CN106661233A - 在n‑甲酰基‑或n‑乙酰基吗啉中的聚偏二氟乙烯溶液 - Google Patents

在n‑甲酰基‑或n‑乙酰基吗啉中的聚偏二氟乙烯溶液 Download PDF

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CN106661233A
CN106661233A CN201580034082.4A CN201580034082A CN106661233A CN 106661233 A CN106661233 A CN 106661233A CN 201580034082 A CN201580034082 A CN 201580034082A CN 106661233 A CN106661233 A CN 106661233A
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U·卡尔
C·埃尔克
M·多恩布什
水野秀彦
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Abstract

公开了聚偏二氟乙烯(PVDF)或1,1‑二氟乙烯共聚物在含有N‑甲酰基吗啉(NFM)、N‑乙酰基吗啉(NAM)或其混合物且额外包含选自碳酸亚烷基酯、单‑、二‑或聚亚烷基二醇二烷基醚或其混合物的共溶剂的溶剂中的溶液。

Description

在N-甲酰基-或N-乙酰基吗啉中的聚偏二氟乙烯溶液
本发明涉及聚偏二氟乙烯(PVDF)或1,1-二氟乙烯共聚物在包含N-甲酰基吗啉(NFM)、N-乙酰基吗啉(NAM)或其混合物且额外包含选自碳酸亚烷基酯、单-、二-或聚亚烷基二醇二烷基醚或其混合物的共溶剂的溶剂中的溶液。
聚偏二氟乙烯(PVDF)用于生产涂料和模制品，例如纤维、薄膜、管道、软管、嵌板、电缆、配件、法兰、固定件、砂浆、密封件、粉末、薄膜。考虑到其耐热性和耐化学品性，例如将PVDF用于涂敷管道或用于生产膜和密封件。在电极的制造中，将PVDF用作粘合剂。它同样可以在电池组合蓄电池中用作隔片膜，用于涂敷电气测量探头或光伏单元。PVDF通常作为熔体加工或者溶于溶剂中并作为溶液施加于所需表面或者例如通过旋涂、铸膜、刮涂、压延、模塑或注塑方法转化成所需形状。在涂敷操作或模制品生产过程中或其之后除去溶剂。因此，所用溶剂必须满足特定要求：它必须尽可能容易溶解PVDF。同时，在该溶剂的随后除去过程中，目的是要产生尽可能均匀且具有均匀表面和良好机械性能的涂层或模制品。
由JP 4071845、WO 2010/057917和JP 11071346已知使用N-甲基吡咯烷酮或其他N-烷基吡咯烷酮作为PVDF的溶剂。
US 5296318提到了四氢呋喃(THF)和THF与碳酸亚乙酯或碳酸亚丙酯的混合物作为PVDF的溶剂。
US 3110692公开了将NFM和NAM用作聚氟乙烯的溶剂。聚氟乙烯为氟乙烯(C2H3F)的聚合物。相反，PVDF不溶于纯NFM或者在纯NFM中仅具有有限溶解度。
NFM和不同于其的非质子溶剂的溶剂混合物在WO 2011/147822中被描述为农药用溶剂。
本发明的目的是要找到一种用于PVDF的溶剂，其具有最低可能的毒性，尤其不具有致癌、致突变或生殖毒性性能，具有最高可能的闪点且尽可能好地溶解PVDF并因此允许生产由PVDF制成的极为均匀涂层和模制品。
因此，发现了上面定义的溶液及其用途。
溶剂
优选该溶剂由至少20重量％，特别优选至少30重量％，非常特别优选至少50重量％的NFM、NAM或其混合物构成。
在特别优选的实施方案中，该溶剂包含NFM；它优选以上述量包含NFM。
该共溶剂为碳酸亚烷基酯、单-、二-或聚亚烷基二醇二烷基醚或其混合物。
碳酸亚烷基酯尤其为碳酸亚乙酯或碳酸1,2-亚丙基酯；特别优选碳酸1,2-亚丙基酯。
单-、二-或聚亚烷基二醇二醚尤其是在标准条件(20℃，1巴)下为液体的化合物。
单-、二-或聚亚烷基二醇二醚优选为式I的那些：
R1O-R3-(O-R4-)nOR2
其中
R1和R2相互独立地为C1-C4烷基，
R3和R4相互独立地为亚乙基、亚丙基或亚丁基，以及
n为0-4的整数。
优选R1和R2相同。特别优选R1和R2为甲基。
优选R3和R4相同。特别优选R3和R4为亚丙基。
优选n为1或2；特别优选n为1；即特别优选式I的二亚烷基二醇二烷基醚。
特别优选的二亚烷基二醇二烷基醚为二丙二醇二甲基醚(R1和R2均为甲基，R3和R4均为亚丙基且n为1)。
二丙二醇二甲基醚可以以各种异构形式或者作为异构体混合物存在。
因此，作为Proglyme已知的标准市售二丙二醇二甲基醚通常为亚丙基的位置不同的三种区域异构体的混合物：
此外，二丙二醇二甲基醚(Proglyme)通常也为立体异构体(对映体和非对映体)的混合物。
优选该共溶剂为碳酸1,2-亚丙基酯或式I的二亚烷基二醇二烷基醚。
特别优选该共溶剂为碳酸1,2-亚丙基酯或二丙二醇二甲基醚。
非常特别优选该共溶剂为二丙二醇二甲基醚。
除了上述量或优选量的NFM和/或NAM外，该实施方案中的溶剂混合物尤其包含至少5重量％，特别优选至少10重量％的共溶剂。
除了NFM、NAM、其混合物和共溶剂外，该溶剂可以额外包含其他溶剂。
其他溶剂在该溶剂混合物中的含量尤其为至多20重量％，尤其是至多10重量％，特别优选至多5重量％。
可以提到的其他溶剂是疏水性溶剂，如甲苯、邻二甲苯、对二甲苯、枯烯、氯苯、乙苯或烷基芳烃的工业级混合物。
其他溶剂还可以是亲水性质子性化合物，例如水或醇类如甲醇、乙醇、丙醇或丁醇，或亲水性非质子化合物，例如酮类如丙酮、环己酮、丁-2-酮(甲基乙基酮，MEK)、甲基异丁基酮(MIBK)或异佛尔酮，醚类如四氢呋喃、二烷、乙醚、叔丁基甲基醚，酯类如甲酸、乙酸、琥珀酸、戊二酸、己二酸、邻苯二甲酸或磷酸的甲基、乙基、丙基或丁基酯，以及它们的混合物，内酯如g-丁内酯，以及还有碳酸亚乙酯。作为其他溶剂，优选亲水性非质子溶剂。
特别合适的例如是由如下组分构成的溶剂混合物：
5-95重量％NFM、NAM或其混合物，尤其是NFM，和
5-95重量％共溶剂，和
0-10重量％其他溶剂。
特别优选由如下组分构成的溶剂混合物：
20-80重量％NFM、NAM或其混合物，尤其是NFM，和
20-80重量％共溶剂，和
0-5重量％其他溶剂。
非常特别优选合适的是由如下组分构成的溶剂混合物：
45-80重量％NFM、NAM或其混合物，尤其是NFM，和
20-55重量％共溶剂，和
0-5重量％其他溶剂。
在一个特殊实施方案中，该溶剂混合物不包含其他溶剂；此时，该溶剂混合物仅由NFM、NAM或其混合物和共溶剂构成。非常特别优选该溶剂混合物仅由NFM和二丙二醇二甲基醚(Proglyme)构成。
聚合物
溶液包含PVDF或1,1-二氟乙烯共聚物，优选由至少70重量％1,1-二氟乙烯构成的共聚物。PVDF仅由1,1-二氟乙烯构成。
PVDF和上述共聚物可以具有例如10 000-3 000 000g/mol，尤其是50 000-2 000000g/mol的数均分子量Mn。分子量可以通过凝胶渗透色谱法(GPC)(洗脱剂：二甲基乙酰胺；标准：聚苯乙烯)测定。
溶液优选包含PVDF或由至少90重量％，特别优选至少95重量％1,1-二氟乙烯构成的共聚物。
非常特别优选溶液包含PVDF。
在共聚物情况下，它们尤其可以是1,1-二氟乙烯与其他可自由基共聚的化合物(单体)的共聚物。
这类单体可以是亲水性单体或非亲水性单体。单体可以不含氟或含氟。含氟单体例如为单-、三-或四氟乙烯。
亲水性单体尤其为具有任选也可以作为盐存在的酸基、羟基、腈基、任选也可以作为盐存在的氨基、酰胺基、内酰胺基团或环氧基的那些。
具有酸基的单体例如为具有羧酸、磺酸或膦酸基团的那些，其中上述酸基也可以作为盐存在。合适的例如是具有无机阳离子如碱金属阳离子或铵阳离子或有机阳离子，例如被有机基团取代的铵阳离子的盐。
尤其可以提到丙烯酸、甲基丙烯酸[简述为(甲基)丙烯酸]、乙烯基磺酸、乙烯基膦酸或其盐。
具有羟基的单体例如为(甲基)丙烯酸羟烷基酯，尤其是(甲基)丙烯酸羟基-C2-C8烷基酯如(甲基)丙烯酸羟乙基酯、(甲基)丙烯酸羟丁基酯或(甲基)丙烯酸羟基-2-乙基己基酯。
具有腈基的单体例如为丙烯腈或甲基丙烯腈。
具有氨基的单体例如为被氨基取代的(甲基)丙烯酸烷基酯。
具有酰胺基的单体例如为丙烯酰胺或甲基丙烯酰胺。
具有内酰胺基团的单体例如为N-乙烯基吡咯烷酮、N-乙烯基咪唑或N-乙烯基己内酰胺。
具有环氧基的单体例如为(甲基)丙烯酸缩水甘油酯。
非亲水性单体例如为具有丙烯酸系或甲基丙烯酸系基团的单体，例如(甲基)丙烯酸C1-C8烷基酯，如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己基酯，乙烯基芳族单体如苯乙烯，乙烯基酯如乙酸乙烯酯，乙烯基醚如乙基乙烯基醚或丁基乙烯基醚，或烯烃如乙烯或丙烯。
溶液尤其包含基于溶液总重量为1-60重量％，特别优选1-50重量％，非常特别优选1-40重量％的PVDF或1,1-二氟乙烯共聚物。优选溶液包含基于溶液总重量为至少5重量％，尤其是至少10重量％，非常特别优选至少20重量％的PVDF或1,1-二氟乙烯共聚物。
PVDF或共聚物可以容易地溶于该溶剂中，任选通过提高温度来支持。PVDF或共聚物也可以首先作为在另一溶剂，例如N-甲基吡咯烷酮中的溶液存在，然后借助溶剂交换转化成本发明的上述溶液。
为了将PVDF或共聚物溶于该溶剂或溶剂混合物中，可以将该溶剂或溶剂混合物的温度提高到例如30-175℃，尤其是40-165℃，特别优选50-160℃。
PVDF或共聚物也可以例如通过1,1-二氟乙烯和任选其他单体的自由基聚合而直接在上述溶剂中生产。
除了该溶剂和PVDF或共聚物外，本发明溶液可以包含其他成分。合适的例如是引发剂，若PVDF或共聚物已经在该溶剂中生产的话，以及还有稳定剂，如抗氧化剂、UV抑制剂、乳化剂、流动助剂或对于该溶液的特定意欲用途有帮助或必要的其他添加剂。
其他成分的重量比例例如可以为0-40重量％，尤其是0-20重量％或0-10重量％或0-5重量％。
该溶液可以用于生产涂层或模制品。除了管道、软管、嵌板、电缆、配件、法兰、固定件、密封件外，模制品例如还有涂层、粉末、纤维、薄膜、箔和膜。
它们尤其适合生产膜。
它们还尤其适合在电极，尤其是用于锂蓄电池中的电极上生产涂层。
为了生产涂层或模制品，可以将该溶液引入所需模具的中空体中或者可以涂敷于所需表面上。该溶剂可以被容易地除去，例如通过提高温度。由此形成所需模制品或所需涂层。
包含N-甲酰基吗啉(NFM)、N-乙酰基吗啉(NAM)或其混合物的溶剂也可以用于除去PVDF或1,1-二氟乙烯共聚物的残余物或涂层。为此，用该溶剂处理残余物或涂层并作为溶液除去。
本发明溶剂非常容易地溶解PVDF和1,1-二氟乙烯共聚物。可以得到稳定溶液。这些溶液尤其在15-100℃下稳定且PVDF或共聚物在该温度范围内保持溶解。当使用本发明溶液时，得到非常均匀的涂层和具有良好机械性能的模制品。
实施例
实施例1
将聚偏二氟乙烯(PVDF；Mw 180 000g/mol，Mn 71 000g/mol)溶于150g由105克NFM和45克Proglyme构成的溶剂混合物中。
为此将该溶剂混合物加热至100-120℃。
然后以7.5克的量将PVDF逐步加入该溶剂混合物中并在各步骤之后在100-120℃下搅拌，直到全部溶解。
由此总共将52.5克PVDF完全溶于该溶剂混合物中。因此该溶液包含26重量％PVDF且甚至在冷却至室温之后也稳定。
实施例2
将聚偏二氟乙烯(PVDF)溶于150g由105克NFM和45克碳酸亚丙酯构成的溶剂混合物中。
为此将该溶剂混合物加热至100-120℃。
然后以7.5克的量将PVDF逐步加入该溶剂混合物中并在各步骤之后将该混合物在100-120℃下搅拌，直到全部溶解。
在该溶液达到15重量％PVDF含量之后，考虑到在使用磁棒作为搅拌器的设备中粘度的提高而再也不能加入进一步的PVDF。所得溶液具有15重量％的PVDF含量。PVDF完全溶解。该溶液甚至在冷却至室温之后也稳定。
对比例
所用溶剂仅为NFM。首先如上所述加入7.5克PVDF。甚至在加热至100-120℃时，该量的PVDF不能溶于纯NFM中，或者仅很少溶于纯NFM中。甚至加热至该溶剂的沸点也不会得到所加入的PVDF的溶液。

Claims (12)

1.一种聚偏二氟乙烯(PVDF)或1,1-二氟乙烯共聚物在包含N-甲酰基吗啉(NFM)、N-乙酰基吗啉(NAM)或其混合物且额外包含选自碳酸亚烷基酯、单-、二-或聚亚烷基二醇二烷基醚或其混合物的共溶剂的溶剂中的溶液。
2.根据权利要求1的溶液，其中所述单-、二-或聚亚烷基二醇二烷基醚为式I的那些：
R1O-R3-(O-R4-)nOR2
其中
R1和R2相互独立地为C1-C4烷基，
R3和R4相互独立地为亚乙基、亚丙基或亚丁基，以及
n为0-4的整数。
3.根据权利要求1或2的溶液，其中所述共溶剂为式I的二亚烷基二醇二烷基醚或碳酸1,2-亚丙基酯。
4.根据权利要求1-3中任一项的溶液，其中所述溶剂为由如下组分构成的溶剂混合物：
5-95重量％NFM、NAM或其混合物，
5-95重量％共溶剂，
0-10重量％其他溶剂。
5.根据权利要求1-4中任一项的溶液，其中它为PVDF或由至少70重量％1,1-二氟乙烯构成的共聚物的溶液。
6.根据权利要求1-5中任一项的溶液，其中所述溶液包含基于所述溶液的总重量为1-60重量％的PVDF或1,1-二氟乙烯共聚物。
7.根据权利要求1-6中任一项的溶液在生产涂层或模制品中的用途。
8.根据权利要求1-6中任一项的溶液在生产膜、薄膜或纤维中的用途。
9.根据权利要求1-6中任一项的溶液在电极上产生涂层的用途。
10.包含N-甲酰基吗啉(NFM)、N-乙酰基吗啉(NAM)或其混合物且额外包含选自碳酸1,2-亚丙基酯、二-或聚亚烷基二醇二烷基醚或其混合物的共溶剂的溶剂在除去PVDF或1,1-二氟乙烯共聚物的残余物或涂层中的用途。
11.一种由如下组分构成的溶剂混合物：
5-95重量％NFM、NAM或其混合物，
5-95重量％选自单-、二-或聚亚烷基二醇二烷基醚或其混合物的共溶剂，和
0-10重量％其他溶剂。
12.根据权利要求11的溶剂混合物在生产聚偏二氟乙烯(PVDF)或1,1-二氟乙烯共聚物的溶液中的用途。
CN201580034082.4A 2014-06-24 2015-06-12 在n‑甲酰基‑或n‑乙酰基吗啉中的聚偏二氟乙烯溶液 Withdrawn CN106661233A (zh)

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