CN102742143A - 具有反应性或不饱和聚烯烃的边缘密封剂组合物 - Google Patents
具有反应性或不饱和聚烯烃的边缘密封剂组合物 Download PDFInfo
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- CN102742143A CN102742143A CN2010800568607A CN201080056860A CN102742143A CN 102742143 A CN102742143 A CN 102742143A CN 2010800568607 A CN2010800568607 A CN 2010800568607A CN 201080056860 A CN201080056860 A CN 201080056860A CN 102742143 A CN102742143 A CN 102742143A
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Abstract
一种包括具有边缘密封的光电装置的太阳能模块。所述边缘密封的密封剂组合物包括不饱和或反应性聚烯烃、烯烃聚合物、硅烷改性聚烯烃、惰性填料、除水剂或干燥剂、抗氧化剂和紫外稳定剂。平衡这些组分以产生密封剂，所述密封剂具有期望的密封特征、高耐气候性、期望的流变能力、低导电率和良好的热稳定性。
Description
相关专利申请的交叉引用
本专利申请要求2009年10月14日提交的美国临时专利申请号61/251,542的优先权益，并为2010年3月19日提交的共同待审的美国专利申请号12/679,250的继续申请，所述美国专利申请号12,679,250要求2008年9月22日提交的国际申请号PCT/DE/2008/001564的优先权，所述国际申请号PCT/DE/2008/001564要求2007年9月20日提交的德国优先权文件DE/10 2007 045 104.2的优先权。上述申请的内容通过引用全文结合到本文中。
领域
本发明涉及具有反应性或不饱和聚烯烃的边缘密封剂组合物，更特别是可用于太阳能模块的具有反应性或不饱和聚烯烃的边缘密封剂。
背景
光电太阳能电池板或模块一般包括层叠和/或夹在多个层之间的光电装置。大多数光电装置为基于刚性晶片的晶体硅电池或薄膜模块，其在基片上沉积了碲化镉(Cd-Te)、非晶硅或铜-铟-二硒化物(CuInSe2)。薄膜太阳能模块可为刚性或柔性。柔性薄膜电池和模块通过将光敏层和任何其它必要的物质沉积在柔性基片上生产。光电装置相互电连接，并同其它太阳能电池板或模块电连接，以形成综合***。
光电太阳能电池板的效率因水分的侵入而减小。减小水分从环境到太阳能模块的内部、水分敏感部分的这种转移的一种有效方法是使用边缘密封剂。这些边缘密封剂具有水分传输速率或MVT低的性质。
太阳能模块中的边缘密封剂暴露于高温下，例如在建造太阳能模块期间的层叠步骤中。因此，期望这些边缘密封剂具有热稳定性。大多数边缘密封剂实际上为聚烯烃。因此，在高温暴露期间的主要降解机理为链无规则断裂。一旦这些自由基形成(由于链无规则断裂)，降解蔓延。除此以外，在密封剂暴露于热/光引发剂(如封装物，例如太阳能模块中的EVA)的应用中，那些引发剂倾向于使密封剂降解。对于密封剂的整体和表面性质，这可造成有害后果(例如强度损失、对玻璃的粘合性损失)。因此，本领域对边缘密封剂存在空间，所述边缘密封剂在高温条件下显示良好的热稳定性并在暴露于太阳能模块中的引发剂(封装物)时显示抗降解性(在野外的长期稳定性)。
概要
太阳能模块包括具有边缘密封的光电装置。边缘密封的密封剂组合物包括不饱和或反应性聚烯烃、烯烃聚合物、硅烷改性聚烯烃、惰性填料、除水剂或干燥剂、抗氧化剂和紫外稳定剂。平衡这些组分以生产密封剂，所述密封剂具有期望的密封特征、高耐气候性、期望的流变能力、低导电率和良好的热稳定性。
进一步的特征、优势和应用领域在本文提供的描述中显而易见。应理解所述描述和具体实施例旨在仅用于说明目的，而不旨在限制本公开的范围。
附图
本文描述的附图仅用于说明目的而不旨在以任何方式限制本公开的范围。图中的组分不必按比例，而是重点在于说明本发明的原理。在附图中：
图1为具有根据本发明原理的边沿密封组合物的太阳能模块实施方案的顶视图；
图2为具有根据本发明的边沿密封组合物的太阳能模块实施方案的一部分的截面图；
图3为显示不饱和或反应性聚合物在180℃空气循环炉中保温七天后的重量损失的条形图；且
图4为显示非反应性聚异丁烯(PIB)在180℃空气循环炉中保温七天后的重量损失的条形图。
详述
以下描述仅为示例性性质，且不旨在限制本公开、应用或用途。
参考图1和2，采用根据本发明原理的密封剂组合物的示例性太阳能模块总的通过参考数字10指出。所述太阳能模块10可采用各种不脱离本发明范围的形式且一般包括至少一个位于室13内的光电电池12，所述室13通过第一基片14和第二基片16限定。尽管说明了多个光电电池12，应理解可采用任何数目的光电电池12。
可操作所述光电电池12以从照射光电电池12的日光产生电流。相应地，所述光电电池12可采用各种不脱离本发明范围的形式。例如，所述光电电池12可为具有碲化镉(Cd-Te)、非晶硅或铜-铟-二硒化物(CuInSe2)层的薄膜电池。或者，所述光电电池12可为嵌入层叠膜的晶体硅晶片或沉积在锗或另一基片上的砷化镓。可采用的其他种类的光电装置12包括有机半导体电池，所述有机半导体电池具有共轭聚合物以及染料-敏化金属氧化物，包括湿金属氧化物和固体金属氧化物。所述光电装置12可为刚性或柔性。所述光电电池12以串联或并联或者其组合而连接。光电装置12产生的电流通过汇线条或其它导电材料或层传送到离开太阳能模块10的电线或导线15。所述导线15与接线盒17相联以便把太阳能模块10产生的电流分配到电源电路。
所述第一基片14或面板，由可操作以允许日光的波长从中穿过的材料形成。例如，所述第一基片14为玻璃或塑料膜如聚氟乙烯。选择第二基片16或背板以为太阳能模块10提供另外的强度。例如，第二基片16为塑料如氟化乙烯-丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物(ETFE)、聚偏二氟乙烯(PVDF)、聚氟乙烯(PVF)、聚(四氟乙烯)(PTFE)和这些塑料与其它聚合材料的组合。
所述光电电池12被层叠层19封装，所述层叠层19优选为可交联的乙基乙烯基乙酸酯(EVA)。然而，应理解可采用其它不脱离本发明范围的层叠物或热塑性封装物。所述层叠层19用来将光电装置12局部封装以保护所述光电装置12免受污染、机械应力和远离环境。
边沿或边缘密封18位于靠近太阳能模块10的边缘，位于第一基片14和第二基片16之间。所述边沿密封18可具有各种宽度。另外，还可包括第二边沿密封(未显示)。第二边沿密封可由例如硅酮、MS聚合物、硅烷化聚氨酯、丁基橡胶或多硫化物组成。可操作所述边沿密封18以将所述层叠层19和光电装置12密封。所述边沿密封18必须具有足够的耐气候性以承受对外界环境的暴露包括延长的紫外辐射暴露，具有低水分和蒸汽传输(MVT)，并具有低导电率。所述边沿密封20由密封剂组合物组成，所述密封剂组合物具有以下独特特征：高耐气候性与低导电率和MVT(将在以下更详细描述)，以及良好的热稳定性和氧化稳定性。
边沿密封18的密封剂组合物包括不饱和或反应性聚烯烃、烯烃聚合物、硅烷改性聚烯烃、惰性填料、除水剂、抗氧化剂和紫外稳定剂。平衡这些组分以生产密封剂，所述密封剂具有期望的密封特征、高耐气候性、期望的流变能力、低导电率和良好的热稳定性。
在密封剂的一些实施方案中，所述不饱和或反应性聚烯烃选自EPDM、聚烯烃丙烯酸酯和卤代丁基橡胶。所述烯烃聚合物选自聚异丁烯、聚丁烯、丁基橡胶(聚异丁烯-异戊二烯)、苯乙烯嵌段共聚物，尤其是SBS、SIS、SEBS、SEPS、SIBS、SPIBS以及改性形式和α-烯烃的非晶共聚物和/或三元共聚物(APAO)。
本发明的范围提供改性聚合物，其选自聚异丁烯、聚丁烯、丁基橡胶(聚异丁烯-异戊二烯)、苯乙烯嵌段共聚物，尤其是SBS、SIS、SEBS、SEPS、SIBS、SPIBS以及改性形式和α-烯烃的非晶共聚物和/或三元共聚物(APAO)，所述聚合物用至少一个式(1)的基团改性，所述基团为端基或统计学分布在链中
其中-A-为
-(CH2)m- (2)，
-S-(CH2)m- (3)或
且R1和R2相同或不同，并为具有1至20个碳原子的烷基、具有6至20个碳原子的芳基或具有7至20个碳原子的芳烷基，
X为羟基或可水解的基团，
a为0、1、2或3且b为0、1或2，a和b的总和大于或等于1，且其中n为0和18之间的整数，m为0和4之间的整数且R3为
此外，在本发明范围内的填料选自重质碳酸钙和沉淀碳酸钙、硅酸盐、石灰、氧化硅和炭黑。
在这一点上，本发明还提供碳酸钙经表面处理。
然而，还可使用未经表面处理的碳酸钙。
此外本发明提供硅酸盐选自滑石粉、高岭土、云母、氧化硅、硅石和硅酸钙或硅酸镁。
此外，在本发明范围内的干燥剂或除水剂选自3A至10A型分子筛(沸石)。
当然，还可使用其它化学上或物理上结合水的物质。
可将密封化合物配制为一部分密封化合物或两部分密封化合物。在一部分密封化合物的情况下，所有的组分在生产过程期间混合在一起。在两部分密封化合物的情况下，一些组分形成一部分而其它组分形成另一部分。随后在应用前即刻将所述化合物的两个部分混合在一起。
本发明还提供防老化剂选自空间位阻酚、硫醚、巯基化合物、磷酯、苯并***、二苯甲酮、HALS和抗臭氧剂。
在各种实施中，所述密封化合物可用来制造用于窗户、温室、结构和屋顶玻璃窗的绝缘玻璃，用于限于陆地(land-bound)的汽车、船舶和飞行器的玻璃窗，和用于制造太阳能模块，包括热电太阳能模块。除硅烷改性聚合物以外，具有不饱和或反应性聚烯烃的密封化合物设计成在层叠期间固化以提供另外的结构强度。
作为原理的证据，试验以下不饱和或反应性聚烯烃：Exxpro 3433(Exxon)、Lanxess溴代丁基橡胶2030(Lanxess)、EPDM(Vistalon 5601)(Exxon)和Exxon氯代丁基橡胶1068。将所有样品在180℃空气循环炉中保温7天并称重以计算重量损失。所述重量损失与热降解的程度(热稳定性相反)成比例。于180℃空气循环炉暴露7天作为极端条件而选择以研究聚合物的热稳定性。在这些极端条件下，丁基橡胶倾向于经受广泛的热降解，导致显著的重量损失。在这些条件下主要的降解机理更可能为链无规则断裂，直到形成足够小的分子的点，所述分子会被空气带走，导致重量损失。此外，氧气会加速热降解的速率，因为一旦通过链无规则断裂形成基团，氧分子会与它反应形成烷氧基和过氧基。不饱和橡胶的反应性倾向于使用这些自由基并停止进一步降解。在许多情况下，已观察到不饱和和基团的组合导致分子量累积和/或交联，进一步增大强度。从图3可清楚地看出，所选的反应性或不饱和聚烯烃于180℃空气循环炉暴露7天后显示最小的重量损失(不足5%)。暴露于相似条件下的非反应性聚烯烃(来自BASF的Oppanol B-100和B-50)显示(见图4)超过95%的重量损失。
观察到反应性和/或不饱和部位与在高温暴露下形成的自由基反应导致最小程度的降解(如果有的话)和改进的热稳定性。所述边缘密封显示低的MVTR并可在与自由基反应时交联，其中所述自由基可能是热降解或热氧化降解或与太阳能模块的封装物中含有的过氧化物反应的结果。另外，在180℃空气循环炉中老化7天(一种加速老化试验，作为热稳定性和热氧化稳定性的度量)后，所述边缘密封剂显示不到10%的重量损失。更优选地，在180℃空气循环炉中老化7天后，所述边缘密封剂显示不到7.5%的重量损失。
特别关注的是EPDM聚合物，其含有不饱和聚合骨架，所述聚合骨架由乙烯和丙烯单体与小但是显著量的至少一种非共轭二烯(如降冰片二烯、二环戊二烯和/或1,5-己二烯)组成。意义在于，各种EPDM聚合物存在优先的二元性：尽管骨架完全饱和，从而对大多数部分包括过氧化物及其他氧化剂高度稳定和非反应性，但在侧链中偶然存在的双键允许交联，且假如这些侧链键断裂，骨架保持完整。
注意在图1中，尽管所有含有全部列出的聚合物的制品给出令人印象深刻的低重量损失结果，但是含有EPDM(Vistalon)的制剂给出的重量损失结果最低。理论上，在更有挑战性的环境中，预期含EPDM制剂更好地承受更苛刻的环境，使之与其它相区别。
EPDM还提供反应性和不包含卤素如氯或溴的饱和骨架。盐酸和氢溴酸废气排放对于EPDM是不可能的。
为了使本发明可以更容易地理解，参考以下实施例，所述实施例旨在说明本发明的原理，但不限制其范围。
其中对于各实施例，组分为：
不饱和反应性聚烯烃比如EPDM、聚烯烃丙烯酸酯和分子量Mn为100-100,000 Da，优选100-500,000 Da的卤代丁基橡胶；
烯烃聚合物：聚乙烯、聚丙烯、聚丁烯、聚异丁烯、丁基橡胶(聚异丁烯-异戊二烯)、苯乙烯嵌段共聚物(以及改性形式)：对于所有烯烃聚合物分子量(Mn为100-1,000,000 Da，优选100-300,000 Da)；
硅烷：DFDA-5451NT(来自Dow Chemical的硅烷接枝PE)、DFDA-5481 NT(来自Dow Chemical的水分固化催化剂)、非晶聚α-烯烃(比如但不局限于Vestoplast 206、Vestoplast 2412)、烷氧基硅烷、氨基硅烷；
惰性填料：重质碳酸钙和沉淀碳酸钙、硅酸盐、氧化硅和炭黑、CaCO3、Ca(OH)2、二氧化钛，
硅酸盐选自滑石粉、高岭土、云母、氧化硅、硅石和硅酸钙或硅酸镁；
除水剂如CaO或干燥剂如分子筛、硅胶和硫酸钙；
防老化剂：位阻酚、位阻胺、硫醚、巯基化合物、磷酯、苯并***、二苯甲酮和抗臭氧剂。
本发明的描述仅为示例性性质，且不脱离本发明要旨的变化旨在属于本发明的范围内。这些变化不看作偏离本发明的精神和范围。
Claims (20)
1. 一种用于制造两面或多面绝缘玻璃或太阳能模块的边缘密封，所述边缘密封包括密封剂和结合剂，其中所述密封剂含有用特殊反应性基团改性的聚合物并具有以下总体组成：
a)不饱和或反应性聚烯烃或其组合，其量为总组合物的约10重量%-80重量%；
b)烯烃聚合物或其组合，其包括量为总组合物的约5重量%-约80重量%；
c)至少一种填料，其包括量为总组合物的约10重量%-约60重量%；
d)干燥剂或除水剂中的至少一种，其包括量为总组合物的约2.5重量%-约25重量%；和
e)至少一种包括抗氧化剂或紫外稳定剂的防老化剂，其包括量为总组合物的约0.1重量%-约3重量%。
2. 权利要求1的边缘密封，其中烯烃聚合物的包括量为总组合物的约5重量%-约50重量%，且硅烷改性聚合物的包括量为总组合物的约5重量%-约30重量%。
3. 权利要求2的边缘密封，其中所述填料还包括微粒填料，其量为总组合物的约5重量%-约50重量%。
4. 权利要求2的边缘密封，其中所述烯烃聚合物选自聚异丁烯、聚丁烯、丁基橡胶(聚异丁烯-异戊二烯)、苯乙烯嵌段共聚物、SBS(苯乙烯-丁二烯-苯乙烯)、SIS(苯乙烯-异戊二烯-苯乙烯)、SEBS(苯乙烯-乙烯-丁烯-苯乙烯)、SEPS(苯乙烯-乙烯-丙烯-苯乙烯)、SIBS(苯乙烯-异戊二烯-丁二烯-苯乙烯)、SPIBS(苯乙烯-聚异丁烯-苯乙烯)以及改性形式和α-烯烃的非晶共聚物和/或三元共聚物(APAO)。
5. 权利要求2的边缘密封，其中所述硅烷改性聚合物选自聚异丁烯、聚丁烯、丁基橡胶(聚异丁烯-异戊二烯)、苯乙烯嵌段共聚物、SBS(苯乙烯-丁二烯-苯乙烯)、SIS(苯乙烯-异戊二烯-苯乙烯)、SEBS(苯乙烯-乙烯-丁烯-苯乙烯)、SEPS(苯乙烯-乙烯-丙烯-苯乙烯)、SIBS(苯乙烯-异戊二烯-丁二烯-苯乙烯)、SPIBS(苯乙烯-聚异丁烯-苯乙烯)和α-烯烃的非晶共聚物和/或三元共聚物(APAO)。
6. 权利要求5的边缘密封，其中所述APAO聚合物用至少一个式(1)的基团改性，所述基团为端基或统计学分布在链中
，
其中-A-为
-(CH2)m- (2)，
-S-(CH2)m- (3)或
(4)
且R1和R2相同或不同，并为具有1至20个碳原子的烷基、具有6至20个碳原子的芳基或具有7至20个碳原子的芳烷基，
X为羟基或可水解的基团，
a为0、1、2或3且b为0、1或2，a和b的总和大于或等于1，且其中n为0和18之间的整数，m为0和4之间的整数且R3为
。
7. 权利要求3的边缘密封，其中所述密封剂的微粒填料选自重质碳酸钙和沉淀碳酸钙、硅酸盐、石灰、氧化硅和炭黑。
8. 权利要求7的边缘密封，其中所述密封剂的碳酸钙为经表面处理的碳酸钙。
9. 权利要求7的边缘密封，其中所述密封剂的硅酸盐选自滑石粉、高岭土、云母、氧化硅、硅石和硅酸钙或硅酸镁。
10. 权利要求1的边缘密封，其中所述密封剂的干燥剂或除水剂选自分子筛、五氧化二磷、氧化钙、无水盐、环氧化植物油、碳二亚胺、对甲苯磺酰基异氰酸酯或它们的组合。
11. 权利要求1的边缘密封，其中所述密封剂的干燥剂或除水剂选自3A至10A型的分子筛(沸石)。
12. 权利要求1的边缘密封，其中所述密封剂的防老化剂选自空间位阻酚、硫醚、巯基化合物、磷酯、苯并***、二苯甲酮、HALS(位阻胺光稳定剂)和抗氧化剂。
13. 权利要求1的边缘密封，其中所述不饱和或反应性聚烯烃选自EPDM、聚烯烃丙烯酸酯和卤代丁基橡胶。
14. 权利要求2的边缘密封，其中烯烃聚合物的包括量为约30重量%-约50重量%，且其Mn为约5,000 D至约1,000,000 D，硅烷改性聚合物的包括量为约5重量%-25重量%，且干燥剂或除水剂的包括量最多为总组合物的约15重量%。
15. 一种太阳能模块，其包括：
第一基片；
第二基片；
至少一个设置于第一和第二基片之间的光电电池；
密封剂，所述密封剂与第一和第二基片接触形成水蒸汽阻挡层，以阻碍水蒸汽到达至少一个光电电池，其中所述密封剂包括：
不饱和或反应性聚烯烃；
烯烃聚合物；
硅烷改性APAO和硅烷改性聚异丁烯中的至少一种；
至少一种填料；
除水剂或干燥剂中的至少一种；和
至少一种防老化剂，且
其中所述密封剂使光电电池电绝缘。
16. 权利要求15的太阳能模块，其中第一和第二基片中的至少一种为玻璃、聚合物和金属中的至少一种。
17. 权利要求15的太阳能模块，其中所述不饱和或反应性聚烯烃的包括量为总组合物的约10重量%-约80重量%，所述烯烃聚合物包括总组合物的约5重量%-约50重量%的量的聚异丁烯，所述硅烷改性APAO和硅烷改性聚异丁烯中的至少一种的包括量为总组合物的约5重量%-约30重量%，所述填料的包括量为总组合物的约10重量%-约60重量%，所述除水剂或干燥剂中的至少一种的包括量为总组合物的约2.5重量%-约25重量%，且所述防老化剂的包括量为总组合物的0.1重量%-约3重量%。
18. 一种用于具有光电电池的太阳能模块的化合物，所述化合物包含：
不饱和或反应性聚烯烃；
烯烃聚合物；
硅烷改性APAO和硅烷改性聚异丁烯中的至少一种；
至少一种填料；
除水剂或干燥剂中的至少一种；和
至少一种防老化剂，且
其中所述化合物使光电电池电绝缘。
19. 权利要求18的化合物，其中所述不饱和或反应性聚烯烃的包括量为总组合物的约10重量%-约80重量%，所述烯烃聚合物包括总组合物的约5重量%-约50重量%的量的聚异丁烯，所述硅烷改性APAO和硅烷改性聚异丁烯中的至少一种的包括量为总组合物的约5重量%-约30重量%，所述填料的包括量为总组合物的约10重量%-约60重量%，所述除水剂或干燥剂中的至少一种的包括量为总组合物的约2.5重量%-约25重量%，且所述防老化剂的包括量为总组合物的0.1重量%-约3重量%。
20. 一种用于具有第一基片和第二基片的太阳能模块的密封化合物，其中所述密封化合物设置于第一基片和第二基片之间，所述密封化合物包含：
不饱和或反应性聚烯烃；
大于总组合物的约30重量%的量的烯烃聚合物；
硅烷改性APAO和硅烷改性聚合物中的至少一种，其量小于总组合物的35重量%；
填料；
初级粒径小于约60nm的炭黑；
除水剂或干燥剂中的至少一种；和
防老化剂。
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| CN1703781A (zh) * | 2002-08-21 | 2005-11-30 | 特鲁西尔技术公司 | 包含低湿气渗透率粘合剂组合物的太阳能电池板 |
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| CN104766897A (zh) * | 2014-01-08 | 2015-07-08 | 明尼苏达矿业制造特殊材料（上海）有限公司 | 一种太阳能电池组件 |
| WO2017114291A1 (zh) * | 2015-12-31 | 2017-07-06 | 比亚迪股份有限公司 | 密封胶带组合物和密封胶带及其用途 |
| CN106928883A (zh) * | 2015-12-31 | 2017-07-07 | 比亚迪股份有限公司 | 一种密封胶带组合物和密封胶带及其应用 |
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| CN114316809A (zh) * | 2022-01-10 | 2022-04-12 | 南亚新材料科技股份有限公司 | 锂电池用密封胶及其制备方法 |
| CN114316809B (zh) * | 2022-01-10 | 2023-10-20 | 南亚新材料科技股份有限公司 | 锂电池用密封胶及其制备方法 |
| CN114605947A (zh) * | 2022-01-27 | 2022-06-10 | 北京东方雨虹防水技术股份有限公司 | 一种基于硅烷改性的热熔压敏胶及其制备方法 |
| CN114605947B (zh) * | 2022-01-27 | 2023-05-02 | 北京东方雨虹防水技术股份有限公司 | 一种基于硅烷改性的热熔压敏胶及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013509694A (ja) | 2013-03-14 |
| EP2489117A4 (en) | 2014-12-31 |
| WO2011047185A1 (en) | 2011-04-21 |
| EP2489117A1 (en) | 2012-08-22 |
| KR20120085803A (ko) | 2012-08-01 |
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