CN105814122A - 在低温耐撕裂的且不易燃的pvdf薄膜 - Google Patents
在低温耐撕裂的且不易燃的pvdf薄膜 Download PDFInfo
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Abstract
本发明涉及具有使得它适合于外界使用,尤其在农业领域中用作为用于动物的温室薄膜的性质的氟化薄膜。根据本发明的薄膜是包含聚偏二氟乙烯(PVDF)基质,至少一种冲击改性剂和阻燃剂的单层聚合物薄膜,其中该冲击改性剂的质量含量在2.5%至低于40%之间。根据一种实施方案,本发明涉及包含至少一个所述氟化薄膜的层和至少一个非改性的PVDF层的多层薄膜。
Description
本发明涉及具有使得它适合于外界使用,尤其在畜牧业领域中使用的性质的氟化薄膜,如用于覆盖牲畜的住所或者庇护所的薄膜。根据本发明的薄膜包含聚偏二氟乙烯基质,至少一种冲击改性剂和阻燃剂。
在具有严酷气候的区域中,应该为动物提供最低保护,尤其在寒冷和潮湿的季节期间。防风保护的缺少特别地可以具有对于动物的健康有害的结果。农业温室通过保护牲畜不受上述元素伤害而允许庇护它们。这些温室的覆盖物是半透明的并且通常由玻璃以及刚性或者挠性塑料(例如聚乙烯薄膜或者半刚性PVC片材)制成,其通常进行处理以抗紫外辐射。这种薄膜可以进行增强以提高它的抗撕裂性。
一般而言,用于所述畜牧业用建筑物的屋顶的薄膜必须具有数种性质:
- 机械性质,如:在-20℃至+60℃的温度范围内的抗撕裂性、抗蠕变强度、可拉制性;
- 光学性质,如可见光的部分透射和透射光的漫射性质;
- 耐化学性,尤其对富氨环境的耐受性;耐久性:对湿热和对寒冷的耐受性,对紫外辐射的耐受性;使白天来自太阳的红外辐射和在晚上来自该建筑物内部的红外辐射反射的高能力,以便确保在该建筑物内的温度稳定性;
- 耐火性;
- 防雾和防尘性质。
已知使用氟化聚合物,尤其基于1,1-二氟乙烯的氟化聚合物以制备用于制备农业建筑物(在封闭空间的意义上)的单层薄膜。通过薄膜吹塑或者通过流延薄膜技术获得的基于PVDF(聚偏二氟乙烯)或者基于VDF/HFP(偏二氟乙烯/六氟丙烯)共聚物的单层薄膜具有优良的机械性质、光学性质、耐化学性和耐久性,因而这是用于农业温室应用的优良候选者。然而这些薄膜的抗撕裂性,尤其在挤出方向(MD)中的抗撕裂性是不足的。
文件WO2011/121228描述了包含至少3个层的多层氟化薄膜,包括由具有结晶温度TcA的第一种偏二氟乙烯共聚物制成的层A和由具有结晶温度TcB的第二种偏二氟乙烯共聚物制成的层B,TcA高于TcB,该层A和B是交替的,该层A位于外侧和该层B设置在两个层A之间。这些薄膜的抗撕裂性相对于已知的氟化薄膜得到显著地改善;然而,它在低温时仍然是不足的。
因此将合意的是,具有用于作为用于畜牧业用建筑物的覆盖物和/或外立面应用的氟化薄膜,其,除上面陈列的一般特征之外,还具有在-20℃至+60℃的温度范围中优良的抗撕裂性质并且允许光部分地漫射,由此通过自然光的协调分布有助于动物的健康,同时具有优良的耐火性。
现在已经发现,通过加入芯-壳类型的冲击改性剂来改性聚偏二氟乙烯聚合物,获得该薄膜的抗撕裂性,尤其在低温时的抗撕裂性的显著改善,同时保持与薄膜作为用于农业建筑物用薄膜的用途可相容的在可见光区中的透射水平。另一方面,阻燃剂的添加提供优良的耐火性,其对作为用于动物的温室薄膜的用途是不可缺少的。
本发明的主题之一由PVDF单层薄膜组成,该PVDF单层薄膜通过添加至少一种芯-壳类型的冲击改性剂进行改性并且包含阻燃剂。
本发明的另一主题涉及包含至少一个如上所述的改性PVDF层和至少一个未改性PVDF层,即不包含冲击改性剂和阻燃剂的PVDF层(以下简称“PVDF层”)的多层薄膜。根据一种实施方案,这种PVDF层位于多层薄膜的外侧。
本发明的另一主题涉及根据本发明的薄膜作为用于覆盖农业建筑物的材料,尤其作为用于动物的温室的屋顶和/或外立面的用途。
本发明的其它特征和优点在阅读后面的描述后将变得明显。
根据第一方面,本发明涉及单层聚合物薄膜,其包含聚偏二氟乙烯(PVDF)基质,至少一种冲击改性剂和阻燃剂,其中该冲击改性剂的质量含量在2.5%至低于40%之间。
虽然允许获得期望的机械性质,在薄膜中添加冲击改性剂通常还具有使得它们易燃的结果。本发明主题因此涉及第二种阻燃添加剂的添加,其允许恢复产品的耐火性同时通过存在冲击改性剂而保持改善的抗撕裂性。数种种类阻燃剂可以满足这种作用。举例来说,可以提到:
- 含卤素阻燃剂,
- 基于磷的阻燃剂,例如金属或者有机金属膦酸盐,
- 钨酸钙,和
- 硅酸铝。
可以同时地使用这些化合物中多种作为阻燃剂。阻燃剂的总量相对于冲击改性剂的总量的比率为1/30至1/1,优选地1/15至1/7。
根据本发明的薄膜的厚度为30至200微米,优选地为80至150微米(包括端值)。
根据一种实施方案,冲击改性剂的含量高于薄膜的总重量的5%并且小于或等于30%。优选地,冲击改性剂的含量大于或等于10%并且小于或等于30%。
根据一种实施方案,根据本发明的单层薄膜由PVDF基质,至少一种芯-壳冲击改性剂和阻燃剂组成。
该PVDF基质由PVDF均聚物或者由通过偏二氟乙烯(VDF,CH2=CF2)与氟化共聚单体的共聚合反应制备的共聚物构成,该氟化共聚单体选自:乙烯基氟,三氟乙烯(VF3),三氟氯乙烯(CTFE),1,2-二氟乙烯,四氟乙烯(TFE),六氟丙烯(HFP),全氟代(烷基乙烯基)醚,如全氟代(甲基乙烯基)醚(PMVE),全氟代(乙基乙烯基)醚(PEVE)和全氟代(丙基乙烯)醚(PPVE),全氟代(1,3-间二氧杂环戊烯)和全氟代(2,2-二甲基-1,3-间二氧杂环戊烯)(PDD)。
根据一种实施方案,所述基质由PVDF均聚物构成。
根据另一种实施方案,所述基质由VDF共聚物组成。优选地,该氟化共聚单体选自三氟氯乙烯(CTFE),六氟丙烯(HFP),三氟乙烯(VF3)和四氟乙烯(TFE),和其混合物。
该共聚单体有利地是HFP。优选地,该共聚物仅仅包含VDF和HFP。
优选地,该氟化聚合物是VDF共聚物,如VDF-HFP,其包含至少50%质量的VDF,有利地至少75%质量的VDF和优选地至少80%质量的VDF。例如,更特别地可以提到包含大于75%的VDF和余量的HFP的VDF共聚物,其由Arkema公司以名称Kynar Flex®销售。
根据一种实施方案,芯-壳冲击改性剂呈具有弹性体芯(其具有低于25℃,优选地低于0℃,更优选地低于-5℃,更优选地低于-25℃的玻璃化转变温度)和至少一种热塑性壳(其包含至少一种具有高于25℃的玻璃化转变温度的聚合物)的微粒形式。该粒子的尺寸通常低于微米并且有利地为50-300纳米。作为芯的实例,可以提到异戊二烯或者丁二烯的均聚物,异戊二烯与最多30mol%的乙烯基单体的共聚物和丁二烯与最多30mol%的乙烯基单体的共聚物。该乙烯基单体可以是苯乙烯,烷基苯乙烯,丙烯腈或者(甲基)丙烯酸烷基酯。由(甲基)丙烯酸烷基酯均聚物和(甲基)丙烯酸烷基酯与最多30mol%单体(选自另一种(甲基)丙烯酸烷基酯和乙烯基单体)的共聚物构成的另一种芯种类。该(甲基)丙烯酸烷基酯有利地是丙烯酸丁酯。根据一种实施方案,该冲击改性剂的芯由丙烯酸2-乙基己基酯构成,其提供抗撕裂性质的增强,其相当于基于丙烯酸丁酯的产品的抗撕裂性。
该芯-壳共聚物的芯可以完全地或者部分地进行交联。在制备该芯期间加入至少双官能的单体是足够的;这些单体可以选自聚(甲基)丙烯酸多元醇酯,如二(甲基)丙烯酸丁二醇酯和三羟甲基丙烷三甲基丙烯酸酯。其它双官能单体是例如二乙烯基苯,三乙烯基苯,丙烯酸乙烯基酯和甲基丙烯酸乙烯基酯。还可以通过在其中通过接枝或者作为在聚合反应期间的共聚单体引入不饱和官能单体(如不饱和羧酸酐、不饱和羧酸和不饱和环氧化物)使该芯交联。举例来说,可以提到马来酸酐、(甲基)丙烯酸和甲基丙烯酸缩水甘油酯。
所述一种或多种壳是苯乙烯、烷基苯乙烯或者甲基丙烯酸甲酯的均聚物或者是包含至少70mol%的上面这些单体之一和至少一种选自上面其它单体、另一种(甲基)丙烯酸烷基酯、醋酸乙烯酯和丙烯腈的共聚单体的共聚物。该壳可以通过在其中通过接枝或者作为在聚合反应期间的共聚单体引入不饱和官能单体(如不饱和羧酸酐、不饱和羧酸和不饱和环氧化物)进行官能化。举例来说,可以提到马来酸酐、(甲基)丙烯酸和甲基丙烯酸缩水甘油酯。该壳可以部分地进行交联。
根据一种实施方案,该壳聚合物由聚苯乙烯或者PMMA构成。还存在具有两个壳的芯-壳聚合物,一个壳由聚苯乙烯制成和另一个在外侧,由PMMA制成。
有利地,该芯按重量计占该芯-壳聚合物的70至98%,和该壳占30至2%。
所有这些芯-壳类型的冲击改性剂有时被称为软/硬,这是由于该芯由弹性体制成。还存在其它类型的芯-壳类型的冲击改性剂,如硬/软/硬类型,即它们以这种顺序具有硬芯、软壳和硬壳。该硬部分可以由前述软/硬类型的壳的聚合物构成和该软部分可以由前述软/硬类型的芯的聚合物组成。例如可以提到由以这种顺序构成的那些:
●由甲基丙烯酸甲酯和丙烯酸乙酯共聚物制成的芯,
●由丙烯酸丁酯和苯乙烯共聚物制成的壳,
●由甲基丙烯酸甲酯和丙烯酸乙酯共聚物制成的壳。
还存在其它类型的芯-壳类型冲击改性剂,如硬(芯)/软/中度硬的那些。与前述那些相比较,该差异来自"中度硬"外壳,其由两个壳组成:一个是在中间和另一个在外侧。中间壳是甲基丙烯酸甲酯、苯乙烯和至少一种选自丙烯酸烷基酯、丁二烯和异戊二烯的单体的共聚物。该外壳是PMMA均聚物或者共聚物。例如可以提到由以如下这种顺序构成的那些:
●由甲基丙烯酸甲酯和丙烯酸乙酯共聚物制成的芯,由丙烯酸丁酯和苯乙烯共聚物制成的壳,
●由甲基丙烯酸甲酯、丙烯酸丁酯和苯乙烯的共聚物制成的壳,
●由甲基丙烯酸甲酯和丙烯酸乙酯共聚物制成的壳。
根据一种优选的实施方案,该冲击改性剂包含由丙烯酸亚丁酯或者丙烯酸亚丁酯-共-丁二烯,或丙烯酸2-乙基己基酯构成的芯。该壳由聚(甲基丙烯酸甲酯)或者甲基丙烯酸甲酯和另一种丙烯酸单体的共聚物形成。这尤其涉及来自Arkema公司的Durastrength®系列的产品。可以使用其它聚丙烯酸酯类冲击改性剂,如来自Dow的Paraloid™ EXL系列,或来自Kaneka的Kane Ace®系列,来自Kaneka的基于丙烯酸的Kane Ace®系列。
根据另一种实施方案,该冲击改性剂包含由丙烯酸酯-聚硅氧烷共聚物制成的芯和由硬树脂制成的壳。在这种情况下,该芯是在由单体(如丙烯酸烷基酯或者甲基丙烯酸烷基酯,其中所述烷基包含2至10个碳原子)获得的橡胶类型聚合物存在时,通过一种或多种乙烯基单体的聚合反应制备的挠性橡胶类型材料。在该聚合反应期间,作为交联剂可以加入多官能单体,如二乙烯基苯,二甲基丙烯酸乙二醇酯,氰脲酸三烯丙酯或者异氰脲酸三烯丙基酯。使如此获得的橡胶类型的聚合物与包含聚硅氧烷的橡胶相结合。如此制备的弹性体包含至少20%重量,优选地至少40%重量的橡胶类型的聚合物。这种类型冲击改性剂的实例是通过共聚合反应(通过复合材料橡胶用至少一种乙烯基单体接枝)制备的基于橡胶的接枝共聚物,其中该复合橡胶包含5至95%重量的聚硅氧烷基橡胶和5至95%重量的聚((甲基)丙烯酸丙烯基酯)橡胶。这些冲击改性剂的颗粒的尺寸为0.01至1微米。优选地,这种类型冲击改性剂由聚硅氧烷和丙烯酸丁酯的共聚物的芯构成,该芯由聚(甲基丙烯酸甲酯)壳围绕。这种类型的产品由Mitsubishi Rayon以商标Metablen® S-2001销售。
根据另一种实施方案,该冲击改性剂由聚(有机硅氧烷)芯和热塑性树脂壳组成。聚(有机硅氧烷)芯的有机基团优选地是包含1至18个碳原子,有利地1至6个碳原子的烷基或者乙烯基,或者被取代的芳基或者烃。该聚(有机硅氧烷)包含一个或多个这些基团。该硅氧烷具有不同的官能度,其定义聚(有机硅氧烷)的交联度。优选地,平均官能度为2至3,由此形成部分交联的芯。该壳由衍生自单体的聚合物或者共聚物形成,所述单体如丙烯酸烷基酯或者甲基丙烯酸烷基酯,丙烯腈,苯乙烯,二乙烯基苯,丙酸乙烯酯,马来酰亚胺,氯乙烯,乙烯,丁二烯,异戊二烯和氯丁二烯。优选地,该壳由苯乙烯或者丙烯酸烷基酯或者甲基丙烯酸烷基酯组成,该烷基具有1至4个碳原子。该芯部分占该颗粒的0.05至90%质量,优选地60至80%质量。该颗粒的尺寸为10至400纳米。这种冲击改性剂还可以为由2个连续的壳围绕的芯的形式。该芯和该外壳的描述仍然是和上面介绍的具有单一壳的基于硅氧烷的冲击改性剂相同的。该中间壳由与芯的聚(有机硅氧烷)不同的但是选自相同组合物种类的聚(有机硅氧烷)组成。优选地,这种类型冲击改性剂由聚二甲硅氧烷的芯和聚(甲基丙烯酸甲酯)的壳构成。举例来说,可以提到来自Wacker Silicones的Genioperl®系列。
根据一种实施方案,该根据本发明的单层薄膜包含反射红外辐射的添加剂。这种添加剂可以是氧化钛或者混合化合物,如在其中心由云母构成并且用氧化钛层覆盖的珍珠母。金属合金还可以用作为红外线反射体。它们包含两种或多种以下元素:铁,铬,钴,铝,锰,锑,锌,钛和镁。优选地,这种合金由两种元素:钴和铝构成或者它是钴,铬和铝的三元合金。
根据另一种实施方案,根据本发明的单层薄膜还包含至少一种添加剂,其选自:
- 哑光剂(les agents matifyiants)
- 遮光剂
- 丙烯酸均聚物或者共聚物,
- 增塑剂,其优选地选自癸二酸二丁酯,邻苯二甲酸二辛酯,N-(正丁基)磺酰胺和聚合物聚酯,如来自己二酸,壬二酸或者癸二酸和二醇的组合的那些。还可以使用这些化合物的组合。
根据本发明的薄膜具有兼具高的低温抗撕裂性与耐火性(其与PVDF的耐火性相当)的特定特征。
根据一种实施方案,根据本发明的薄膜包含VDF/HFP共聚物基质(在实施例中的化合物A1),具有包围聚二甲硅氧烷芯(70%)的聚(甲基丙烯酸甲酯)壳(30%)的冲击改性剂,和2%重量的钨酸钙作为阻燃剂。
根据另一种实施方案,根据本发明的薄膜包含PVDF均聚物基质,具有围绕聚二甲基-硅氧烷芯(70%)的聚(甲基丙烯酸甲酯)壳(30%)的冲击改性剂,和2%重量的钨酸钙作为阻燃剂。
根据另一种实施方案,根据本发明的薄膜包含VDF/HFP共聚物基质(在实施例中的化合物A1),包含部分交联的聚(丙烯酸丁酯)芯(90%重量)和由甲基丙烯酸甲酯和丙烯酸乙酯的共聚物构成的壳(10%)的冲击改性剂,和3%的钨酸钙作为阻燃剂。
根据另一种实施方案,根据本发明的薄膜包含VDF/HFP共聚物基质(在实施例中的化合物A1),包含部分交联的聚(丙烯酸丁酯)芯(90%重量)和由甲基丙烯酸甲酯和丙烯酸乙酯的共聚物构成的壳(10%)的冲击改性剂,和2%重量的聚(丙烯酸五溴苄基酯)作为阻燃剂。
根据第二个方面,本发明涉及包含至少一个所述单层薄膜的层和至少一个其它PVDF层的多层薄膜。“PVDF层”理解为由PVDF均聚物或者通过偏二氟乙烯(VDF,CH2=CF2)与氟化共聚单体的共聚合反应制备的共聚物构成的层,该氟化共聚单体选自:乙烯基氟,三氟乙烯(VF3),三氟氯乙烯(CTFE),1,2-二氟乙烯,四氟乙烯(TFE),六氟丙烯(HFP),全氟代(烷基乙烯)醚,如全氟代(甲基乙烯基)醚(PMVE),全氟代(乙基乙烯基)醚(PEVE)和全氟代(丙基乙烯)醚(PPVE),全氟代(1,3-间二氧杂环戊烯)和全氟代(2,2-二甲基-1,3-间二氧杂环戊烯)(PDD)。
在多层薄膜的情况下,总厚度位于30至200微米之间。根据一种实施方案,该多层薄膜由用芯-壳冲击改性剂改性的并且包含阻燃剂的PVDF中间层,和两个PVDF外层组成。后两个层可以具有相同的结构,或它们可以具有不同的结构。
该厚度的分布(以该结构的最终厚度的百分比计)为如下:改性的PVDF层:20%-95%,未改性的PVDF层:5%-80%,即,例如对于30微米的总厚度和70/30分布:改性的PVDF层:21微米,和未改性的PVDF层:9微米。
根据另一个方面,本发明涉及用于制备如上所述的薄膜的方法。通过本领域的技术人员已知的熔融介质配混技术,如BUSS或者双螺杆技术获得该PVDF/冲击改性剂/阻燃剂混合物。然后通过薄膜吹塑或者通过流延薄膜技术获得薄膜,这些技术有利地允许获得非常宽的薄膜。薄膜可以在200至280℃的温度下被挤出。吹胀比必须在1.2至4之间,优选地在1.5至3之间。拉伸比对于它本身必须在2至15之间,优选地在5至10之间。
根据另一个方面,本发明涉及该单层薄膜或者包含至少一个所述单层薄膜的层的多层薄膜作为用于制备用于建筑物,尤其农业建筑物,如用于畜牧业的建筑物的屋顶和/或外立面的薄膜的材料的用途。这些薄膜这时显示出具有与优良的抗变形性和抗火性结合的改善的耐久性的优点。
以下实施例可以举例说明本发明而不限制它。
配制剂
配混物根据本领域的规则使用同向旋转的双螺杆挤出机进行制备。薄膜然后通过在220℃使用具有1mm间隙的平模的流延薄膜挤出进行制备,并通过压延机进行拉制以调节该产品的厚度至期望的目标(100微米)。
研究的材料
基质:
A1:VDF/HFP共聚物,其具有7g/10min(5kg,230℃)的熔体流动指数(MFR),142℃的熔点(Tf)和在23℃为650MPa的杨氏模量,其根据标准ISO 178进行测量。Tf在以10℃/min速度的温度上升期间通过DSC(差示扫描量热法)进行测量。熔体流动指数根据标准ISO 1133进行测量。
A2:PVDF均聚物,具有0.14g/10min(5千克,230℃)的熔体流动指数和168℃的熔点。
冲击改性剂:
B1:来自Arkema公司的Durastrength® D380丙烯酸系冲击改性剂,呈直径为250nm的芯-壳颗粒形式。90%的部分交联的聚(丙烯酸丁酯)形成颗粒的芯。该壳(10%)由甲基丙烯酸甲酯和丙烯酸乙酯的共聚物构成。
B2:来自Arkema公司的Durastrength® D200丙烯酸系冲击改性剂,其由通过甲基丙烯酸甲酯和丙烯酸乙酯的共聚物的壳(30%)围绕的部分交联的聚(丙烯酸丁酯)芯(70%)形成。
B3:来自Wacker的Genioperl® P52的芯-壳颗粒。该聚(甲基丙烯酸甲酯)壳(30%)围绕聚二甲基-硅氧烷芯(70%)。
增塑剂:
C:癸二酸二丁酯。
阻燃剂:
D1:来自ICL公司的FR-1025聚(丙烯酸五溴苄基酯)
D2:来自Chem-Met公司的为粉末形式的钨酸钙。
实施的测试为以下:
-耐火性的表征:使薄膜置于垂直支承体上并且经受用根据标准UL94的校准火焰的点燃。使该火焰置于离薄膜的底端10 mm并且保持5s。记录火焰的持续时间、燃烧的表面以及着火滴状物的存在。对于每种样品分析5个试样。
-低温抗撕裂性的表征:100微米厚的薄膜通过框架进行支撑以便通过对它施用1N应力使它展开。从230mm高度掉下980g圆锥撞针(striker)并且刺穿样品。根据薄膜的破裂情况(在薄膜中蔓延的长裂纹或者局部拉薄),可估计该变形的脆性或者韧性特征。这种测试在不同温度进行实施以估计该产品的韧-脆转变温度。
实施例1:无阻燃剂的参照配方的冷穿孔稳定性
如通过在以下表1中的实施例1至7所说明,对薄膜的穿孔的稳定性的最大影响的参数是加入到该配制剂中的冲击改性剂。它的质量分数和它的物质种类对在冷冲击之后的变形的韧性或者脆性特征具有直接影响。
实施例5和8以及7和9的比较显示用VDF/HFP共聚物基质交换PVDF均聚物对薄膜的穿孔性能仅仅具有有限的影响。
增塑剂在该混合物中的存在允许轻微改善薄膜在低温的延展性,但是它的效果仍然是有限的,如由在实施例10和11以及12和13之间不存在增强的性质所证明。在后2个实施例中冲击改性剂的物质种类的改变还引起韧-脆转换的显著变化。
实施例2:耐火性和机械性质的保持
*5890mm2的值对应于整个所分析样品的燃烧。
获得的结果显示在表2中。这些结果显示在薄膜配方中加入2%或者3%阻燃剂(即与冲击改性剂的量的2/15或者1/5的比率)允许使薄膜的耐火性恢复至相当于纯基质的耐火性的水平。
薄膜的固有耐火性由于存在被分散在样品中的冲击改性剂颗粒而被降低,如由实施例1至5所说明。在薄膜配方中添加特定的阻燃剂允许同时地获得该薄膜的高耐火性和在低温时的低韧-脆转变温度(如由实施例14至17所示)。
Claims (17)
1.单层聚合物薄膜,其包含聚偏二氟乙烯(PVDF)基质,至少一种芯-壳冲击改性剂和阻燃剂,其中该冲击改性剂的质量含量在2.5%至低于40%之间变化。
2.根据权利要求1的薄膜,其中冲击改性剂的质量含量高于5%并且小于或等于30%。
3.根据权利要求1和2任一项的薄膜,其中阻燃剂的量相对于冲击改性剂的量的比率为1/30至1/1,优选地1/15至1/7。
4.根据权利要求1-3任一项的薄膜,其中该PVDF基质由PVDF均聚物或者由通过偏二氟乙烯与氟化共聚单体的共聚合反应制备的共聚物构成,该氟化共聚单体选自:乙烯基氟,三氟乙烯,三氟氯乙烯,1,2-二氟乙烯,四氟乙烯,六氟丙烯,全氟代(烷基乙烯基)醚,其选自全氟代(甲基乙烯基)醚、全氟代(乙基乙烯基)醚(PEVE)和全氟代(丙基乙烯基)醚;全氟代(1,3-间二氧杂环戊烯)和全氟代(2,2-二甲基-1,3-间二氧杂环戊烯)。
5.根据权利要求1-4任一项的薄膜,其中该冲击改性剂包含弹性体芯和至少一种热塑性壳。
6.根据权利要求5的薄膜,其中该芯由聚(有机硅氧烷)组成,该聚(有机硅氧烷)携带一个或多个选自包含1至18个碳原子的烷基或者乙烯基,芳基和被取代的烃的基团。
7.根据权利要求5的薄膜,其中该芯包含选自以下的聚合物:异戊二烯或者丁二烯的均聚物,异戊二烯与最多30mol%的乙烯基单体的共聚物和丁二烯与最多30mol%的乙烯基单体的共聚物,(甲基)丙烯酸烷基酯的均聚物,和(甲基)丙烯酸烷基酯与最多30mol%的选自以下的单体的共聚物:另一种(甲基)丙烯酸烷基酯和乙烯基单体,该乙烯基单体是苯乙烯,烷基苯乙烯,丙烯腈,丁二烯或者异戊二烯。
8.根据权利要求6的薄膜,其中该壳由产生自单体的聚合物或者共聚物形成,所述单体选自:丙烯酸烷基酯或者甲基丙烯酸烷基酯,该烷基具有1至4个碳原子,丙烯腈,苯乙烯,二乙烯基苯,丙酸乙烯基酯马来酰亚胺,氯乙烯,乙烯,丁二烯,异戊二烯和氯丁二烯。
9.根据权利要求5或7任一项的薄膜,其中所述芯使用选自聚(甲基)丙烯酸多元醇酯,二乙烯基苯,三乙烯基苯,丙烯酸乙烯基酯和甲基丙烯酸乙烯基酯的至少双官能的单体全部或部分地进行交联,或使用选自不饱和羧酸酐、不饱和羧酸和不饱和环氧化物的不饱和官能单体全部或部分地进行交联。
10.根据权利要求5的薄膜,其中该芯是与包含聚硅氧烷的橡胶组合的挠性橡胶类型材料,所述挠性橡胶在由丙烯酸烷基酯或者甲基丙烯酸烷基酯获得的橡胶类型聚合物存在时,通过一种或多种乙烯基单体的聚合反应进行制备,其中所述烷基包含2至10个碳原子。
11.根据权利要求5、7、9或10任一项的薄膜,其中所述一个或多个壳是苯乙烯、烷基苯乙烯或者甲基丙烯酸甲酯的均聚物或者是包含至少70mol%的上述这些单体之一和至少一种选自剩余单体、另一种(甲基)丙烯酸烷基酯、醋酸乙烯酯和丙烯腈的共聚单体的共聚物。
12.根据前述权利要求任一项的薄膜,其具有为30至200微米,优选地为80至150微米的厚度。
13.根据前述权利要求任一项的薄膜,其中所述薄膜包含至少一种选自以下的添加剂:哑光剂、遮光剂、丙烯酸均聚物或者共聚物、增塑剂和反射红外射线的试剂,该试剂选自氧化钛或者基于云母和氧化钛的珍珠母颜料和金属合金。
14.根据前述权利要求任一项的薄膜,其中阻燃剂选自含卤素阻燃剂,含磷阻燃剂,钨酸钙,和硅酸铝。
15.包含至少一个根据权利要求1-14任一项的薄膜的层和至少一个PVDF层的多层薄膜。
16.根据权利要求15的薄膜,其由根据权利要求1-14任一项的内层和两个PVDF外层组成,所述外层具有相同或不同的结构。
17.根据权利要求1-14任一项的薄膜或根据权利要求15或16任一项的薄膜的用途,其作为用于制备用于建筑物,特别地农业建筑物,如畜牧业建筑物的屋顶和/或外立面的材料。
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FR1362876A FR3014878B1 (fr) | 2013-12-18 | 2013-12-18 | Film pvdf resistant a la dechirure a basse temperature et ininflammable |
PCT/FR2014/053399 WO2015092282A1 (fr) | 2013-12-18 | 2014-12-17 | Film pvdf résistant a la déchirure a basse température et ininflammable |
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JP6712445B2 (ja) * | 2015-05-27 | 2020-06-24 | 株式会社バルカー | 熱可塑性フッ素樹脂組成物、及び架橋体の製造方法 |
FR3070042B1 (fr) | 2017-08-09 | 2020-08-21 | Arkema France | Transistor organique a effet de champ contenant une couche dielectrique a haute permittivite dielectrique et stable en temperature |
FR3070041B1 (fr) * | 2017-08-09 | 2019-08-30 | Arkema France | Formulations a base de fluoropolymeres electroactifs et leurs applications |
US11952471B2 (en) * | 2019-09-20 | 2024-04-09 | Korea Advanced Institute Of Science And Technology | Ultrathin and stretchable polymer dielectric and its formation method |
CN116948238B (zh) * | 2023-07-20 | 2024-01-30 | 嘉兴高正新材料科技股份有限公司 | 一种超耐低温耐紫外透明聚偏氟乙烯薄膜及其制备方法 |
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JP2017502136A (ja) | 2017-01-19 |
WO2015092282A1 (fr) | 2015-06-25 |
KR20160101995A (ko) | 2016-08-26 |
CA2933636A1 (fr) | 2015-06-25 |
EP3083780A1 (fr) | 2016-10-26 |
FR3014878B1 (fr) | 2015-12-18 |
US20180163041A1 (en) | 2018-06-14 |
FR3014878A1 (fr) | 2015-06-19 |
AU2014369588A1 (en) | 2016-06-30 |
AU2014369588B2 (en) | 2018-01-04 |
MX2016007847A (es) | 2017-02-13 |
IL246198A0 (en) | 2016-07-31 |
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