CN110892018B - 高强度聚偏二氟乙烯复合材料 - Google Patents
高强度聚偏二氟乙烯复合材料 Download PDFInfo
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- CN110892018B CN110892018B CN201880046999.XA CN201880046999A CN110892018B CN 110892018 B CN110892018 B CN 110892018B CN 201880046999 A CN201880046999 A CN 201880046999A CN 110892018 B CN110892018 B CN 110892018B
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- fluoropolymer
- alkali metal
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- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 151
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 151
- 239000000835 fiber Substances 0.000 claims abstract description 83
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims description 76
- -1 Ammonium ions Chemical class 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 31
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- 125000000524 functional group Chemical group 0.000 claims description 30
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical group [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 10
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
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- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 7
- 150000007942 carboxylates Chemical group 0.000 claims 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims 2
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 16
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- 239000004416 thermosoftening plastic Substances 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
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- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 3
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- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 2
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- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明涉及含氟聚合物复合材料,其具有含官能化含氟聚合物组合物的含氟聚合物基质,并用纤维增强。纤维可以是短切纤维、长纤维或它们的混合物,并且含氟聚合物基质优选基于聚偏二氟乙烯。可以将上胶或未上胶的任何类型的纤维与官能化的含氟聚合物基质组合物一起使用,以形成含氟聚合物复合材料。
Description
发明领域
本发明涉及含氟聚合物复合材料,其具有含官能化含氟聚合物组合物的含氟聚合物基质,并用纤维增强。纤维可以是短切纤维、长纤维或它们的混合物,并且含氟聚合物基质优选基于聚偏二氟乙烯。可以将上胶或未上胶的任何类型的纤维与官能化的含氟聚合物基质组合物一起使用,以形成含氟聚合物复合材料。
发明背景
已知含氟聚合物,例如基于偏二氟乙烯CF2=CH2(VDF)的含氟聚合物具有出色的机械稳定性能,非常好的化学惰性,较低的表面能,电化学稳定性和良好的耐老化性。这些品质在各种最终用途应用中得到了利用。糟糕的是,由于其惰性,很难将含氟聚合物结合到其他材料上或使其与其他材料良好粘合。
官能团已被添加到含氟聚合物中,以增加与其他材料的粘合性,增加一定水平的亲水性和润湿性,并提供反应性位点,例如用于交联和随后的化学改性。官能团已经通过几种方式添加,例如通过官能单体与含氟单体的直接共聚,以及通过聚合后接枝机理,例如将马来酸酐接枝到聚偏二氟乙烯均聚物或共聚物上(如US 7,241,817中所述),以形成可得自阿科玛公司(Arkema Inc.)的ADX树脂。WO 2013/110740和US 7,351,498还描述了通过单体接枝或通过共聚来使含氟聚合物官能化。
已知纤维在许多类型的聚合物复合材料中用作增强材料。长纤维可以上胶或涂覆有聚合物或预聚物,该聚合物或预聚物可充当粘合剂以将纤维固定在一起或起到与长纤维复合材料的聚合物基质相容或反应的作用。然后可以通过一系列不同的方法用聚合物基质浸渍上胶的长纤维,以形成带材或片材。然后通过一系列不同的方法(压缩成型,自动铺带等)将该浸渍的片材或带材固结为最终制品,以制造固结的热塑性复合材料制品。由长纤维制成的制品通常包含至少45重量%,优选大于50重量%,并且经常大于60至70重量%的增强纤维。
在连续纤维制品中,制品的性质受纤维性质支配,聚合物充当粘合剂/基质以将纤维保持在一起。
US 8,883,898公开了用已被官能化的含氟聚合物浸渍连续纤维,所述官能化优选通过用马来酸酐接枝来进行。
已经针对不同的聚合物基质开发了不同的纤维上胶剂,以改善上胶纤维与基质聚合物之间的相容性。不幸的是,当前的纤维上胶剂与含氟聚合物的相容性差。没有良好的相容性,因此在纤维与含氟聚合物基质之间没有良好的分布和良好的粘合性,使用纤维增强材料的好处还没有得到充分实现。
令人惊讶地,现已发现,使用官能化的含氟聚合物基质以及经过处理或上胶以包含官能团的纤维,会导致纤维与基质发生化学相互作用,这种相互作用可改善纤维对基质的粘附性,从而提高了复合材料的拉伸和挠曲强度。
发明概述
本发明涉及纤维增强的含氟聚合物复合材料,其具有官能化的含氟聚合物组合物基质,和纤维。基质占复合材料的2至100重量%,优选10至100重量%,最优选40至60重量%,并且所述纤维为15至60重量%。
官能化的含氟聚合物基质可以是:
a)包含长含氟聚合物嵌段和一个或多个短聚丙烯酸末端嵌段的含氟聚合物嵌段共聚物;
b)具有含氟聚合物主链以及一个或多个接枝官能团的接枝共聚物,其中在一个实施方式中,接枝单体不是马来酸酐;
c)具有官能共聚单体单元作为主链聚合物的一部分的含氟聚合物;
d)非官能含氟聚合物和相容性官能非氟聚合物的混合物;
e)具有官能共聚单体和一个或多个短聚丙烯酸末端嵌段的嵌段含氟聚合物,所述官能共聚单体具有偏二氟乙烯单体单元;
f)一种或多种非官能含氟聚合物与a),b)或c)的任何官能含氟聚合物的混合物。
优选地,含氟聚合物基质是聚偏二氟乙烯均聚物,或具有至少60重量%的偏二氟乙烯单体单元的共聚物。
在一个实施方式中,如权利要求3的纤维增强的含氟聚合物复合材料,其中所述相容性官能非氟聚合物包括一种或多种官能(甲基)丙烯酸类聚合物。
在一个优选的实施方式中,如权利要求1的纤维增强的含氟聚合物复合材料,其中所述纤维选自下组:碳纤维、玻璃纤维和芳族聚酰胺纤维,或它们的混合物。
在一个实施方式中,如权利要求1的纤维增强的含氟聚合物复合材料,其中所述纤维包括具有能够与官能化的含氟聚合物基质组合物结合的官能团的上胶剂。
在一个实施方式中,如权利要求11的纤维增强的含氟聚合物复合材料,其中所述上胶剂是官能化的含氟聚合物组合物。
发明详述
如本文所用,“共聚物”是指具有两种或更多种不同单体单元的任何聚合物,并且将包括三元共聚物以及具有多于三种不同单体单元的共聚物。
本申请中引用的参考文献通过引用纳入本文。
除非另有说明,否则本文所用的百分数是重量百分数,除非另有说明,否则分子量是通过GPC使用PMMA参比测量的重均分子量。或者,可以通过在给定条件下测量熔体粘度或熔体流动速率来间接测量分子量。
本发明涉及具有官能化的含氟聚合物基质组合物和纤维增强物的含氟聚合物复合材料。
含氟聚合物:
可用于本发明的含氟聚合物是热塑性均聚物和共聚物,所述共聚物具有按重量计大于50重量%的含氟单体单元,优选大于65重量%,更优选大于75重量%,最优选大于90重量%的一种或多种含氟单体。可用于形成含氟聚合物的含氟单体包括但不限于:偏二氟乙烯(VDF或VF2),四氟乙烯(TFE),三氟乙烯(TrFE),氯三氟乙烯(CTFE),六氟丙烯(HFP),氟乙烯(VF),六氟异丁烯(HFIB),全氟丁基乙烯(PFBE),五氟丙烯,3,3,3-三氟-1-丙烯,2-三氟甲基-3,3,3-三氟丙烯,氟化乙烯基醚,包括全氟甲基醚(PMVE),全氟乙基乙烯基醚(PEVE),全氟丙基乙烯基醚(PPVE),全氟丁基乙烯基醚(PBVE),长链全氟化乙烯基醚,氟化间二氧化环戊烯,C4和更高碳的部分氟化或全氟化的α烯烃,C3和更高碳的部分氟化或全氟化的环烯烃,以及它们的组合。
特别优选的含氟聚合物是聚偏二氟乙烯(PVDF)均聚物和共聚物,例如来自阿科玛公司的树脂,以及乙烯四氟乙烯(ETFE)共聚物。尽管本发明适用于所有含氟聚合物及其共聚物,但偏二氟乙烯聚合物将用于说明本发明。本领域普通技术人员将理解并且能够将对PVDF的特定叙述应用于这些其他热塑性聚合物,这些被认为是在本发明的范围内并且在本发明中实施。
本发明中使用的PVDF通常通过本领域已知的方法,使用水性自由基乳液聚合来制备,但是也可以使用悬浮聚合、溶液聚合和超临界CO2聚合方法。在一般的乳液聚合方法中,向反应器中加入去离子水,能够在聚合过程中乳化反应物质的水溶性表面活性剂,和任选的石蜡防污剂。在一个优选的实施方式中,表面活性剂是非氟表面活性剂,并且产生的最终产物是不含氟表面活性剂的。对混合物进行搅拌和脱氧。然后将预定量的链转移剂CTA引入反应器中,将反应器温度升高至所需水平,并将偏二氟乙烯(和可能的一种或多种共聚单体)进料至反应器中。一旦引入了偏二氟乙烯的初始进料并且反应器中的压力已经达到所需水平,就引入引发剂乳液或溶液以开始聚合反应。反应温度可根据所用引发剂的特性而变化,本领域技术人员将知道如何调整。温度通常为约30℃至150℃,优选约60℃至120℃。一旦在反应器中达到所需的聚合物量,将停止单体进料,但是任选地继续引发剂进料以消耗残留单体。排出残余气体(包含未反应的单体),并从反应器中回收胶乳或悬浮液。
PVDF聚合产生的胶乳通常具有10至60重量%,优选10至50重量%的固体含量。通常通过喷雾干燥、凝结或其他已知方法将胶乳减小为粉末形式,以产生干粉。
官能化的含氟聚合物组合物:
形成本发明的纤维增强的含氟聚合物复合材料的基质的官能化的含氟聚合物组合物可以采取任何形式。用于该基质的特别优选的官能化的含氟聚合物组合物包括:
a)包含长含氟聚合物嵌段和一个或多个短官能末端嵌段的含氟聚合物嵌段共聚物;
b)具有含氟聚合物主链和一个或多个接枝官能团的接枝共聚物;
c)具有官能共聚单体单元作为主链聚合物的一部分的含氟聚合物;
d)非官能含氟聚合物和相容性官能非氟聚合物的混合物;
e)具有官能共聚单体和一个或多个短聚丙烯酸末端嵌段的嵌段含氟聚合物,所述官能共聚单体具有偏二氟乙烯单体单元;
f)一种或多种非官能含氟聚合物与a),b)或c)的任何官能含氟聚合物的混合物。
官能化的含氟聚合物嵌段共聚物:
官能化的含氟聚合物可以是具有长的含氟聚合物或含氟共聚物链以及一个或多个短官能末端嵌段的嵌段共聚物。官能末端嵌段由官能链转移剂形成。
一些实施方式的官能链转移剂是低分子量官能聚合物。低分子量是指聚合物的聚合度小于或等于1,000,优选小于800。在一个优选的实施方式中,通过GPC测量的聚合物链转移剂的重均分子量为20,000克/摩尔以下,更优选15,000克/摩尔,更优选小于10,000克/摩尔。在一个实施方式中,重均分子量小于5,000克/摩尔。低分子量官能链转移剂是具有两个或更多个单体单元,优选至少三个或更多个单体单元的聚合物或低聚物。在一些实施方式中,低分子量官能链转移剂是具有十个或更多个单体单元的聚合物或低聚物。
如在一些实施方式中使用的,官能聚合物链转移剂是指低分子量聚合物链转移剂包含一个或多个不同的官能团。链转移剂具有式(CH2-CH-(X)-R)y,其中y是2至1000之间的整数,X是连接基团,包括但不限于共价键或离子键,烷基,烯基,炔基,取代的烷基,取代的烯基,芳基,酯基,醚基,酮基,胺基,氨化物基(amid),酰胺基,有机硅烷基,且R为官能团。
官能团(R)提供官能性,并且可以通过官能单体(作为单一单体或共聚单体)的聚合来提供。可以通过在聚合之前和/或聚合反应期间将官能链转移剂引入聚合介质中来添加官能性。可用的官能团包括但不限于羧基,羟基,硅氧烷基,醚基,酯基,磺酸基,磷酸基,膦酸基,硫酸基,酰胺基和环氧基,或它们的组合。一些实施方式包括官能链转移剂,其包括但不限于聚丙烯酸,聚乳酸,聚膦酸,聚磺酸和聚马来酸。在酸基的情况下,官能团可以被部分或完全中和和/或酯化。聚丙烯酸链转移剂是优选的实施方式。
基于单体的总量,低分子量官能链转移剂在聚合反应中的存在量为0.1至25重量%。优选该量为0.25至15重量%,更优选为0.5至10重量%。在一个实施方式中,链转移剂的量为大于2重量%至10重量%,甚至为2.2至8重量%。如果官能化链转移剂的量太低,则提供给PVDF的官能性不足以提供任何显著的性能优势,也不足以获得所需的分子量。
低分子量聚合物官能链转移剂与生长的聚合物链的活性中心反应,导致夺取CH的H并使残留的低分子量官能团与聚合物链连接。该聚合物链转移剂与共聚单体的不同之处在于,它不会破坏PVDF主链的序列分布。可以通过NMR在官能化PVDF中检测残留的低分子量官能聚合物链转移剂的存在。
除了一些实施方式的低分子量官能链转移剂之外,还可以以提供期望分子量所需的量添加常用于PVDF聚合中的其他链转移剂。
通常,将一部分或全部低分子量链转移剂添加到初始进料中,以防止形成不溶于极性溶剂且以凝胶形式存在的极高分子量聚合物。然后可以将其余的链转移剂连续地或小批量地在剩余的聚合过程中加入。
官能链转移剂产生具有含氟聚合物嵌段和官能非氟聚合物末端嵌段的嵌段共聚物。在另一个实施方式中,亲水性官能团既作为低含量的官能单体(作为含氟聚合物主链的一部分)存在,又作为亲水性非氟聚合物末端嵌段存在。出乎意料的是,即使在含氟聚合物嵌段中具有非常低的亲水性单体含量,该嵌段共聚物也显示出协同作用。含氟聚合物嵌段中的亲水性共聚单体的用量可以例如为基于全部单体的约0.0001至约10重量%。基于含氟聚合物嵌段中的全部单体,亲水性单体含量小于500ppm,小于250ppm,小于100ppm,小于50ppm,甚至低至10ppm提供了粘合性和其他性能的协同改善。
在含氟聚合物嵌段的合成过程中,亲水性单体要么随机分布在聚合物背景中,要么形成均聚物,要么未反应。在一个实施方式中,亲水性单体是(甲基)丙烯酸类单体,并且非氟聚合物嵌段是(甲基)丙烯酸类单体的聚合物。在这种情况下,无规分布在含氟聚合物嵌段中的(甲基)丙烯酸类单体单元的总量小于整个嵌段共聚物中全部(甲基)丙烯酸类单体单元的40摩尔%,优选小于30摩尔%,优选小于25摩尔%,甚至小于20摩尔%,小于15摩尔%,甚至小于10摩尔%。由于在含氟聚合物嵌段中的(甲基)丙烯酸类单体的摩尔百分数低并且结合到非氟聚合物嵌段中的(甲基)丙烯酸类单体单元的含量较高,因此无规分布在嵌段共聚物的含氟聚合物嵌段中的(甲基)丙烯酸类单体单元的摩尔百分数低。含氟聚合物嵌段中的(甲基)丙烯酸类单体可以与非氟聚合物嵌段中的(甲基)丙烯酸类单体相同或不同。在一个优选的实施方式中,丙烯酸单体单元同时存在于含氟聚合物嵌段和非氟聚合物嵌段中。
嵌段共聚物的官能含氟聚合物嵌段具有高分子量,其中具有式–CF2H和/或-OSO3H和/或-OH的端基的量小于30毫摩尔/千克偏二氟乙烯(VDF)重复单元,优选小于25毫摩尔/千克VDF,更优选小于20毫摩尔/千克VDF。
在一个优选的实施方式中,链转移剂与表面活性剂结合使用以稳定生长的聚合物链。表面活性剂可以是已知的能稳定含氟聚合物的任何表面活性剂,并且可以是一种或多种氟化表面活性剂,一种或多种非氟化表面活性剂,或氟化和非氟化表面活性剂的混合物。在一个优选的实施方式中,如申请人在先前的专利申请中所表明的,聚合是在没有任何氟化表面活性剂的情况下进行的。可用的非氟化表面活性剂可产生粒度为50至250nm的稳定乳液。
官能化的接枝含氟共聚物:
本发明复合材料的官能含氟聚合物基质可包含一定量的已被不饱和羧酸官能单体接枝(如US 7,241,817中所述)或被环氧或酰胺官能团接枝的含氟聚合物。接枝过程涉及以下步骤:
a)将含氟聚合物与不饱和单体熔融混合;
b)将a)中获得的混合物形成膜、片、颗粒或粉末;
c)在无空气的情况下,将步骤b)的产物暴露于剂量为1-15Mrad的光子(γ)或电子(β)辐射;和
d)任选地处理在c)中获得的产物,以除去未接枝到含氟聚合物上的全部或部分不饱和单体。
所获得的接枝含氟聚合物可以就这样使用,或者作为与相同但未接枝的含氟聚合物或另一种含氟聚合物的混合物使用。基质中接枝含氟聚合物的含量为1至100重量%,优选为3至50重量%,最优选为5至20重量%。
可用的不饱和羧酸单体的实例包括具有2至20个碳原子的羧酸,例如丙烯酸,甲基丙烯酸,马来酸,富马酸和衣康酸;这些酸的官能衍生物,包括但不限于不饱和羧酸的酸酐、酯衍生物、酰胺衍生物、酰亚胺衍生物和金属盐(例如碱金属盐)。还可以提及十一碳烯酸;具有4-10个碳原子的不饱和二羧酸及其官能衍生物,特别是它们的酸酐,是特别优选的接枝单体。
其他接枝单体的实例包括不饱和羧酸的C1-C8烷基酯或缩水甘油酯衍生物,例如丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸乙酯,甲基丙烯酸乙酯,丙烯酸丁酯,甲基丙烯酸丁酯,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,马来酸单乙酯,马来酸二乙酯,富马酸单甲酯,富马酸二甲酯,衣康酸单甲酯和衣康酸二乙酯;不饱和羧酸的酰胺衍生物,例如丙烯酰胺,甲基丙烯酰胺,马来酸的单酰胺,马来酸的二酰胺,马来酸的N-单乙酰胺,马来酸的N,N-二乙酰胺,马来酸的N-单丁酰胺,马来酸的N,N-二丁酰胺,富马酸的单酰胺,富马酸的二酰胺,富马酸的N-单乙酰胺,富马酸的N,N-二乙酰胺,富马酸的N-单丁酰胺和富马酸的N,N-二丁酰胺;不饱和羧酸的酰亚胺衍生物,例如马来酰亚胺,N-丁基马来酰亚胺和N-苯基马来酰亚胺;以及不饱和羧酸的金属盐,例如丙烯酸钠,甲基丙烯酸钠,丙烯酸钾和甲基丙烯酸钾。
步骤a)在任何混合设备中进行,例如在热塑性塑料工业中使用的挤出机或混合机中进行。
关于含氟聚合物和不饱和单体的比例,按重量计,含氟聚合物的比例有利地为90至99.9%,不饱和单体相应地为0.1至10%。优选地,含氟聚合物的比例为92至99.0%,而不饱和单体相应地为1.0至8%,更优选地为1至5重量%的不饱和接枝单体。
关于步骤c),将在步骤b)之后回收的产物有利地包装在聚乙烯袋中,将空气排出,然后将袋封闭。关于辐射方法,可以同等使用电子辐射(通常称为β辐射)和光子辐射(通常称为γ辐射)。有利地,剂量在2至6Mrad之间,优选地在3至5Mrad之间。
关于步骤d),可以通过任何方式除去未接枝的单体。相对于在步骤c)开始时存在的单体,接枝单体的比例为50至100%。可以用对含氟聚合物和接枝官能团呈惰性的溶剂进行洗涤操作。例如,当将马来酸酐用于接枝时,可以将氯苯用于洗涤。也可以更简单地对步骤c)中回收的产物进行真空脱气。
在一个实施方式中,马来酸酐接枝的含氟聚合物基质仅与短(短切)纤维一起使用。在另一个实施方式中,马来酸酐接枝的官能基质与含氟聚合物上胶的纤维一起使用。
在一实施方式中,接枝单体不是马来酸酐。
具有官能共聚单体的官能含氟聚合物
本发明的官能PVDF基质可以是80至99摩尔%,优选85至98.8摩尔%的一种或多种含氟单体的共聚物,所述含氟单体包括但不限于偏二氟乙烯(VDF),四氟乙烯(TFE),乙烯-四氟乙烯(ETFE)和/或氯三氟乙烯(CTFE)。与非氟聚合物相比,含氟聚合物的化学惰性提供了较长的复合材料寿命。在一个优选的实施方式中,共聚物包含80至99摩尔%的VDF单体单元。
共聚物还包括一种或多种改善粘合性的官能共聚单体,该官能共聚单体以基于共聚物0.005至20摩尔%,优选0.01至10摩尔%,最优选0.03至5摩尔%的低含量使用。官能共聚单体的存在为共聚物提供了比含氟均聚物更好的粘合性。
无规共聚物是最有用的,因为其提供了更好的粘合基团分布,从而导致了更好的粘合性。本发明还考虑了接枝共聚物。
可用的共聚单体通常包含极性基团,或者具有高表面能。可用的共聚单体的实例包括但不限于以下的一种或多种:乙酸乙烯酯,2,3,3,3-四氟丙烯(HFO-1234yf),2,3,3三氟丙烯,六氟丙烯(HFP)和2-氯-1-1-二氟乙烯(R-1122)。HFP提供了良好的粘合性,但可能会降低耐溶剂性。磷酸(甲基)丙烯酸酯,(甲基)丙烯酸和羟基官能(甲基)丙烯酸类共聚单体也可以用作共聚单体。
与一种或多种含氟单体组合使用的其他可用的粘合剂共聚单体包括但不限于以下的一种或多种:
A)乙烯基烷基酸,具有共聚单体(M1)的结构:
其中R1、R2和R3是氢或卤素(F,Cl,Br,I)。
其中R4为C1-C16直链、支化、芳基或环烷基,C1-C16氟化的直链、支化、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物。
其中R5是羧酸(C(O)OH),碱金属羧酸盐(COO-M+),羧酸铵盐(COO-NH4 +),羧酸烷基铵盐(COO-N(烷基)4 +),醇(OH),酰胺(C(O)NH2),二烷基酰胺(C(O)N烷基2),磺酸(S(O)(O)OH),碱金属磺酸盐(S(O)(O)O-M+),磺酸铵盐(S(O)(O)O-NH4 +),磺酸烷基铵盐(S(O)(O)O-N(烷基)4 +)。
B)乙烯基烷基酸,具有下式(M2)的结构:
其中:R1、R2和R3是氢或卤素(F,Cl,Br,I);
其中:R4和R5各自是氢,C1-C16直链烷基、支化烷基、芳基或环烷基,C1-C16氟化的直链烷基、支化烷基、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物,碱金属离子(Li+,Na+,K+,Rb+,Cs+),铵离子(NH4 +)或烷基铵(N烷基4 +)。
C)官能丙烯酸酯,具有共聚单体(M3)的结构:
其中R1、R2和R3是氢或卤素(F,Cl,Br,I);
其中R4为键,C1-C16直链、支化、芳基或环烷基,C1-C16氟化的直链、支化、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物。
其中R5是羧酸(C(O)OH),碱金属羧酸盐(COO-M+),羧酸铵盐(COO-NH4 +),羧酸烷基铵盐(COO-N(烷基)4 +),醇(OH),酰胺(C(O)NH2),二烷基酰胺(C(O)N烷基2),磺酸(S(O)(O)OH),碱金属磺酸盐(S(O)(O)O-M+),磺酸铵盐(S(O)(O)O-NH4 +),磺酸烷基铵盐(S(O)(O)O-N(烷基)4 +),环氧化物,C1-C16烷基或环烷基碳酸酯。
在一个实施方式中,发现两种或更多种不同的官能丙烯酸酯提供增加的粘合性。尽管不受任何特定理论的束缚,但据信,不同的官能团,例如醇和酸官能团,可以反应或交联形成酯基。两种或更多种不同的官能团优选存在于同一三元共聚物中,但是也可以是两种或更多种不同共聚物的混合物。
D)官能丙烯酰胺,具有共聚单体(M4)的结构:
其中:R1、R2和R3是氢或卤素(F,Cl,Br,I)。
其中:R4和R6各自是C1-C16直链、支化、芳基或环烷基,C1-C16氟化的直链、支化、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物。
其中:R5和R7分别是羧酸(C(O)OH),碱金属羧酸盐(COO-M+),羧酸铵盐(COO-NH4 +),羧酸烷基铵盐(COO-N(烷基)4 +),醇(OH),酰胺(C(O)NH2),二烷基酰胺(C(O)N烷基2),磺酸(S(O)(O)OH),碱金属磺酸盐(S(O)(O)O-M+),磺酸铵盐(S(O)(O)O-NH4 +),磺酸烷基铵盐(S(O)(O)O-N(烷基)4 +),或膦酸盐/酯(P(O)(OH)2),碱金属磷酸盐或磷酸铵。
E)碳酸盐/酯,含有共聚单体M5:
其中:R1、R2和R3是氢或卤素(F,Cl,Br,I)。
其中:其中R4是键,C1-C16直链烷基、支化烷基、芳基或环烷基,C1-C16氟化的直链烷基、支化烷基、芳基或环烷基。
其中:R5是C1-C16环烷基,C1-C16氟化环烷基,其含有碳酸根/碳酸酯基作为环状结构的一部分。
F)乙烯基醚,具有共聚单体(M6)的结构:
其中:R1、R2和R3是氢或卤素(F,Cl,Br,I)。
其中:R4是C1-C16直链、支化、芳基或环烷基,C1-C16氟化的直链、支化、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物。
其中:R5是羧酸(C(O)OH),碱金属羧酸盐(COO-M+),羧酸铵盐(COO-NH4 +),羧酸烷基铵盐(COO-N(烷基)4 +),醇(OH),酰胺(C(O)NH2),二烷基酰胺(C(O)N烷基2),磺酸(S(O)(O)OH),碱金属磺酸盐(S(O)(O)O-M+),磺酸铵盐(S(O)(O)O-NH4 +),磺酸烷基铵盐(S(O)(O)O-N(烷基)4 +)。
G)烯丙氧基化合物,具有作为共聚单体(M7)的结构:
其中:R1、R2和R3是氢或卤素(F,Cl,Br,I)。
其中:R4是C1-C16直链、支化、芳基或环烷基,C1-C16氟化的直链、支化、芳基或环烷基,六氟环氧丙烷的低聚物或四氟环氧乙烷的低聚物。
其中:R5是羧酸(C(O)OH),碱金属羧酸盐(COO-M+),羧酸铵盐(COO-NH4 +),羧酸烷基铵盐(COO-N(烷基)4 +),醇(OH),酰胺(C(O)NH2),二烷基酰胺(C(O)N烷基2),磺酸(S(O)(O)OH),碱金属磺酸盐(S(O)(O)O-M+),磺酸铵盐(S(O)(O)O-NH4 +),磺酸烷基铵盐(S(O)(O)O-N(烷基)4 +),或膦酸盐/酯(P(O)(OH)2),碱金属磷酸盐或磷酸铵。
非官能含氟聚合物与官能相容性聚合物的混合物
在一些实施方式中,官能含氟聚合物是包含聚偏二氟乙烯和相容性官能非氟化聚合物(如至少一种甲基丙烯酸单体和至少一种甲基丙烯酸甲酯单体的官能丙烯酸类共聚物)的混合物。相容性官能非氟化聚合物与聚偏二氟乙烯相容。将聚偏二氟乙烯和相容性官能非氟化聚合物熔融混合以形成本发明的官能PVDF。
在一些实施方式中,相容性官能非氟化聚合物包括至少一种选自下组的单体:α,β不饱和羧酸,含有羟基的丙烯酸类单体,含有环氧基的单体,含有硅烷醇的单体,含有醛的单体,烯基氰化物和甲基丙烯酸乙酰乙酰氧基乙酯。
在一些实施方式中,包含α,β不饱和羧酸的单体是至少一种选自下组的单体:丙烯酸,甲基丙烯酸,富马酸,巴豆酸和衣康酸。
在一些实施方式中,含有羟基的丙烯酸类单体选自下组:甲基丙烯酸羟乙酯,丙烯酸羟乙酯,丙烯酸羟丙酯,甲基丙烯酸羟丙酯和二甘醇乙基醚丙烯酸酯。
在一些实施方式中,含有环氧基的单体选自下组:丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。
在一些实施方式中,含硅烷醇的单体选自下组:γ-三甲氧基硅烷甲基丙烯酸酯和γ-三乙氧基硅烷甲基丙烯酸酯。
在一些实施方式中,含有醛的单体是丙烯醛。
在一些实施方式中,烯基氰化物单体选自下组:丙烯腈和甲基丙烯腈。
在一些实施方式中,相容性官能非氟化聚合物包括至少一种选自下组的单体:丙烯酸,甲基丙烯酸,富马酸,巴豆酸,衣康酸,甲基丙烯酸羟乙酯,丙烯酸羟乙酯,丙烯酸羟丙酯,甲基丙烯酸羟丙酯,二甘醇乙基醚丙烯酸酯,丙烯酸缩水甘油酯,甲基丙烯酸缩水甘油酯,γ-三甲氧基硅烷甲基丙烯酸酯,γ-三乙氧基硅烷甲基丙烯酸酯,丙烯醛,丙烯腈,甲基丙烯腈和甲基丙烯酸乙酰乙酰氧基乙酯。
在一些实施方式中,相容性官能非氟化聚合物是包含至少一种甲基丙烯酸单体和至少一种甲基丙烯酸甲酯单体的官能丙烯酸类共聚物。在一些实施方式中,相容性官能非氟化共聚物是酸共聚物,其中酸基部分转化为酸酐官能团。
在一些实施方式中,含氟聚合物不含官能团。在一些实施方式中,含氟聚合物是偏二氟乙烯聚合物,乙烯四氟乙烯聚合物或乙烯氯三氟乙烯聚合物。
在一些实施方式中,将含氟聚合物官能化。官能化的含氟聚合物可以是官能化的偏二氟乙烯聚合物,官能化的乙烯四氟乙烯聚合物或官能化的乙烯氯三氟乙烯聚合物。
在一些实施方式中,官能聚偏乙烯聚合物混合物包含约1重量%至约20重量%的官能丙烯酸类共聚物。在一些实施方式中,聚偏乙烯聚合物混合物包含小于5重量%的官能丙烯酸类共聚物。不受理论的束缚,过量的官能丙烯酸类共聚物(例如大于20重量%)可能降低通过混合由该官能PVDF制备的热塑性复合材料的耐化学性。
官能丙烯酸类共聚物可包含约1.5重量%至约15重量%的(甲基)丙烯酸单体或马来酸酐。在一些实施方式中,官能丙烯酸类共聚物可包含约5重量%至约15重量%的(甲基)丙烯酸单体或马来酸酐。在一些实施方式中,官能丙烯酸类共聚物可包含约6重量%至约11重量%的(甲基)丙烯酸单体或马来酸酐。
如上所述,在一些实施方式中,聚偏乙烯聚合物混合物包含PVDF和官能丙烯酸类共聚物。甲基丙烯酸单体的总含量可以描述为全部聚偏乙烯聚合物混合物的一部分或官能丙烯酸类共聚物的一部分。除非另有说明,否则将甲基丙烯酸单体描述为聚偏乙烯聚合物混合物的一部分。
聚偏乙烯聚合物混合物可包含按重量计约50ppm至约30,000ppm的甲基丙烯酸单体。在一些实施方式中,聚偏乙烯聚合物混合物可包含按重量计约500ppm至约10,000ppm的甲基丙烯酸单体。
在一些实施方式中,聚偏乙烯聚合物混合物可包含按重量计至少约100ppm,约200ppm,约300ppm,约400ppm,约500ppm,约600ppm,约700ppm,约800ppm,约900ppm,约1000ppm,约2000ppm,约3000ppm,约4000ppm或约5000ppm的甲基丙烯酸单体。
在一些实施方式中,聚偏乙烯聚合物混合物可包含按重量计最多约10,000ppm,约5000ppm,约2800ppm,约2600ppm,约2500ppm,约2400ppm,约2300ppm,约2200ppm,约2100ppm,约2000ppm,约1900ppm,约1800ppm,约1700ppm,约1600ppm,约1500ppm,约1400ppm,约1300ppm,约1200ppm,约1100ppm或约1000ppm的甲基丙烯酸单体。
同时具有官能末端嵌段和官能共聚单体的嵌段共聚物。
所述官能含氟聚合物基质可包括含氟聚合物,该含氟聚合物在所述含氟聚合物嵌段的主链中具有低含量的官能单体,并且该含氟聚合物还具有官能非氟聚合物短末端嵌段。这将是类似的含氟聚合物嵌段共聚物,例如如上所述的具有PAA链转移剂末端嵌段,但在含氟聚合物嵌段中存在额外的官能团。尽管官能共聚单体的含量可以与上述官能含氟共聚物的范围相同,但是由于含氟聚合物嵌段中的官能共聚单体是在由官能末端嵌段贡献的官能团之外附加的,所以官能共聚单体的含量不应太高。少量无规分布的共聚单体可有效改善复合材料的官能基质与纤维之间的粘合性。基于含氟聚合物嵌段,官能共聚单体的含量可以最高达15摩尔%,但基于含氟聚合物嵌段,低至小于1摩尔%,小于500ppm,小于250ppm,小于150ppm,甚至小于100ppm也是有效的。
非官能含氟聚合物与官能含氟聚合物的混合物
在上述官能含氟聚合物的各情况中,可以进一步与相容性非官能聚合物混合,该相容性非官能聚合物包括但不限于含氟聚合物和(甲基)丙烯酸类聚合物。在一个优选的实施方式中,将官能PVDF和非官能PVDF混合在一起以形成聚合物/纤维复合材料的基质。
纤维
本发明的纤维可以具有各种形式和尺寸,可以是一维、二维或三维的。纤维基材包含一种或多种纤维的组装件。当纤维是连续的时候,其组装件形成织物。
一维形式对应于线性纤维。纤维可以是不连续的、短切的或连续的。纤维可以是短纤维(短切纤维),或者是长的连续纤维,其纵横比为至少1000,优选至少1500,更优选至少2000,有利地至少3000,最有利地至少5000。
二维形式对应于纤维垫或非织造增强物或织造粗纱或纤维束,其也可以是编织的。
三维形式对应于例如堆叠或折叠的纤维垫或非织造增强物或纤维束或其混合物,即二维形式的三维组装件。
纤维材料的来源通常是合成。合成材料包括选自热固性聚合物纤维,热塑性聚合物纤维或其混合物的聚合物纤维。聚合物纤维可以由聚酰胺(脂族或芳族)、聚酯、聚乙烯醇、聚烯烃、芳族聚酰胺、聚氨酯、聚氯乙烯、聚乙烯、不饱和聚酯、环氧树脂和乙烯基酯组成。矿物纤维也可以选自玻璃纤维,特别是E、R或S2型玻璃纤维,碳纤维,硼纤维或二氧化硅纤维。含氟聚合物复合材料的优选纤维是碳纤维、玻璃纤维和芳族聚酰胺纤维。
纤维需要一些表面官能度,以便与含氟聚合物基质的官能团相互作用。可以通过纤维的表面处理或上胶来增加官能度。
在一个实施方式中,纤维用官能含氟聚合物上胶剂上胶,该官能含氟聚合物如以上针对基质的官能含氟聚合物所述形成。纤维上的官能团和基质中的官能团可以相同或不同,只要官能团能够相互作用形成粘合性结合即可。在另一些实施方式中,在不需要额外上胶剂与官能PVDF基质相互作用的情况下,用氧化酸、等离子体或高温氧化处理对纤维进行官能化。
在一些实施方式中,增强纤维是碳纤维并且被活化以形成官能团。在一个实施方式中,官能团是含氧官能团。在一些实施方式中,含氧官能团为C=O基团。在一些实施方式中,未对氧化的碳纤维上胶,而是直接使用该氧化的碳纤维。在另一些实施方式中,则用官能化的PVDF或非氟聚合物官能上胶剂如环氧树脂、聚酰亚胺、聚酰胺等对碳纤维进行上胶。然后,基质的官能粘合剂与“上胶的”或官能化的碳纤维相互作用或粘附到其上以增加基质/粘合剂与碳纤维之间的粘合性。
在一些实施方式中,增强纤维是玻璃纤维,其用硅烷或其他官能聚合物成分(包括可能的官能PVDF上胶剂)上胶。在一些实施方式中,上胶的增强纤维包含硅烷偶联剂。硅烷偶联剂包括官能团和可与玻璃纤维硅烷键合的基团。在一些实施方式中,硅烷偶联剂的官能团是环氧基或酰胺基。硅烷偶联剂的官能团结合至官能聚合物上胶剂,该上胶剂任选地为官能PVDF。在所有实施方式中,官能PVDF基质与纤维增强物相互作用或粘附至纤维增强物以改善性质。
在一些实施方式中,首先用官能硅烷对玻璃纤维上胶,然后用官能含氟聚合物上胶剂进行二次上胶(over-sizing),然后与上述官能PVDF基质一起使用。
实施例
碳纤维上胶:
在本申请中,用官能PVDF制备的经过上胶的碳纤维的所有实施例均以完全相同的方式制成。在所有实施例中均使用了赫氏(Hexcel)AS412,000丝束未上胶碳纤维,要注意的是使用了官能PVDF上胶剂,因为这些在市场上无法买到。将“官能PVDF”溶解在5%DMAC(二甲基乙酰胺)中制成流体溶液。设置了实验室规模的装置,以连续地对该碳纤维上胶,其中对丝束进行涂覆,然后将多余的物料挤出,除去溶剂,将经过上胶的纤维缠绕到卷轴上。
润湿盘盛有5%固含量的溶液,利用辊使AS4丝束通过该溶液,从而将其保持在表面之下。然后使纤维丝束在两个不动的软辊之间通过,以挤出多余的溶液,并促进上胶溶液在碳纤维周围的良好润湿。然后,将“湿上胶的”丝束通过加热到150℃并具有大量空气流的热室,停留时间为90秒,以除去所有溶剂,最后得到“干燥的”经过上胶的碳纤维丝束。通过在上胶前后称重一米的碳纤维,我们计算出上胶量。通过该方法生产的上胶纤维在下表1中显示为实施例A和实施例B。然后使用FG公司(Fiber Glast)提供的专为玻璃纤维设计的空气驱动切碎机,将经过上胶的碳丝束切成6毫米长。
用于这些试验的商业对照碳纤维上胶剂来自帝人东邦特耐克丝公司(TeijinToho Tenax)。牌号为HT C702,其是一种为用于高温热塑性塑料而上胶的碳纤维。将该纤维切成6毫米的标准长度。
除非另有说明,否则100秒-1时熔体粘度约为6千泊的PVDF均聚物用于这些实验。
制备丙烯酸官能PVDF,其中将2500ppm丙烯酸加入到上述聚合反应中,以产生在230℃下100秒-1时熔体粘度为14千泊的官能PVDF均聚物。用该产物作为官能上胶剂(表1中的实施例B和表3中的实施例4和5)和官能基质(表2中的实施例1和2)进行测试。
表1
使用可容纳65克化合物的布拉班德(Brabender)混合碗来制备增强复合材料。首先将基质树脂在混合碗中在230℃和45rpm下熔化(持续1分钟)。然后将预先称重的碳纤维(15重量%)添加到碗中,继续混合2分钟。手动将材料从混合碗中取出,将60克放入压缩模具中。在卡弗(Carver)热压机中于230℃下在3英寸x 5英寸x 1/8英寸的正位移模具中在230℃下将材料压缩成型,在1000psi下进行1分钟,在5000psi下进行2分钟,然后在10,000psi下进行1分钟。移出模具并在冷却压力机中于10,000psi的压力下冷却。然后使用湿的金刚石磨粒瓷砖锯将板材切成0.5英寸x 5英寸的挠曲棒。在50%RH,73℉受控温度实验室中干燥和调理该棒过夜,然后根据ASTM D790在英斯特朗(Instron)4201中进行测试,并以0.05英寸/分钟的挠曲棒配置进行测试。记录挠曲强度。表2列出了碳纤维与官能或非官能基质的各种组合。
表2
结果显示在表2中,其记录了本发明的构思,即官能PVDF基质可以与官能PVDF上胶剂组合,或者与标准的市售上胶碳纤维一起使用时,可以提高热塑性复合材料的强度。
双螺杆挤出测试:
通过上面提到的相同过程产生了其他上胶碳纤维,只要足以完成双螺杆挤出复配研究即可。所生产的上胶碳纤维是上面表1中指出的实施例B-切成6mm的长度。第二种对照碳纤维是HT C702,其可商购并被切成6毫米的长度。
将两个实施例(3和4)和对照配制物在230℃的30mm ZSK双螺杆挤出机上配混,并使用失重侧填充器添加短切碳纤维,以在6千泊粘度的PVDF均聚物中产生15重量%的短切碳纤维。将挤出的线料造粒,然后在220℃下注塑成ASTM D790挠曲棒。将挠曲棒在50%RH和73℉下平衡24小时,然后如上所述测试挠曲强度。
结果如下表3所示。这些结果表明与市售上胶剂相比,官能PVDF上胶剂显示强度增加(实例3)。还表明,将官能PVDF上胶剂与官能PVDF基质组合使用可以进一步提高强度(实施例4)。
表3
其他双螺杆复配实验
对照实施例1:将在100秒-1下熔体粘度(MFR)为6千泊的PVDF均聚物在30mm W&P同向双螺杆挤出机上以36:1的L/D熔融配混,采用下游添加短切碳纤维线料。使用失重进料器将PVDF添加到挤出机的后部,并使用失重进料器,用下游侧填充器添加碳纤维。挤出温度保持在230℃,双螺杆的rpm为200rpm。控制进料以产生具有15重量%碳纤维的最终产物。然后将粒料在230℃的熔融温度和50℃的模具温度下注塑成ASTM D638 1型拉伸棒和ASTM D790挠曲棒。根据这些ASTM程序测试性能。说明:
1)CT-702是可从东邦特耐克丝公司(Toho Tenax)获得的短切碳纤维
2)除非另有说明,否则在所有情况下均使用6千泊的PVDF均聚物
3)使用MMA/MAA-官能丙烯酸类物质,其包含90重量%的甲基丙烯酸甲酯和10重量%的甲基丙烯酸
4)说明(3)的MMA/MAA-酸酐(Anhy)-官能丙烯酸类物质,其中60%至80%的MAA官能团已通过二次反应挤出工艺转化为酸酐官能团
通过将95重量%的230℃和100秒-1下MV为6千泊的PVDF均聚物与5重量%的官能丙烯酸类共聚物MMA/MAA(上述说明3)熔融混合来生产官能PVDF(混合物4)。该丙烯酸类物质与PVDF均聚物相容。实施例5的相容性官能丙烯酸类物质改善了对现有碳纤维上胶剂的粘合性,从而增加了界面粘合性和复合强度。
通过将95重量%的PVDF均聚物与5重量%的官能丙烯酸类共聚物MMA/MAA-酸酐(上述说明4)熔融混合来生产另一种官能PVDF(混合物5)。在实施例4和5中,官能丙烯酸类物质在分子水平上可与PVDF均聚物完全混溶。因此,尽管PMMA上的官能团似乎与所使用的碳纤维结合,但由于其与PVDF完全相容,因此其也改善了向基质的应力传递,从而提高了拉伸强度、挠曲强度和断裂伸长率,如下表4所示。
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Claims (13)
1.一种纤维增强含氟聚合物复合材料,其包含:
a)官能化的含氟聚合物组合物基质;和
b)纤维,
其中,所述官能化的含氟聚合物组合物基质包含以下至少一种:
i)包含长含氟聚合物嵌段和一个或多个短聚丙烯酸末端嵌段的含氟聚合物嵌段共聚物;
ii)具有官能共聚单体单元作为主链聚合物的一部分的含氟聚合物;
iii)非官能含氟聚合物和相容性官能非氟聚合物的混合物;
iv)具有官能共聚单体和一个或多个短聚丙烯酸末端嵌段的嵌段含氟聚合物,所述官能共聚单体具有偏二氟乙烯单体单元;
v)一种或多种非官能含氟聚合物与i),ii)或iv)的混合物,
其中,所述纤维包含具有能够与官能化的含氟聚合物组合物结合的官能团的上胶剂。
2.如权利要求1所述的纤维增强含氟聚合物复合材料,其包含:
a)40-60重量%的所述含氟聚合物基质,和
b)15-60重量%的所述纤维。
3.如权利要求1所述的纤维增强含氟聚合物复合材料,其中所述含氟聚合物基质包含聚偏二氟乙烯均聚物,或包含至少60重量%的偏二氟乙烯单体单元的共聚物。
4.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述嵌段共聚物的末端嵌段包含聚丙烯酸嵌段。
5.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述官能共聚单体选自下组:
乙酸乙烯酯;
2,3,3,3-四氟丙烯;
2,3,3-三氟丙烯;
六氟丙烯;
2-氯-1,1-二氟乙烯;
磷酸(甲基)丙烯酸酯;
(甲基)丙烯酸;
羟基官能(甲基)丙烯酸类物质;
具有下式(M1)的结构的官能共聚单体:
其中R1、R2和R3是氢或者卤素F、Cl、Br或I,其中R4是C1-C16直链或支化的基团,C1-C16氟化的直链或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,其中R5是羧基,碱金属羧酸盐基团,羧酸铵盐基团,羧酸烷基铵盐基团,羟基,酰胺基,二烷基酰胺基,磺酸基,碱金属磺酸盐基团,磺酸铵盐基团,磺酸烷基铵盐基团;
具有下式(M2)的结构的官能共聚单体:
其中:R1、R2和R3是氢或者卤素F、Cl、Br或I,其中:R4和R5各自是氢,C1-C16直链烷基或支化的基团,C1-C16氟化的直链烷基或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,碱金属离子Li+、Na+、K+、Rb+或Cs+,铵离子或烷基铵离子;
官能丙烯酸酯,具有下式(M3)的结构:
其中R1、R2和R3是氢或者卤素F、Cl、Br或I;其中R4是键,C1-C16直链或支化的基团,C1-C16氟化的直链或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,其中R5是羧基,碱金属羧酸盐基团,羧酸铵盐基团,羧酸烷基铵盐基团,羟基,酰胺基,二烷基酰胺基,磺酸基,碱金属磺酸盐基团,磺酸铵盐基团,磺酸烷基铵盐基团,环氧基,C1-C16烷基或环烷基碳酸酯基团;
官能丙烯酰胺,具有下式(M4)的结构:
其中:R1、R2和R3是氢或者卤素F、Cl、Br或I,其中:R4和R6各自是C1-C16直链或支化的基团,C1-C16氟化的直链或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,其中:R5和R7各自是羧基,碱金属羧酸盐基团,羧酸铵盐基团,羧酸烷基铵盐基团,羟基,酰胺基,二烷基酰胺基,磺酸基,碱金属磺酸盐基团,磺酸铵盐基团,磺酸烷基铵盐基团,或膦酸盐/酯基团,碱金属磷酸盐或磷酸铵基团;
碳酸盐/酯,含有下式(M5):
其中:R1、R2和R3是氢或者卤素F、Cl、Br或I,其中:R4是键,C1-C16直链烷基或支化烷基,C1-C16氟化的直链烷基或支化烷基,其中:R5是C1-C16环烷基,C1-C16氟化环烷基,其含有碳酸根/碳酸酯基作为环状结构的一部分;
乙烯基醚,具有下式(M6)的结构:
其中:R1、R2和R3是氢或者卤素F、Cl、Br或I,其中:R4是C1-C16直链或支化的基团,C1-C16氟化的直链或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,其中:R5是羧基,碱金属羧酸盐基团,羧酸铵盐基团,羧酸烷基铵盐基团,羟基,酰胺基,二烷基酰胺基,磺酸基,碱金属磺酸盐基团,磺酸铵盐基团,磺酸烷基铵盐基团;和
烯丙氧基化合物,具有下式(M7)的结构:
其中:R1、R2和R3是氢或者卤素F、Cl、Br或I,其中:R4是C1-C16直链或支化的基团,C1-C16氟化的直链或支化的基团,六氟环氧丙烷的低聚物基团或四氟环氧乙烷的低聚物基团,其中:R5是羧基,碱金属羧酸盐基团,羧酸铵盐基团,羧酸烷基铵盐基团,羟基,酰胺基,二烷基酰胺基,磺酸基,碱金属磺酸盐基团,磺酸铵盐基团,磺酸烷基铵盐基团,或膦酸盐/酯基团,碱金属磷酸盐或磷酸铵基团。
6.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述相容性官能非氟聚合物包含一种或多种官能(甲基)丙烯酸类聚合物。
7.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述纤维选自下组:碳纤维、玻璃纤维和芳族聚酰胺纤维,或它们的混合物。
8.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述纤维包括短切纤维。
9.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述纤维是纵横比至少为1000的长纤维。
10.如权利要求1所述的纤维增强含氟聚合物复合材料,其中,所述上胶剂是官能化的含氟聚合物组合物。
11.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述官能共聚单体选自下组:乙酸乙烯酯,2,3,3,3-四氟丙烯,2,3,3-三氟丙烯,六氟丙烯和2-氯-1,1-二氟乙烯。
12.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述官能共聚单体包含(甲基)丙烯酸酯、(甲基)丙烯酸和羟基官能(甲基)丙烯酸类中的至少一种。
13.如权利要求1-3中任一项所述的纤维增强含氟聚合物复合材料,其中,所述官能共聚单体包含丙烯酸、甲基丙烯酸、羟基官能丙烯酸类或羟基官能甲基丙烯酸类中的至少一种。
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PCT/US2018/042227 WO2019014661A1 (en) | 2017-07-14 | 2018-07-16 | HIGH RESISTANCE POLYVINYLIDENE FLUORIDE COMPOSITE |
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