CN102408649A - 用于太阳能电池防护膜的改性聚偏氟乙烯材料及制备方法 - Google Patents

用于太阳能电池防护膜的改性聚偏氟乙烯材料及制备方法 Download PDF

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CN102408649A
CN102408649A CN2011102815605A CN201110281560A CN102408649A CN 102408649 A CN102408649 A CN 102408649A CN 2011102815605 A CN2011102815605 A CN 2011102815605A CN 201110281560 A CN201110281560 A CN 201110281560A CN 102408649 A CN102408649 A CN 102408649A
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cell protective
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CN102408649B (zh
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汪倩文
赵东明
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SUZHOU HECHANG JUHE 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
    • B29C48/022Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • B29C2948/9258Velocity
    • 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
    • B29C2948/92885Screw or gear
    • 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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

本发明提供一种用于太阳能电池防护膜的改性聚偏氟乙烯材料及制造方法,成分为:聚偏氯乙烯55~70%,聚乙烯10~20%,聚乙烯接枝马来酸酐3~6%,乙烯辛烯共聚物10~20%,抗氧剂0.3~0.6%,润滑剂0.2~0.5%;其工艺:先按照配比将各组分材料加入高速混合桶中使之混合均匀;将得到的混合物加入双螺杆挤出机内混炼;双螺杆挤出机共有六段,第一段和第二段挤出温度在150~170℃,其它几段挤出温度在170~200℃之间;反应物在双螺杆挤出机中的总停留时间为3~6min,双螺杆挤出机转速在300~350r.min-1;将得到的物料挤出后冷却、切粒,即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。通过在PVDF中加入HDPE改性,可明显降低PVDF的结晶程度,有效提高PVDF的加工可塑性。

Description

用于太阳能电池防护膜的改性聚偏氟乙烯材料及制备方法
技术领域
本发明涉及一种聚偏氟乙烯材料,尤其涉及一种用于太阳能电池防护膜的改性聚偏氟乙烯材料及其制造方法。
背景技术
太阳能电池是将太阳光能直接转变为直流电能的阳光发电装置,是具有经济效益、环保效益和可持续发展得清洁能源。太阳能电池组件是由高转换效率的单片太阳能转换硅晶片、乙烯—乙酸乙烯酯共聚物胶膜(E/VAC)、低铁钢化玻璃和由氟塑料膜、聚酯膜复合而成的背膜组成。这些元件在真空下加热层压成为一个整体,最后经安装防腐铝合金边框和接线盒,成为太阳能电池组件成品。
目前太阳能电池组件中背膜中的氟塑料膜,与其他薄膜或组件的粘结问题是一个技术难点,阻碍了国产氟塑料膜应用于太阳能电池背膜,现氟塑料膜仍依靠进口。
聚偏氟乙烯(PVDF)是一种坚韧的热塑性工程塑料,具有高结晶度,低表面自由能,具有优异的耐候性、耐热性、耐污性、耐药性、耐溶剂性,并且还有不粘尘、不吸水、高绝缘强度、耐臭氧、耐自然老化等优点。PVDF树脂制成的防护膜,可应用于太阳能电池、燃料电池。但是由于在应用于太阳能电池背膜时需要与E/VAC、PET等聚合物材料膜进行热压粘合,如何提高粘结强度是目前的技术难题。
发明内容
本发明的目的是克服现有技术存在的不足,提供一种用于太阳能电池防护膜的改性聚偏氟乙烯材料及其制造方法,旨在提高PVDF薄膜的表面自由能,提高其与E/VAC、PET基材的粘结强度。
本发明的目的通过以下技术方案来实现:
用于太阳能电池防护膜的改性聚偏氟乙烯材料,包含以下重量百分比成分:聚偏氯乙烯55~70%,聚乙烯10~20%,聚乙烯接枝马来酸酐3~6%,乙烯辛烯共聚物10~20%,抗氧剂0.3~0.6%,润滑剂0.2~0.5% 。
进一步地,上述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其组分具有如下的重量百分比:聚偏氯乙烯65%,聚乙烯14.3%,聚乙烯接枝马来酸酐5%,乙烯-辛烯共聚物15%,抗氧剂0.4%,润滑剂0.3% 。
更进一步地,上述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,所述聚偏氯乙烯熔点145℃,热分解温度在320℃以上;所述聚乙烯牌号为聚乙烯HDPE 5070;所述聚乙烯接枝马来酸酐接枝率为1%;所述乙烯-辛烯共聚物的熔融指数为0.5g/10min,密度0.868g/cm3;所述抗氧剂为抗氧剂1010与抗氧剂168的复配物;所述润滑剂为乙撑双硬脂酰胺。
本发明用于太阳能电池防护膜的改性聚偏氟乙烯材料的制备方法,包括以下步骤: 
①原料混合均匀:按照配比将各组分材料加入高速混合桶中使之混合均匀;
②在双螺杆挤出机内熔融共混:将步骤①得到的混合物加入双螺杆挤出机内混炼;双螺杆挤出机共有六段,第一段和第二段挤出温度在150~ 170℃ ,其它几段挤出温度在170~200℃ 之间;反应物在双螺杆挤出机中的总停留时间为3~6min,双螺杆挤出机转速在300~350r.min-1
③将得到的物料挤出后冷却、切粒,即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
再进一步地,上述的用于太阳能电池防护膜的改性聚偏氟乙烯材料的制备方法,首先,将65份聚偏氯乙烯,14.3份聚乙烯,5份聚乙烯接枝马来酸酐,15份乙烯-辛烯共聚物,0.4份抗氧剂、0.3份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=150℃,T2=170℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=350r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
本发明技术方案突出的实质性特点和显著的进步主要体现在:
①本发明通过在PVDF中加入HDPE改性,可明显降低PVDF的结晶程度,有效提高PVDF的加工可塑性;
②PVDF/HDPE/POE改性材料具有良好的加工性,可直接注塑、挤出、流延加工,制膜容易;改性材料具有优异的耐老化性、耐光、耐候性和柔韧性;
③改性材料中添加HDPE、POE成分,制备的太阳能电池背膜可以更好的与E/VAC、PET等聚合物材料膜热压粘合,应用于太阳能电池防护膜,有效缓解外力对电池片的冲击破坏有,很好的信价比。
具体实施方式
本发明提供一种用于太阳能电池防护膜的改性聚偏氟乙烯材料及其制备方法,通过对PVDF改性,将PVDF材料与HDPE、POE共混,旨在提高PVDF薄膜的表面自由能,提高其与E/VAC、PET基材的粘结强度。
用于太阳能电池防护膜的改性聚偏氟乙烯材料,成分重量比为:聚偏氯乙烯(PVDF)55~70%,聚乙烯(HDPE)10~20%,聚乙烯接枝马来酸酐3~6%,乙烯辛烯共聚物(POE)10~20%,抗氧剂0.3~0.6%,润滑剂0.2~0.5% 。
优选配方为:聚偏氯乙烯65%,聚乙烯14.3%,聚乙烯接枝马来酸酐5%,乙烯-辛烯共聚物15%,抗氧剂0.4%,润滑剂0.3% 。
其中,聚偏氯乙烯熔点145℃,热分解温度在320℃以上;聚乙烯牌号为聚乙烯HDPE 5070;聚乙烯接枝马来酸酐接枝率为1%;乙烯-辛烯共聚物的熔融指数为0.5g/10min,密度0.868g/cm3;抗氧剂为抗氧剂1010与抗氧剂168的复配物;润滑剂为乙撑双硬脂酰胺。
具体的制备过程为:
①原料混合均匀:按照配比将各组分材料加入高速混合桶中使之混合均匀;
②在双螺杆挤出机内熔融共混:将步骤①得到的混合物加入双螺杆挤出机内混炼;双螺杆挤出机共有六段,第一段和第二段挤出温度在150~ 170℃ ,其它几段挤出温度在170~200℃ 之间;反应物在双螺杆挤出机中的总停留时间为3~6min,双螺杆挤出机转速在300~350r.min-1
③将得到的物料挤出后冷却、切粒,即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
实施例1:
首先,将65份聚偏氯乙烯,14.3份聚乙烯,5份聚乙烯接枝马来酸酐,15份乙烯-辛烯共聚物,0.4份抗氧剂、0.3份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=150℃,T2=170℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=350r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
实施例2:
首先,将55份聚偏氯乙烯,19.9份聚乙烯,4份聚乙烯接枝马来酸酐,20份乙烯-辛烯共聚物,0.6份抗氧剂、0.5份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=150℃,T2=160℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=340r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
实施例3:
首先,将70份聚偏氯乙烯,16份聚乙烯,3份聚乙烯接枝马来酸酐,10份乙烯-辛烯共聚物,0.5份抗氧剂、0.5份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=160℃,T2=170℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=320r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
实施例4:
首先,将60份聚偏氯乙烯,15.5份聚乙烯,6份聚乙烯接枝马来酸酐,18份乙烯-辛烯共聚物,0.3份抗氧剂、0.2份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=150℃,T2=170℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=300r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
按国家标准测试其性能,结果如表1所示。
综上所述,本发明通过对PVDF改性,将PVDF材料与HDPE、POE共混,聚乙烯接枝马来酸酐做增容剂,一方面不会对PVDF的老化性能造成过多的影响,另一方面可降低PVDF的结晶程度,有效提高PVDF的加工可塑性,同时提高改性PVDF薄膜的表面自由能,提高其与E/VAC、PET基材的粘结强度。

Claims (10)

1.用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于包含以下重量百分比成分:聚偏氯乙烯55~70%,聚乙烯10~20%,聚乙烯接枝马来酸酐3~6%,乙烯辛烯共聚物10~20%,抗氧剂0.3~0.6%,润滑剂0.2~0.5% 。
2.根据权利要求1所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于其组分具有如下的重量百分比:聚偏氯乙烯65%,聚乙烯14.3%,聚乙烯接枝马来酸酐5%,乙烯-辛烯共聚物15%,抗氧剂0.4%,润滑剂0.3% 。
3.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述聚偏氯乙烯熔点145℃,热分解温度在320℃以上。
4.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述聚乙烯牌号为聚乙烯HDPE 5070。
5.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述聚乙烯接枝马来酸酐接枝率为1%。
6.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述乙烯-辛烯共聚物的熔融指数为0.5g/10min,密度0.868g/cm3
7.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述抗氧剂为抗氧剂1010与抗氧剂168的复配物。
8.根据权利要求1或2所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料,其特征在于:所述润滑剂为乙撑双硬脂酰胺。
9.权利要求1所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料的制备方法,其特征在于包括以下步骤: 
①原料混合均匀:按照配比将各组分材料加入高速混合桶中使之混合均匀;
②在双螺杆挤出机内熔融共混:将步骤①得到的混合物加入双螺杆挤出机内混炼;双螺杆挤出机共有六段,第一段和第二段挤出温度在150~ 170℃ ,其它几段挤出温度在170~200℃ 之间;反应物在双螺杆挤出机中的总停留时间为3~6min,双螺杆挤出机转速在300~350r.min-1
③将得到的物料挤出后冷却、切粒,即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
10.根据权利要求9所述的用于太阳能电池防护膜的改性聚偏氟乙烯材料的制备方法,其特征在于:首先,将65份聚偏氯乙烯,14.3份聚乙烯,5份聚乙烯接枝马来酸酐,15份乙烯-辛烯共聚物,0.4份抗氧剂、0.3份乙撑双硬脂酰胺加入高速混合桶中使之混合均匀;然后,加入双螺杆挤出机混炼,双螺杆每段的温度分别为:T1=150℃,T2=170℃,T3=170℃,T4=180℃,T5=190℃,T6=200℃,双螺杆挤出机转速为r=350r.min-1,最后,挤出、冷却、切粒即得到用于太阳能电池防护膜的改性聚偏氟乙烯材料。
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CN114085478A (zh) * 2021-12-02 2022-02-25 苏州佳尔特新材料科技股份有限公司 一种太阳能背板用聚偏氟乙烯薄膜及其制备方法

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