CN114599510A - 使用基于硅烷的底漆将高度氟化的塑料粘合到弹性体 - Google Patents
使用基于硅烷的底漆将高度氟化的塑料粘合到弹性体 Download PDFInfo
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- CN114599510A CN114599510A CN202080075629.6A CN202080075629A CN114599510A CN 114599510 A CN114599510 A CN 114599510A CN 202080075629 A CN202080075629 A CN 202080075629A CN 114599510 A CN114599510 A CN 114599510A
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- Prior art keywords
- primer
- highly fluorinated
- elastomer
- fluorinated thermoplastic
- uncured
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Abstract
描述了将高度氟化的热塑性塑料粘合到弹性体的方法。该方法包括将包含至少一种芳香族硅烷和至少一种氨基硅烷的底漆施加到未固化的弹性体,以及在施加该述高度氟化的热塑性塑料之前或之后用光化辐射照射该底漆。然后可以固化该弹性体以提供在该高度氟化的热塑性塑料与该固化的弹性体之间具有良好粘附性的制品。
Description
技术领域
本公开涉及使用基于硅烷的底漆***将高度氟化的塑料(例如,全氟塑料)粘合到弹性体(包括含氟弹性体)的方法。还描述了使用此类方法制备的粘合制品。
发明内容
简言之,在一个方面,本公开提供了形成多层制品的方法,该方法包括:(a)将包含(i)芳香族硅烷和(ii)氨基硅烷的底漆施加到包含未固化的弹性体的组合物上;(b)将高度氟化的热塑性塑料施加到该底漆上;(c)用光化辐射照射该底漆;以及(d)在该高度氟化的热塑性塑料与该组合物之间形成粘合。在一些实施方案中,该方法还包括在用光化辐射照射该底漆之后,(e)固化该未固化的弹性体以形成固化的弹性体。
在另一方面,本公开提供了通过根据本公开的方法制备的制品,例如软管。在一些实施方案中,根据层间粘附性测试进行测量,该高度氟化的热塑性塑料与该固化的弹性体之间的粘附力为至少5N/cm。
在下面的具体实施方式中还列出了本发明的一个或多个实施方案的细节。本发明的其它特征、目的和优点从具体实施方式和权利要求书中将显而易见。
附图说明
图1示出了根据本公开的一些实施方案的方法。
图2示出了根据本公开的一些实施方案的替代方法。
图3示出了通过根据本公开的方法制备的示例性制品。
具体实施方式
含有氟的聚合物(也称为“含氟聚合物”)包括例如含氟弹性体和含氟热塑性塑料(也称为“氟塑料”)。含氟聚合物通常具有高热稳定性并且在高温下适用。它们在非常低的温度下还显示出极端的韧性和柔韧性。这些含氟聚合物中的许多含氟聚合物,特别是高度氟化的聚合物(例如,全氟化聚合物)通常具有耐化学性并且可能几乎完全不溶于各种溶剂。
含氟聚合物用于各种工业应用。这些应用中的一些应用需要含氟聚合物的有益特征的组合,诸如良好的耐化学性、高温稳定性和低温柔韧性。此类应用可以使用多层构造。例如,在一些应用中,高度氟化的聚合物可以与弹性体组合。此类构造可用于例如燃料管线软管、涡轮增压器软管以及用于化学处理的容器、软管、垫圈和密封件。
多层制品的层之间的粘附性可能需要满足多种性能标准,这取决于成品的用途。然而,当该层中的一层为含氟聚合物时,通常难以建立高粘合强度,这部分是由于含氟聚合物的非粘性品质。当含氟聚合物高度氟化或全氟化时,粘合可能特别具有挑战性。
已提出各种方法来解决该问题。一种方法是在含氟聚合物层与第二层之间使用粘合剂层或接合层。还已采用对含氟聚合物层的表面处理,包括使用强力还原剂或电晕放电,以增强粘附性。
尽管这些和其它方法在高度氟化的热塑性塑料(例如,全氟塑料)与弹性体之间获得良好的粘附性,但仍然具有挑战性。令人惊讶的是,本发明人已经发现用于粘合此类材料的方法对于实现良好粘附性可能是至关重要的。
通常,本公开涉及多层制品,该多层制品包含用粘合组合物(也称为底漆)粘合到弹性体的至少一种高度氟化的热塑性塑料。尽管此类制品的形式没有特别限制并且可以包括片材和模制品,但是此类构造可能特别有益于在软管,例如在燃料管线软管和涡轮增压器软管中使用。
如本文所用,“高度氟化”意指聚合物中卤原子和氢原子总数的至少90%是氟原子。在一些实施方案中,聚合物中卤原子和氢原子总数的至少95%或甚至至少99%是氟原子。例如,在一些实施方案中,聚合物是“完全氟化的”,这意指高度氟化的热塑性塑料的重复单体单元不包含任何碳-氢键;然而含氟聚合物可以包含一些碳-氢键,这些碳-氢键源于聚合中使用的方法和材料,例如乳化剂、引发剂***和/或链转移剂(如果使用的话)。在一些实施方案中,高度氟化的热塑性塑料可以是全氟塑料。
通常,高度氟化的热塑性塑料的选择不受限制。示例性高度氟化的热塑性塑料包括四氟乙烯(TFE)和六氟丙烯(HFP)的共聚物,通常称为FEP;TFE和氟化乙烯基醚的共聚物,例如TFE和全氟丙基乙烯基醚的共聚物,通常称为PFA;TFE、HFP、少量偏二氟乙烯(VF2,也称为VDF)和任选地全氟化乙烯基醚和烯丙基醚(例如,全氟甲基乙烯基醚(PMVE)和全氟(丙基乙烯基醚(PPVE))的共聚物,包括以商品名THV从3M公司(3M Company)获得的聚合物。适合用于制备高度氟化的热塑性塑料的其它单体包括氯三氟乙烯、3-氯五氟丙烯、全氟化乙烯基醚和烯丙基醚以及全氟烷氧基乙烯基醚和烯丙基醚。在一些实施方案中,还可以存在少量烃二烯,诸如乙烯和丙烯,条件是聚合物中卤原子和氢原子总数的至少90%(例如,至少95%或甚至至少99%)为氟原子。
合适的弹性体包括氟化弹性体(“含氟弹性体”)和非氟化弹性体。氟化弹性体包括部分氟化弹性体(“FKM”ASTM D1418-17,在ISO/DIN 1629标准下也称为“FPM”)、全氟化弹性体(“FFKM”)和氟化乙烯/丙烯橡胶(TFE/P称为“FEPM”)。通常,FKM弹性体是包括偏二氟乙烯重复单元的共聚物,例如HFP和VF2的共聚物;三元共聚物,诸如TFE/HFP/VF2;TFE/VF2/丙烯;和TFE/VF2/PMVE。通常,FFKM弹性体是TFE和全氟化醚的共聚物,该全氟化醚包括全氟烷基乙烯基醚、全氟烷氧基乙烯基醚、全氟烷基烯丙基醚和全氟烷氧基烯丙基醚。
示例性的非氟化弹性体包括丙烯腈-丁二烯橡胶(NBR)、丁二烯橡胶、氯化聚乙烯和氯磺化聚乙烯、氯丁二烯橡胶、乙烯-丙烯单体(EPM)橡胶、乙烯-丙烯-二烯单体(EPDM)橡胶、表氯醇(ECO)橡胶、聚异丁烯橡胶、聚异戊二烯橡胶、聚硫橡胶、聚氨酯、硅酮橡胶、聚氯乙烯和NBR的共混物、苯乙烯丁二烯(SBR)橡胶、乙烯-丙烯酸酯共聚物橡胶和乙烯乙酸乙烯酯橡胶。
已经使用包含吸光化合物和电子供体的粘合组合物将含氟聚合物粘合到各种基底上。例如美国专利第6,630,047号描述使用包含吸光化合物和电子供体的粘合组合物将含氟聚合物粘附到各种基底上。描述了各种合适的吸光化合物,包括具有能够受光化辐射激发的部分(诸如芳香族部分)的那些吸光化合物。还描述了多种电子供体,包括胺,诸如伯胺和氨基取代的有机硅烷。类似地,美国专利第6,685,793号描述了使用包含吸光电子供体的粘合组合物将含氟聚合物粘附到基底上。合适的吸光电子供体包括氟化胺和氟化苯胺。粘合组合物还可以包括脂肪族胺或芳香族胺,包括氨基取代的有机硅烷。
本公开的粘合组合物包含(i)芳香族硅烷和(ii)氨基硅烷。
适合用于本公开的芳香族硅烷包括根据式(I)的那些芳香族硅烷:
Ar-L-Si-Y3(I),
其中Ar是芳香族基团并且L是共价键或二价连接基团。在一些实施方案中,每个Y独立地选自-OH和-OR1,其中R1是烷基,例如C1至C6的直链或支链烷基。在一些实施方案中,假如至少一个Y是-OH或-OR1,则该Y基团中的一个或两个Y基团可以是C1至C4烷基。在一些实施方案中,Ar是苄基,任选地经取代的苄基,诸如苯基。在一些实施方案中,L是具有例如1至12个碳原子的直链烯烃或具有例如3至8个碳原子的环烯烃。在一些实施方案中,连接基团包含杂原子(例如,氧、磷、硫或氮)。在一些实施方案中,连接基团包含氮原子并且芳香族硅烷是芳香族氨基硅烷。在一些实施方案中,芳香族氨基硅烷是根据式(II)的芳香族氨基硅烷:
Ar-N(X)-Si-Y3(II),
其中Ar是芳香族基团(例如,苯基)。在一些实施方案中,X是氢并且该化合物包含仲胺。在一些实施方案中,X是有机基团,任选地含有杂原子(例如,氧),并且该化合物包含叔胺。在一些实施方案中,X是具有例如1至8个碳原子,例如1至4个碳原子的直链或支链烷基。在一些实施方案中,每个Y独立地选自-OH和-OR1,其中R1是烷基,例如C1至C6的直链或支链烷基。在一些实施方案中,假如至少一个Y是-OH或-OR1,则该Y基团中的一个或两个Y基团可以是C1至C4烷基。
适合用于本公开的一些实施方案中的示例性芳香族硅烷包括N-苯基氨基烷基三烷基硅烷和N-苯基氨基烷基三烷氧基硅烷,例如N-苯基氨基甲基三乙氧基硅烷。
适合用于本公开的粘合组合物中的氨基硅烷包括根据式(III)的那些氨基硅烷:
R2R3N-Q-SiZ3(III),
其中:R2和R3中的每一个独立地是H、C1至C12烯基、烯基或炔基或芳香族基团,并且Q是二价连接基团。在一些实施方案中,Q是二价直链C1-12亚烷基、C3-8亚环烷基、3-8元环杂环亚烷基、C1-12亚烯基、C3-8亚环烯基、3-8元环杂环亚烯基、亚芳基或亚杂芳基。在一些实施方案中,Q任选地被以下基团取代:C1-4烷基、C2-4烯基、C2-4炔基、C1-4烷氧基、羟基、卤基、羧基、氨基、硝基、氰基、C3-6环烷基、3-6元杂环烷基、单环芳基、5-6元环杂芳基、C1-4烷基羰氧基、C1-4烷基氧基羰基、C1-4烷基羰基、甲酰基、C1-4烷基羰基氨基或C1-4氨基羰基。
在式(III)中,每个Z独立地选自卤素、烷基(例如,C1至C8烷基)、烷氧基(例如,C1至C8烷氧基)、烷基羰氧基(例如,C1至C8烷基羰氧基)或氨基。
适合用于本公开的一些实施方案中的示例性氨基硅烷包括(氨基烷基)三烷基硅烷、(氨基烷基)三烷氧基硅烷、(氨基烷基)二烷基烷氧基硅烷和(氨基烷基)二烷氧基烷基硅烷。在一些实施方案中,可以使用(3-氨基丙基)三甲氧基硅烷。在一些实施方案中,连接基团Q包含一个或多个氨基。例如,在一些实施方案中,合适的氨基硅烷包括N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷和3-[2-(2-氨基乙基氨基)乙基氨基]丙基三甲氧基硅烷等。
通常,含有粘合组合物的涂层通过将至少一种芳香族硅烷(例如芳香族氨基硅烷)与至少一种不同于该芳香族硅烷的氨基硅烷在溶剂中组合而制备。在一些实施方案中,按涂层组合物(包括溶剂)的总重量计,涂层包含1重量%至10重量%,例如2重量%至10重量%,或甚至3重量%至6重量%的芳香族硅烷。在一些实施方案中,按涂层组合物(包括溶剂)的总重量计,涂层包含0.05重量%至5重量%,例如0.1重量%至5重量%、0.1重量%至3重量%或甚至0.1重量%至1重量%的氨基硅烷。涂层组合物可以包括其它材料,诸如染料、干燥助剂、涂层助剂等。
这些组分可以与任何合适的溶剂组合。合适的溶剂是本领域已知的,并且可以取决于所选择的特定硅烷以及将施加底漆的基底。合适的溶剂包括包含以下的那些溶剂:至少一种有机溶剂,诸如醇(例如,甲醇、乙醇和丙醇)和/或氟化溶剂。在一些实施方案中,溶剂可包含水。尽管没有特别限制,但是涂层组合物可以包含至多98重量%,例如至多96重量%或至多94重量%的溶剂。在一些实施方案中,涂层组合物包含至少80重量%,例如至少90重量%或甚至至少95重量%的溶剂。
除了选择在粘合组合物中使用的组分以外,本发明人还发现当试图将高度氟化的热塑性塑料粘合到弹性体时,用于形成粘合的方法在实现所需粘合强度方面起关键作用。这通过以下实施例举例说明。
实施例:
表1:实施例的制备中所使用的材料汇总。
底漆A。通过将2.01重量%的APMS和0.67重量%的苯基硅烷混合在甲醇中制备底漆A作为涂层组合物。
氟化弹性体(FE-1)。通过使表2A中列出的材料复合制备FE-1。
表2A:可固化含氟弹性体的组成(量以重量份(pbw)为单位示出)。
组分 | FE-1 |
ELAST-1 | 100 |
N-990 | 30 |
CaO | 6 |
Ca(OH)2 | 3 |
MgO | 3 |
蜡 | 1 |
非氟化弹性体(NFE-1)。通过使表2B中列出的材料复合制备NFE-1。
表2B:可固化非氟化弹性体的组成(量以pbw为单位示出)。
组分 | NFE-1 |
ELAST-2 | 100 |
N-762 | 60 |
CaO | 5 |
Ca(OH)2 | 5 |
Plast-1 | 5 |
POx | 3.5 |
硬脂酸 | 2 |
DBU | 0.7 |
通过在93℃(200℉)下以2mm(0.08英寸)的厚度将所需的弹性体组合物(例如,FE-1或NFE-1)按压在两个释放衬垫之间来制备未固化的弹性体的片材。
实施例1-实施例3根据图1所示的本发明的一种示例性方法制备。通常,将底漆(103)以涂层组合物形式施加到未固化的弹性体(101)上并干燥以去除溶剂(步骤120)。接下来,将高度氟化的热塑性塑料(104)施加到涂有底漆的未固化的弹性体上(步骤130)。将底漆暴露于穿过高度氟化的热塑性塑料和/或弹性体的光化辐射(步骤140)以形成中间制品(105),在未固化的弹性体(101)与高度氟化的热塑性塑料(104)之间的界面处有经照射的底漆(113)。在一些实施方案中,然后将这种层压结构中的未固化的弹性体固化(步骤150)以形成制品(106),该制品包含通过经照射的底漆(113)粘合到高度氟化的热塑性塑料(104)的固化弹性体(111)。任选地,该构造可以在固化弹性体之前或之后形成(例如,模制)为所需形状。
在一些实施方案中,底漆可以暴露于穿过弹性体,或穿过弹性体和氟塑料两者的光化辐射。在一些实施方案中,在施加高度氟化的热塑性塑料之前底漆可以直接地和/或穿过弹性体暴露于光化辐射。
光化辐射是具有能够影响高度氟化的热塑性塑料与弹性体之间在粘合组合物(底漆)存在下的粘合的波长的电磁辐射。光化辐射的波长和强度将部分取决于选择的材料(包括芳香族硅烷)。在一些实施方案中,光化辐射的波长可以介于190nm至700nm之间,例如介于200nm至400nm之间、介于205nm至320nm之间、介于210nm至290nm之间或甚至介于240nm至260nm之间。用于传递光化辐射的合适设备和程序是本领域已知的。
可以使用针对所用特定弹性体选择的已知手段来固化弹性体。在一些实施方案中,将弹性体在例如烘箱或高压釜中热固化。
实施例1(EX-1):未固化的FE-1片材用底漆A涂覆并干燥。将FTP-1片材(大约7.6cm×7.6cm×0.25mm厚)层压在两个释放衬垫之间涂有底漆的FE-1片材之上,在93℃下按压五分钟,从压机中取出并使其冷却。用FUSION 500瓦H灯泡以35%强度对层压结构进行UV照射60秒。照射后,将层压材料置于在163℃和496kPa下的蒸汽高压釜中35分钟以固化弹性体。冷却至室温后,测试层压材料的层间粘附性。
以与EX-1相同的方式制备实例EX-2,不同之处在于使用高度氟化的热塑性塑料FTP-2。同样,以与EX-1相同的方式制备EX-3,不同之处在于弹性体是非氟化弹性体NFE-1。
以类似方式制备比较例CE-1至CE-4,不同之处在于将底漆施加到高度氟化的热塑性片材上而不是未固化的弹性体上,并且在层压之前照射底漆。
比较例1(CE-1)。FTP-1片材(大约7.6cm×7.6cm×0.25mm厚)用底漆A涂覆并干燥。用FUSION 500瓦H灯泡以35%强度对底漆进行UV照射60秒。将这种涂有底漆的高度氟化的热塑性片材层压在未固化的含氟弹性体FE-1片材之上(邻近未固化的弹性体有经照射的底漆),置于两个释放衬垫之间,在93℃下按压五分钟,从压机中取出并冷却。然后将层压材料置于在163℃和496kPa下的蒸汽高压釜中35分钟以固化弹性体。冷却至室温后,测试层压材料的层间粘附性。
以与CE-1相同的方式制备比较例CE-2,不同之处在于使用高度氟化的热塑性FTP-2。
以与CE-1相同的方式制备比较例CE-3,不同之处在于将涂有底漆的FTP-1片材层压在固化FE-1片材(邻近固化的弹性体有经照射的底漆)之上,置于两个释放衬垫之间,在93℃下按压三分钟,从压机中取出并冷却。随着弹性体已经固化,没有进行后续高压釜处理。
以与CE-3相同的方式制备比较例CE-4,不同之处在于使用高度氟化的热塑性FTP-2。
以类似于EX-1的方式制备比较例CE-5,不同之处在于将底漆施加到固化的弹性体上而不是未固化的弹性体上。具体地,含氟弹性体FE-1固化片材用底漆A涂覆并干燥。将FTP-1片材(大约7.6cm×7.6cm×0.25mm厚)层压在两个释放衬垫之间涂有底漆的固化FE-1片材之上,在93℃下按压三分钟,从压机中取出并使其冷却。用FUSION 500瓦H灯泡以35%强度对层压结构进行UV照射60秒。随着弹性体已经固化,没有进行后续高压釜处理。
以类似于EX-1的方式制备比较例CE-6,不同之处在于将底漆施加到高度氟化的热塑性片材而不是未固化的弹性体上。与实施例EX-1一样,在层压之后,不照射底漆。具体地,FTP-1片材(大约7.6cm×7.6cm×0.25mm厚)用底漆A涂覆并干燥。将此涂有底漆的高度氟化的热塑性片材层压在未固化的含氟弹性体FE-1片材(邻近未固化的弹性体有固化的底漆)之上,置于两个释放衬垫之间,在93℃下按压五分钟,从压机中取出并使其冷却。用FUSION500瓦H灯泡以35%强度对层压结构进行UV照射60秒。照射后,将层压材料置于在163℃和496kPa下的蒸汽高压釜中35分钟以固化弹性体。冷却至室温后,测试层压材料的层间粘附性。
层间粘附性测试。遵循ASTM D413-76,类型A测试程序,通过在购自明尼苏达州伊登普雷利的MTS***公司(MTS Systems Corporation,Eden Prairie,Minn.)的张力计中以30.5cm/min(12.0in/min)进行180度剥离测试来评估样本的粘合。
根据层间粘附性测试对样品进行测试。结果汇总于表3中。在表3中,“AF”指示“粘附失效”,其中两层分离。“CF”指示“内聚失效”,其中该层中的一层***,这指示当使用相同或类似材料时与AF相比优异的性能。
在一些实施方案中,根据层间粘附性测试进行测量,高度氟化的热塑性塑料与固化的弹性体之间的所需粘附力为至少5N/cm,在一些实施方案中为至少10N/cm、至少15N/cm或甚至至少20N/cm。当失效模式为CF时,测量的力指示层间的最小粘附力,当低于该值时,该层不分离,但是高于该力,该层中的一层***。因此,当失效模式为CF时,层间的粘附力可以高于表3中报告的力。
表3:层间粘附性测试结果。
本公开的一些实施方案的另一示例性方法在图2中示出。一般来讲,未固化的弹性体(201)被挤出或以其它方式形成(步骤210)为片材、软管或其它所需结构(202)。将底漆(203)施加到未固化的弹性体上并干燥以去除溶剂(步骤220)。接下来,将高度氟化的热塑性塑料(204)施加到涂有底漆的未固化的弹性体上,例如挤出到涂有底漆的未固化的弹性体周围(步骤230)。将底漆暴露于穿过高度氟化的热塑性塑料的光化(例如,UV)辐射(步骤240)以形成中间制品205,在未固化的弹性体(201)与高度氟化的热塑性塑料(204)之间的界面处有经照射的底漆(213)。在一些实施方案中,然后将这种多层结构中未固化的弹性体固化(步骤250)以形成固化制品(206),该制品包含通过经光化辐射处理的底漆(213)粘合到高度氟化的热塑性塑料(204)的固化弹性体(211)。
在一些实施方案中,底漆可以暴露于穿过弹性体,或穿过弹性体和氟塑料两者的光化辐射。在一些实施方案中,在施加高度氟化的热塑性塑料之前底漆可以直接地和/或穿过弹性体暴露于光化辐射。
图3示出了在图2的线3-3处所取的固化制品(206)的横截面,显示了通过经照射的底漆(213)粘合到固化弹性体(211)的高度氟化的热塑性塑料(204)。尽管以圆形横截面显示,但是该制品的形式没有特别限制。尽管以空心管显示,但这不是必需的。在一些实施方案中,可以包括附加层,例如粘合到高度氟化的热塑性塑料(204)或固化弹性体(211)的未涂覆表面中的一个或两个表面的材料。
实施例5(EX-5)根据该一般工艺制备。根据表4中汇总的条件挤出6.4mm未固化的含氟弹性体FE-1绳,用底漆A涂覆,然后用高度氟化的热塑性塑料FTP-2涂覆挤出物。将此多层构造切成大约30cm的长度,然后用FUSION 500瓦H灯泡以35%强度以UV光照射60秒。然后将此构造置于在163℃和496kPa下的蒸汽高压釜中35分钟。
测试层间粘附,导致内聚失效,这指示弹性体与高度氟化的热塑性塑料之间坚固粘合。
在本公开的方法中,可以使用任何已知的手段将粘合组合物施加到未固化的弹性体上。示例性方法包括喷涂和辊涂。
尽管实施例示出两层构造,但也可以生产包括更多层的制品。在一些实施方案中,可以包括高度氟化的热塑性塑料的附加层,有或没有附加底漆层。在一些实施方案中,可以包括弹性体(例如,含氟弹性体)的附加层,同样有或没有附加底漆层。在一些实施方案中,本公开的构造可以与基底组合,例如粘合到其它基底上。合适的附加基底包括但不限于金属、聚合物(例如,塑料和弹性体)、玻璃和陶瓷。
在一些实施方案中,高度氟化层和弹性体层中的一者或两者可以包括本领域已知的各种添加剂中的任何添加剂,以实现所需附加特性,诸如颜色和导热性或导电性或电阻、UV或光稳定性。示例性的添加剂包括例如染料、颜料、填料、UV或光稳定剂和加工添加剂。
本公开的方法可以作为单独的步骤进行。在一些实施方案中,该步骤中的一个或多个步骤可以是单个连续过程的一部分。举例来说,在一些实施方案中,本公开的方法可以包括单线,其中(b)可以将底漆施加(例如喷涂)到未固化的弹性体上,并且如有必要的话,干燥;(c)可以将高度氟化的热塑性塑料施加(例如,挤出)到底漆上;以及(d)可以将底漆暴露于穿过高度氟化的热塑性塑料和未固化的氟弹性体中的一者或两者的光化辐射。在一些实施方案中,这种单一工艺还可包括(a)在施加底漆之前形成(例如,挤出)未固化的含氟弹性体。在一些实施方案中,这种单一工艺还可包括(e)固化(例如,热固化)未固化的含氟弹性体。
Claims (20)
1.一种形成多层制品的方法,所述方法包括:
(a)将包含(i)芳香族硅烷和(ii)氨基硅烷的底漆施加到包含未固化的弹性体的组合物上;
(b)将高度氟化的热塑性塑料施加到所述底漆上;
(c)用光化辐射照射所述底漆;以及
(d)在所述高度氟化的热塑性塑料与所述组合物之间形成粘合。
2.根据权利要求1所述的方法,所述方法还包括在用光化辐射照射所述底漆之后,(e)固化所述未固化的弹性体以形成固化的弹性体。
3.根据权利要求2所述的方法,其中固化所述未固化的弹性体包括热固化所述未固化的弹性体。
4.根据权利要求1至3中的任一项所述的方法,其中在将所述高度氟化的热塑性塑料施加到所述底漆上之后对所述底漆进行照射。
5.根据权利要求1至3中的任一项所述的方法,其中在将所述高度氟化的热塑性塑料施加到所述底漆上之前对所述底漆进行照射。
6.根据前述权利要求中的任一项所述的方法,其中将所述高度氟化的热塑性塑料施加到所述底漆上包括挤出所述高度氟化的热塑性塑料。
7.根据前述权利要求中的任一项所述的方法,所述方法还包括在施加所述底漆之前挤出包含所述未固化的弹性体的所述组合物。
8.根据前述权利要求中的任一项所述的方法,其中所述高度氟化的热塑性塑料是完全氟化的热塑性塑料。
9.根据权利要求8所述的方法,其中所述全氟塑料包含氟化乙烯丙烯(FEP)和全氟烷氧基烷烃(PFA)中的至少一种。
10.根据前述权利要求中的任一项所述的方法,其中所述高度氟化的热塑性塑料包括含有四氟乙烯、六氟丙烯和偏二氟乙烯的共聚物。
11.根据前述权利要求中的任一项所述的方法,其中所述弹性体包含含氟弹性体。
12.根据权利要求1至10中的任一项所述的方法,其中所述弹性体包含丁腈橡胶。
13.根据前述权利要求中的任一项所述的方法,其中所述芳香族硅烷是芳香族仲氨基硅烷或芳香族叔氨基硅烷。
14.根据权利要求13所述的方法,其中所述芳香族硅烷包含N-苯基氨基烷基三烷氧基硅烷。
15.根据前述权利要求中的任一项所述的方法,其中所述氨基硅烷是(氨基烷基)三烷氧基硅烷。
16.一种通过根据权利要求2至15中的任一项所述的方法制备的多层制品。
17.根据权利要求16所述的多层制品,其中根据层间粘附性测试进行测量,所述高度氟化的热塑性塑料与所述固化的弹性体之间的粘附力为至少5N/cm。
18.根据权利要求16所述的多层制品,其中所述粘附力为至少15N/cm。
19.根据权利要求16至18中的任一项所述的多层制品,其中所述多层制品是包括管的软管,所述软管包含被所述高度氟化的热塑性塑料包围并且粘合到所述高度氟化的热塑性塑料的所述固化的弹性体。
20.根据权利要求16至18中的任一项所述的多层制品,其中所述制品是包括管的软管,所述软管包含被所述固化的弹性体包围并且粘合到所述固化的弹性体的所述高度氟化的热塑性塑料。
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US62/932,140 | 2019-11-07 | ||
PCT/IB2020/060279 WO2021090147A1 (en) | 2019-11-07 | 2020-11-02 | Bonding highly-fluorinated plastics to elastomers using silane-based primers |
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US6630047B2 (en) * | 2001-05-21 | 2003-10-07 | 3M Innovative Properties Company | Fluoropolymer bonding composition and method |
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