晶须,是一种硫酸钙的纤维状单晶体。研究表明,本发明使用之改性硫酸钙晶须具有均匀的横截面,完整的内部结构,这一特征赋予其接近晶体理论值-原子间价键的强度。由于其具有极高的强度,细微的尺寸,易与聚丙烯界面粘合,提高与基体的相容性和界面黏结力,当受外力强迫取向时,聚丙烯中的残余应力能很好地传递给硫酸钙晶须,从而提高复合材料的耐冲击强度,同时改善聚丙烯复合材料的韧性,尤其是低温时的韧性;硫酸钙晶须为无机物,在基质中分散均匀,不易团聚,使复合材料性能稳定。
本发明之硫酸钙晶须改性聚丙烯复合材料,由于结晶速率快、冲击强度高和韧性好,特别适于制作各种需求高强度的电器外壳。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
实施例1:
本实施例硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:PP 100份,硫酸钙晶须 10份,SBS 20份,EVA15份,DVB 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
制备方法:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合10min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比24,平均直径2.8
Figure 463100DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于60℃下混合7min,得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为200℃,螺杆转速为120转/分钟。
本实施例产品力学性能测试按ATSM规定方法进行,结果见表1。
实施例2:
本实施例硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:PP 100份,硫酸钙晶须 15份,SBS 20份,EVA20份,DVB 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
制备方法:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合10min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比25,平均直径2.8
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于60℃下混合7min,得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为200℃,螺杆转速为120转/分钟。
本实施例产品力学性能测试按ATSM规定方法进行,结果见表1。
实施例3:
本实施例硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:PP 100份,硫酸钙晶须 20份,SBS10份,EVA15份,DVB 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
制备方法:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合10min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比25,平均直径3
Figure 845857DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于60℃下混合7min,得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为200℃,螺杆转速为120转/分钟。
本实施例产品力学性能测试按ATSM规定方法进行,结果见表1。
实施例4:
本实施例硫酸钙晶须改性聚丙烯复合材料由以下重量份数的原料制成:PP 100份,硫酸钙晶须 30份,SBS 10份,EVA20份,DVB 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
制备方法:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合10min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比28,平均直径2.8
Figure 138298DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于60℃下混合7min,得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为200℃,螺杆转速为120转/分钟。
本实施例产品力学性能测试按ATSM规定方法进行,结果见表1。
表1 实施例1-4产品力学性能比较
Figure 2011100958695100002DEST_PATH_IMAGE002

Claims (4)

1.一种硫酸钙晶须改性聚丙烯复合材料,其特征在于,由以下重量份数的原料制成:聚丙烯100份,硫酸钙晶须 10~40份,苯乙烯-丁二烯嵌段共聚物10~20份,乙烯-醋酸乙烯共聚物10~20份,二乙烯基苯 0.1~0.3份,苯甲酰肼0.5~2份,钛酸酯偶联剂1~3份。
2.根据权利要求1所述的硫酸钙晶须改性聚丙烯复合材料,其特征在于,由以下重量份数的原料制成:聚丙烯100份,硫酸钙晶须 20份,苯乙烯-丁二烯嵌段共聚物10份,乙烯-醋酸乙烯共聚物15份,二乙烯基苯 0.1份,苯甲酰肼1份,钛酸酯偶联剂2份。
3.一种如权利要求1或2所述的硫酸钙晶须改性聚丙烯复合材料的制备方法,其特征在于,包括以下步骤:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合5~12min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比10~30,平均直径0.5~4                                               
Figure DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于55~65℃下混合5~10min;得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为180~230℃,螺杆转速为100~150转/分钟。
4.一种如权利要求3所述的硫酸钙晶须改性聚丙烯复合材料的制备方法,其特征在于,包括以下步骤:
(1)将硫酸钙晶须和钛酸酯偶联剂加入到高速混合机中混合10min,得到改性硫酸钙晶须;改性硫酸钙晶须长径比25,平均直径3
Figure 851586DEST_PATH_IMAGE001
(2)将所述聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼加入高速混合机中,于60℃下混合7min,得聚丙烯、苯乙烯-丁二烯嵌段共聚物、乙烯-醋酸乙烯共聚物、二乙烯基苯、苯甲酰肼与改性硫酸钙晶须的混合物;
(3)将步骤(2)所得混合物于双螺杆中挤出造粒,料筒温度为200℃,螺杆转速为120转/分钟。
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