CN1186503A - 浸渍涂敷器尖头 - Google Patents
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Abstract
涂敷可聚和/或可交联材料(3)的涂敷器尖头(5),它是多孔性的、吸收性的或吸附性的,含聚合或交联引发剂(6)。当可聚和/或可交联材料通过涂敷器尖头进行涂敷时,引发剂引发聚合或交联。可将可聚和/或可交联材料涂敷至各种底材上。
Description
本发明涉及可聚和/或可交联材料的聚合和/或交联。本发明还涉及用涂敷装置将可聚和/或可交联材料涂敷在各种底材上。
背景技术
在本申请中,术语“聚合的”和“可聚”包含术语“可交联的/交联的”和“接枝的/可接枝的”在本领域中所定义的内容。例如,不仅“聚合”一词包括形成低聚物和聚合物的单体和预聚物的组合,而且它还包括低聚物和聚合物通过各种桥连构分的连接(交联)和与具有各种原子构分的侧链的低聚物和聚合物的连接(接枝)。
在一些应用中,聚合和/或交联材料的物理性能是十分重要的。例如,医学、外科和其他体内应用中使用的快速作用的外科用粘合剂、封闭剂、生物活性剂释放基质和植入体要求对聚合和/或交联材料加以严密的控制。这些材料例如包括美国专利No.5,328,687(属于Leung等)、3,527,841(属于Wicker等)、3,722,599(属于Robertson)、3,995,641(属于Kronenthal等)、3,940,362(属于Overhults)和美国专利申请No.08/266,647中公开的2-氰基丙烯酸酯。上述文献的内容在本文中引作参考。
通常,当用作粘合剂和封闭剂时,氰基丙烯酸酯是以单体形式涂敷在需连接或密封的物体表面,在那里,通常发生单体的原位阴离子聚合,产生所需的粘合而密封。植入体,如杆状物、网状物、螺旋状物和片状物等可由氰基丙烯酸酯类聚合物形成,通常通过游离基引发的聚合而形成。
增加α-氰基丙烯酸酯的组织相容性的努力包括对氰基丙烯酸酯的烷酯基团进行改性。例如,发现增加烷酯链键形成高级烷基氰基丙烯酸酯类似物,如丁基-2-氰基丙烯酸酯和辛基-2-氰基丙烯酸酯,不但可改善生物相容性,而且高级类似物的生物降解速率小于低级烷基氰基丙烯酸酯。
其他在生物医学应用中使用的改性α-氰基丙烯酸酯的例子包括α-氰基丙烯酸烷酯基烷酯(例如参见Kronenthal等的美国专利No.3,995,641)、氟代氰基丙烯酸酯(例如参见Robertson等的美国专利No.3,722,599)、、和2-氰基丙烯酸烷氧基烷酯(例如参见Banitt等的美国专利No.3,559,652)。其他努力包括将α-氰基丙烯酸酯与亚甲基丙二酸二甲酯和α-氰基丙烯酸的高级酯混合(例如参见Hawkins等的美国专利No.3,591,676)。
在其他增加用于外科应用的α-氰基丙烯酸酯粘合剂的有效性的努力中,已将某些粘性改善剂与α-氰基丙烯酸甲酯等α-氰基丙烯酸烷酯单体合用。例如参见美国专利No.3,564,078(其中,粘性改善剂为聚(2-氰基丙烯酸乙酯))和3,527,841(其中,粘性改善剂为聚(乳酸))。
在其所有内容在此处引作参考的Leung等的美国专利No.5,328,687中,发明者提出在体内应用中,用甲醛清除剂来改善其生物降解产生甲醛的α-氰基丙烯酸酯聚合物的生物相容性。此外,在其所有内容在此处引作参考的美国专利申请No.08/266,647中,通过调节可生物相容组合物的邻近体内环境的pH来达到α-氰基丙烯酸酯的生物降解速率。另外已知各种化合物可影响α-氰基丙烯酸酯单体的聚合,例如,酸可抑制或减缓聚合(例如,Leonard等的美国专利No.3,896,077),碱可加速聚合(例如,Coover的美国专利No.3,759,264和Dombroski等的美国专利No.4,042,442)。
同样地,许多聚合和/或交联抑制剂常被添加在可聚和/或可交联材料中以增加它们的货架寿命。然而,由于对任一后续聚合进程的负效应,添加在可聚和/或可交联材料中的聚合抑制剂的量受到限制。尤其是为使可聚和/或可交联材料稳定化而添加的大量或高浓度的聚合抑制剂可能使可聚和/或可交联材料稳定至将对聚合产生负效应的程度。因此,惯用的可聚和/或可交联材料可能仅含有有限量的聚合抑制剂。
对某些可聚和/或可交联材料的应用而言,需要控制可聚和/或可交联材料的固化时间。例如,用于一些外科手术的外科用粘合剂根据采用的方法,需要固化迅速或固化不那么快的聚合材料(例如,其内容在此处引作参考的Leung等的美国专利No.5,328,687和美国专利申请No.08/266,647)。包括在建筑和汽车工业中的密封和粘合法、在塑料工业中的模塑法和在纺织和电子工业中的涂布法在内的其他粘合法要求各种各样的固化时间。许多这些应用要求控制固化时间以使聚合材料产生合适的强度、弹性和硬度,同时还可提供必要量的工作时间,以将聚合材料涂敷在所需的底材上。
业已开发出各种用于同时涂敷和混合多个组分的配料装置。例如,Leigh的美国专利No.3,468,548公开了一种用于对二种糊状材料如膏油或凝胶进行配料的配料器。将其中的一种材料储存在管中,将另一种材料储存在与管连接的喷嘴的内腔中。当将第一种材料从管中压出时,它流过喷嘴并与第二种材料混合。
Morane等的美国专利No.3,891,125描述了一种用于分别储存二种产物并在使用之前将产物混合的装置。将一种产物储存在与含第二种产物的容器连接的喷嘴中。喷嘴中的产物由于重力而滴入含第二种产物的容器中并进行混合。然后,可将混合的产物从容器中压出,涂敷在合适的底材上。
Biswas的美国专利No.3,770,523涉及将增稠的易爆炸的料浆涂敷至孔洞或容器中。通过与射在料浆流上的多个射流中的交联剂混合而使易爆炸的料浆流增稠。
Rich的美国专利No.4,801,008公开了一种一次性筒,该筒包括含粘合剂系统的大量反应惰性的组分的内腔。将组分用隔膜分别隔开。组分在从喷嘴喷出时与固定混合成分混合。
发明概述
在高分子、树脂和涂料工业中仍需要通过控制聚合和/或交联速率和/或程度来控制聚合材料的性能的改进的方法。而且,需要提供可将可聚和/或可交联材料简便和经济地涂敷在各种底材上的方法。本发明者已发明了一种廉价的装置和方法,它可将各种各样的可聚和/或可交联材料简便和经济地涂敷在各种底材上,且可控制材料的性能,尤其是快速固化材料和医用材料。
本发明提供一种对来自涂敷器的可聚和/或可交联材料进行配料的系统,它包含涂敷器尖头,所述涂敷器尖头具有材料的聚合和/或交联引发剂。本发明的涂敷器尖头具有若干优点,包括:
a)可控制聚合材料或交联材料的分子量;
b)可控制聚合或交联材料的固化时间;
c)可精确和方便地将材料涂敷在底材上;
d)可延长材料的货架寿命;
e)可减少残余单体的存在,避免相关的单体气味;和
f)可控制涂敷材料的流动性能。
本发明的涂敷器尖头可用来将各种各样的单体和聚合物涂敷各种在底材上,所述单体和聚合物经过使用聚合或交联引发剂的聚合和/或交联。而且,本发明的涂敷器尖头可用于各种单体和聚合物系统,例如,可用于多组分粘合剂系统的应用。
图面的简单描述
图1是用于涂敷可聚和/或可交联材料的本发明涂敷器装置的侧视图。
图2是本发明的另一涂敷器装置的侧视图。
图3是本发明的又一涂敷器装置的侧视图。
最佳实施方式的详细描述
本发明的涂敷器尖头可用于涂敷各种可聚和/或可交联材料的各种方法中。具体地说,可聚和/或可交联材料包括无机和有机材料以及它们的组合。
合适的无机材料包括但不限于硅氧烷、聚硅氧烷、多硫化物和多磷腈。合适的有机可聚和/或可交联材料包括但不限于天然的、合成的和半合成的材料。合适的天然可聚和/或可交联材料包括但不限于多糖类,如淀粉、纤维素、果胶、海藻胶或植物胶;多肽或蛋白质,如酪蛋白、白蛋白、球蛋白,或胡罗卜素;或烃类,如橡胶和聚异戊二烯。
合适的有机合成材料包括但不限于热塑性和热固性高弹体,如尼龙和其他聚酰胺、聚氯乙烯、聚碳酸酯、聚乙烯、聚苯乙烯、聚丙烯、碳氟树脂、聚氨酯和丙烯酸类树脂;或热固性高弹体,如酚醛塑料、聚氨酯树脂、环氧树脂、醇酸树脂或聚酯树脂。合适的有机半合成材料包括但不限于纤维素,如嫘萦、甲基纤维素、或乙酸纤维素;或改性淀粉,如乙酸淀粉等。合适的可聚和/或可交联材料的例子包括但不限于其所有内容均在此处引作参考的美国专利No.5,328,687(属于Leung等)、3,728,375(属于Jr.Coover等)、3,970,505(属于Hauser等)、4,297,160(属于Kusayama等)、4,340,708(属于Gruber)、4,777,230(属于Kamath)、5,130,369(属于Hughes等)和美国专利申请No.08/226,647中所述的那些。可聚和/或可交联材料可包括上述材料中的一个或可含上述材料中的一个或多个的混合物。所述材料还可由上述可聚和/或可交联材料的单体、聚合物或低聚物组成。
例如,合适的可聚和/或可交联材料包括但不限于1,1-二取代的乙烯单体。有用的1,1-二取代的乙烯单体包括但不限于式(I)的单体:
(I) CHR=CXY式中,X和Y各表示强吸电子基团,R表示H、-CH=CH2,或当X和Y均表示氰基时,R表示C1-C4烷基。
式(I)范围内的单体的例子包括α-氰基丙烯酸酯、亚乙烯基二氰、亚乙烯基二氰的C1-C4烷基同系物、2-亚甲基丙二酸二烷酯、酰基丙烯腈、式CH2=CX′Y′的乙烯基亚磺酸酯和乙烯基磺酸酯,式中,X′表示-SO2R′或-SO3R′,Y′表示-CN、-COOR′、-COOH3、-SO2R′或-SO3R′,R′表示H或烃基。
可用于本发明的优选的式(I)单体是α-氰基丙烯酸酯。这些单体在本领域是已知的,具有式(II):式中,R2表示氢,R3表示烃基或取代的烃基;具有式-R4-O-R5-O-R6的基团,其中R4表示具有2 - 4个碳原子的1,2-亚烷基,R5表示具有2-4个碳原子的亚烷基,R6表示具有1-6个碳原子的烷基;或具有式
的基团,其中R7表示
或-C(CH3)2-,R8表示有机基。
合适的烃基和取代的烃基的例子包括具有1-16个碳原子的直链或支链烷基;被酰氧基、卤代烷基、烷氧基、卤原子、氰基取代的直链或支链C1-C16烷基,或卤代烷基;具有2-16个碳原子的直链或支链链烯基;具有2-12个碳原子的直链或支链炔基;环烷基;芳烷基;烷芳基;和芳基。
在式(II)的氰基丙烯酸酯单体中,R3最好是具有1-10个碳原子的烷基或具有式-AOR9的基团,其中A表示具有2-8个碳原子的二价直链或支链链烯基或氧化烯基,R9表示具有1-8个碳原子的直链或支链烷基。
式-AOR9表示的基团的例子包括1-甲氧基-2-丙基、2-丁氧基乙基、2-异丙氧基乙基、2-甲氧基乙基、2-乙氧基乙基和3-甲氧基丁基。
对在本发明中使用尤其有利的α-氰基丙烯酸酯单体是α-氰基丙烯酸甲酯、α-氰基丙烯酸丁酯、α-氰基丙烯酸2-辛酯、氰基丙烯酸1-甲氧基-2-丙酯、氰基丙烯酸2-丁氧基乙酯、氰基丙烯酸2-异丙氧基乙酯和氰基丙烯酸3-甲氧基丁酯。同样有利的是2-亚甲基丙二酸酯,如2-亚甲基丙二酸二甲酯。
其中R3为烃基或取代的烃基的式(II)α-氰基丙烯酸酯可通过本领域公知的方法来制备。参考文献例如有均在此处引作参考的美国专利No.2,721,858和3,254,111。例如,α-氰基丙烯酸酯可通过使氰基丙烯酸烷酯与甲醛在非水有机溶剂中于碱性催化剂的存在下反应,然后在聚合引发剂的存在下将无水中间体聚合物热解来制备。对生物医学应用而言,优选在低水分和基本无杂质的条件下制成的α-氰基丙烯酸酯单体。
其中R3为具有式-R4-O-R5-O-R6的基团的式(II)α-氰基丙烯酸酯可通过在此处引作参考的美国专利No.4,364,876(Kimura等)中公开的方法来制备。在Kimura等的方法中,α-氰基丙烯酸酯通过用下述步骤生产氰基乙酸来制备:用醇酯化氰基乙酸或使氰基乙酸烷酯和醇之间酯基转移;在0.5-1.5∶1,最好为0.8-1.2∶1摩尔比的催化剂的存在下,使氰基乙酸酯和甲醛或仲甲醛缩合,得到缩合物;直接或在除去缩合催化剂之后使缩合反应混合物解聚,产生粗制氰基丙烯酸酯;以及将粗制氰基丙烯酸酯蒸馏,形成高纯度的氰基丙烯酸酯。其中R3为具有式
的基团的式(II)α-氰基丙烯酸酯可通过在此处引作参考的Kronenthal等的美国专利No.3,995,641中描述的方法来制备。在Kronenthal等的方法中,前述α-氰基丙烯酸酯单体通过下述步骤来制备:使α-氰基丙烯酸的烷酯与1,3-环二烯反应,形成狄尔斯-阿德耳加成物,然后将其碱水解,接着酸化,形成相应的α-氰基丙烯酸加成物。最好用溴乙酸烷酯对α-氰基丙烯酸加成物进行酯化,形成相应的α-氰基丙烯酸烷酯基甲酯加成物。或者,可通过与亚硫酰氯的反应将α-氰基丙烯酸加成物转换成α-氰基丙烯酰卤加成物。然后使α-氰基丙烯酰卤加成物与羟基乙酸烷酯或甲基取代的羟基乙酸烷酯反应,分别产生相应的α-氰基丙烯酸烷酯基甲酯加成物或α-氰基丙烯酸烷酯基烷酯加成物。最后在略为不足的马来酐的存在下将加成物加热,除去1,3-环二烯保护基,使α-氰基丙烯酸烷酯基甲酯加成物或α-氰基丙烯酸烷酯基烷酯加成物转换成相应的α-氰基丙烯酸烷酯基烷酯。
式(II)单体的例子包括具有式(III)的氰基戊二烯酸酯和α-氰基丙烯酸酯:式中,Z表示-CH=CH2,R3的定义同上。可通过在催化剂如氯化锌等的存在下使合适的2-氰基乙酸酯与丙烯醛反应而制备R3为1-10个碳原子的烷基的式(III)单体,即2-氰基戊-2,4-二烯酸酯。该制备2-氰基戊-2,4-二烯酸酯的方法例如描述在此处引作参考的美国专利No.3,554,990中。
可聚和/或可交联材料可包括添加剂,如阻聚剂或稳定剂、粘度调节剂、游离基清除剂、pH调节剂(例如,美国专利申请No.08/266,647,其内容在此处引作参考)、其他单体、甲醛清除剂(例如Leung等的美国专利No.5,328,687,其内容在此处引作参考)、着色剂、润滑剂、防粘剂或转粘剂、表面活性剂、消泡剂、增塑剂、它们的混合物和其他添加剂。
可聚和/或可交联材料可以是纯净的(未添加其他化合物),或者在溶剂、乳液或悬浮液中。本发明的合适溶剂包括醇、醚醇、烃、卤代烃、醚、缩醛、酮、酯、酸、含硫或氮的有机化合物、它们的混合物等。其他合适的溶剂公开在其所有内容在此处引作参考的Hughes等的美国专利No.5,130,369和Hattori等的美国专利No.5,216,096中。这些溶剂可单独使用或二种或多种并用。它们可与水合用,其程度可达到使可聚和/或可交联材料溶解或悬浮在这样的混合液中。可掺入可聚和/或可交联材料中的溶剂总量可以是0-99,较好的是1-50,最好是3-25重量%。该量的选择当然将取决于所需的单体和反应条件,在这些范围之外的量也可能是可接受的。
可聚和/或可交联材料还可含聚合引发剂或阻聚剂、链转移剂、稳定剂或它们的混合物。合适的聚合引发剂和稳定剂公开在美国专利No.5,322,912(属于Georges等)、4,581,429(属于Solomon等)、4,340,708(属于Gruber)、4,364,876(属于Kimura等)和4,297,160(属于Kusayama等)。这些专利的所有内容在此处引作参考。加至可聚和/或可交联材料中的稳定剂或阻聚剂的量可以是0-50,较好的是0.001-25,最好是0.002-10重量%。该量的选择当然将取决于所需的单体和反应条件,在这些范围之外的量也可能是可接受的。
可掺入本发明的可聚和/或可交联材料中的合适的链转移剂包括其所有内容在此处引作参考的Hughes等的美国专利No.5,130,369中公开的那些。掺入可聚和/或可交联材料中的链转移剂的量可以是0-25,较好的是1-15,最好是2-10重量%。该量的选择当然将取决于所需的单体和反应条件,在这些范围之外的量也可能是可接受的。
加至本发明的可聚和/或可交联材料中的、其自身可以是或不能为可聚和/或可交联材料的合适的粘度调节剂、增塑剂和润滑剂包括其所有内容在此处引作参考的Kusayama等的美国专利No.4,297,160中所述的那些。本发明的可聚和/或可交联材料还可含分别揭示在其所有内容在此处引作参考的Leung等的美国专利No.5,328,687和美国专利申请No.08/266,647中的甲醛清除剂和pH调节剂。
下面对附图进行详细说明,实施本发明一个方面的的涂敷器装置粗略地显示在图1中。该装置包含容纳可聚和/或可交联材料3的圆柱形涂敷器容器2、用于将材料3从容器2压出的活塞4和具有含聚合和/或交联引发剂的接口6的涂敷器尖头5。
图2显示本发明的另一实施方式,它包括涂敷器装置10。该装置包含容纳可聚和/或可交联材料30的圆柱形涂敷器容器20和具有含聚合和/或交联引发剂的接口60的涂敷器尖头50,所述可聚和/或可交联材料30封装在易碎的小瓶40中。
图3显示又一实施方式,它包括涂敷器装置100。该装置包含容纳可聚和/或可交联材料300的圆柱形涂敷器容器200和含聚合和/或交联引发剂的涂敷器尖头500,所述可聚和/或可交联材料300封装在易碎的瓶400中。
本发明的涂敷器尖头可具有各种合适的形状,包括但不限于圆锥形、圆柱形、凿子形或多边形。例如,尖头可以是筒状、套管状、导管状、单内腔或多内腔状,或包含滚球、刷子、棉纱扫帚或类似的尖头。涂敷器尖头最好是圆锥形的。材料最好经具有缩小的周边的末端从涂敷器尖头出来,将所述末端制作成有助于材料涂敷在任何合适的底材上。涂敷器尖头的长度也可视各种涂敷参数如容纳可聚和/或可交联材料的涂敷器容器与待涂敷材料的底材的接近程度而异。材料从尖头出来所经由的尖头末端的大小可视涂敷而异。
本发明的涂敷器容器也可以是各种形状和大小的,取决于拟定的用途。例如,对涂敷限量的可聚和/或可交联材料而言,涂敷器容器可以是注射器状、管状、小瓶状、球状或吸移管状。例如,如图3所示的在软质容器200中的可聚和/或可交联材料300的易碎的封闭管400是优选的涂敷器类型。对大量涂敷可聚和/或可交联材料而言,可使用例如储罐状或反应罐状涂敷器容器。
本发明的涂敷器尖头可以是与容纳可聚和/或可交联材料的涂敷器容器可分开的。可在使用之前将这样的涂敷器尖头与涂敷器容器连接上,并在使用之后与涂敷器容器分开,以防止未涂敷的可聚或可交联材料在涂敷器容器中过早聚合或交联。这时,可将涂敷器尖头抛弃并将新的涂敷器尖头连接在涂敷器容器上供其后使用,或者可将涂敷器尖头重新使用。
此外,本发明的涂敷器尖头可包含多个部分,其中至少一个部分含引发剂。例如,可分开制造含引发剂的部件与涂敷器尖头的其他部件并在与涂敷器容器连接之前装配在一起。
涂敷器尖头还可以是将液体可聚和/或可交联材料喷成雾状的喷嘴形式。合适的有圆锥形的、扁平的喷嘴或凝聚流喷嘴。
本发明的涂敷器尖头可用于手工涂敷和自动涂敷。例如,手工涂敷方法包括使用手动装置,如注射器、粘合剂枪、吸移管、点眼药器等。自动涂敷方法包括注塑和机械手涂抹/密封/粘附。
涂敷器尖头和涂敷器容器还可以是整体单元。所述单元可以作为单件预形成并装填可聚和/或可交联材料。在涂敷来自涂敷器容器的材料后,可将该单元抛弃。此外,可将这样的整体涂敷器尖头/涂敷器容器单元制作成具有重新装填新材料的能力,作为多用途装置。
涂敷器尖头可由包括塑料、泡沫、橡胶、热固性塑料、膜等聚合材料在内的各种材料中的任一种组成。此外,涂敷器尖头可由金属、玻璃、纸、陶瓷、硬纸板等材料组成。涂敷器尖头材料可以是性质上多孔性的、吸收性的或吸附性的,以促进和有助于将引发剂加料在涂敷器尖头上或之内。例如,涂敷器尖头可由具有无规孔隙的材料、蜂巢型材料、编织型材料等组成。多孔度将取决于所用的材料。
与涂敷器容器连接的本发明的涂敷器尖头可具有长管形部分,混合的可聚和/或可交联材料从此喷出。为避免压力迅速下降和确保恒定的混合比率分布,以涂敷器尖头中在涂敷器容器正下方的部分为多孔性的较有利。其结构最好可夹持任何用来在涂敷器容器中隔离多组分的隔离层或材料。因此,任何这样的隔离层将不会堵塞装置。
可将引发材料聚合和/或交联的引发剂涂敷在涂敷器尖头的表面部分或整个表面,包括尖头的内部和外部。或者,可将引发剂仅涂布在涂敷器尖头的内表面。最好仅在涂敷器尖头的内部的一部分涂布引发剂。
涂敷器尖头上的引发剂可以是粉末或固态膜等固体形式,或者可以是粘性材料或糊样材料等液体形式。引发剂还可包含各种添加剂,如表面活性剂或乳化剂等。引发剂最好可在可聚和/或可交联材料中可溶和/或包含或带有至少一种表面活性剂,该表面活性剂在本发明的实施方式中促进引发剂与可聚和/或可交联材料共溶出。在本发明的实施方式中,表面活性剂可促进引发剂溶解在可聚和/或可交联材料中。
对特定的系统而言,本领域的普通技术人员可容易地选择特定的引发剂而无需过度的实验。合适的引发剂包括但不限于洗涤剂组合物;表面活性剂:例如polysorbate 20(例如,吐温20TM)、polysorbate 80(例如,吐温80TM)和poloxamer等非离子性表面活性剂,四丁基溴化铵等阳离子型表面活性剂,四癸基硫酸钠等阴离子型表面活性剂,和十二烷基二甲基(3-磺丙基)氢氧化铵内盐等两性表面活性剂;胺、亚胺和酰胺,如咪唑、色胺、尿素、精氨酸和聚乙烯吡咯烷(povidine)等;膦、亚磷酸盐和鏻盐,如三苯基膦和亚磷酸三乙酯;醇,如乙二醇、棓酸甲酯、抗坏血酸、单宁和单宁酸;无机碱和盐,如亚硫酸钠、氢氧化镁、硫酸钙和硅酸钠;硫化合物,如硫脲和多硫化物;聚合环醚,如莫能菌素、无活菌素、冠醚、calixarene和环氧聚合物;环状和无环碳酸酯,如碳酸二乙酯;相转移催化剂,如Aliquat 336;有机金属,如环烷酸钴和乙酰丙酮锰;和游离基引发剂和游离基,如二叔丁基过氧化物和偶氮二异丁腈。可聚和/或可交联材料还可含在被涂敷器尖头中的催化剂或促进剂(包括在此处所用的术语“引发剂”的范围内)激活之前为非活性的引发剂。例如,可使用含过氧化苯甲酰的单体作为与含胺促进剂的尖头有关联的可聚材料,环状可使用含甲基·乙基酮过氧化物的单体作为与含环烷酸钴的尖头有关联的可聚材料。若尖头和/或涂敷器被合适地置于热和/或光(例如,紫外光或可见光)等刺激之下,则被这些刺激激活的引发剂也是合适的。
可将引发剂涂敷至涂敷器尖头的表面或浸渍、掺入基质或涂敷器尖头的内部。例如,可通过喷射、蘸涂或用含引发剂的液体介质刷涂涂敷器尖头来将引发剂涂敷至涂敷器尖头上。液体介质可包括非水溶剂,如醚、丙酮、乙醇、戊烷或它们的混合物;或者可包括水溶液。液体介质最好是低沸点的溶剂。
此外,在涂敷器尖头上的引发剂在介质中可为0-50重量%之间的各种浓度,较好的是0.001-25重量%,最好是0.01-10重量%。量的选择当然将取决于所需的单体和反应条件,在这些范围以外的量也可能是可接受的。
可将引发剂以预形成膜的形式涂敷至涂敷器尖头上。可通过溅涂等蒸汽沉积方法将引发剂作为固体涂敷。此外,可将引发剂掺入涂敷器尖头中,例如,在制造尖头的过程中。这可通过在将涂敷器尖头材料模塑成所需形状之前将引发剂与涂敷器尖头材料混合来完成。
将引发剂涂敷至涂敷器尖头之上或之中后,可将涂敷器尖头干燥或加热,使液体介质蒸发或挥发,或者使引发剂在涂敷器尖头中均匀地分布或浸渍。这可通过在室温干燥涂敷器尖头或用惯用的装置如惯用的烘箱、真空烘箱、微波烘箱或UV/可见光等加热涂敷器尖头来完成。
此外,容纳可聚和/或可交联材料的容器可包含引发剂。例如,可将可聚和/或可交联材料在涂敷器容器中分开储存以使其不与引发剂在容器中接触。可用引发剂在涂敷器容器上衬底或涂布,或者可将引发剂储存在涂敷器容器内与可聚和/或可交联材料分开的隔室中。例如,在图3的装置中,可将引发剂涂布在器体200的内表面上。
在涂敷器尖头内,可装备静态或动态混合器以确保可聚和/或可交联材料与引发剂充分混合。优选的静态混合器包括内迂回通路。
也可将本发明的涂敷器尖头与多组分可聚和/或可交联材料系统合用,所述系统的材料在涂敷之前必须在物理上互相分开以避免它们之间发生化学反应。这些多组分筒例如公开在其所有内容均在此处引作参考的Rausch的美国专利No.3,915,297和Rich的美国专利No.4,493,436、4,538,920和4,801,008中。
可在可聚和/或可交联材料上施加压力以将材料从涂敷器容器中经由涂敷器尖头压出。当可聚和/或可交联材料通过涂敷器尖头时,材料与引发剂接触,由此引发材料聚合和/或交联。涂敷器尖头的形状最好促进材料与引发剂的混合以产生均匀混合物。涂敷器尖头的形状还有助于可聚和/或可交联材料涂敷至合适的底材上。引发剂可与可聚和/或可交联材料共溶出,或者可留在尖头中。
可为了保护、密封和将表面粘合在一起的目的,将本发明的材料涂敷在各种底材上。合适的底材包括金属、塑料、橡胶、木材、陶瓷、纺织品、水泥、纸、生物组织等。例如,可聚和/或可交联材料可用作组织粘合剂、防止渗血或覆盖创口的密封剂、传输治疗剂或其他生物活性剂的系统,并可用于其他生物医学应用。它们在例如下述方面具有用途:封闭外科手术的刀口或外伤性受伤组织;固定挫伤的骨结构;减缓血液从伤口流出;促成生物组织修复和再生;提供用于传输生物活性剂的可植入基质;和提供结构移植体。
本发明的涂敷器尖头可控制聚合或交联材料的分子量。例如,可增加涂敷至涂敷器尖头上的引发剂的量至可使可聚和/或可交联材料在惯用方法中达到更完全聚合的程度,所述惯用方法是在涂敷之前将聚合引发剂掺入可聚和/或可交联材料中。
本发明的涂敷器尖头还可控制材料的固化时间。例如,可变化涂敷至涂敷器尖头上的引发剂的量,使各涂敷器尖头上的引发剂的量各不相同,以控制涂敷材料的操作时间长短。此外,可互相交换具有不同量或类型的引发剂的涂敷器尖头,以在涂敷特定材料或不同材料的过程中产生不同的固化时间。
本发明的涂敷器尖头还延长了可聚和/或可交联材料的货架寿命。例如,通过增加聚合引发剂在涂敷器尖头上的量,可在可聚和/或可交联材料掺入更大量的阻聚剂或稳定剂,从而减少过早聚合。
本发明的涂敷器尖头还改善了可聚和/或可交联材料在涂敷至底材上的过程中的流变性能,从而使该材料的涂敷变得更加容易。例如,掺入在涂敷器尖头上的阻聚剂中的表面活性剂可增强从涂敷器尖头压出的聚合材料的流动性,从而有助于引发剂与材料共溶出。
下述实施例描述本发明的具体实施方式。本领域的技术人员将意识到,可根据需要对反应参数、试剂、组分比率/浓度和装置大小进行适当的调节以取得特有的聚合产物特性。所有的份和百分比均以重量计,除非另有说明。实施例
将数个重量百分比的引发剂与丙酮混合并搅拌至少30分钟以使混合物变得均匀。将图3所示的涂敷器的多孔性塑料尖头在引发剂溶液浸泡数分钟,从溶液中取出,与图3所示的含装入玻璃安瓿中的单体材料的软质丁酸(树脂)管的开口连接。(丁酸(树脂)管与丙酮接触即变软,因而可使尖头与涂敷器器体“熔接”。)让涂敷器在通风橱中干燥过夜。用纯丙酮溶剂制备无引发剂的对照用尖头。
在垂直位置,挤压涂敷器管以粉碎玻璃安瓿,由此释放单体材料。然后翻转涂敷器,挤压涂敷器管,将单体材料从尖头压出。当材料从管中出来时,使材料的细线沿人的手背流淌(2-3英寸),记录完全聚合所需的时间。结果见表1,该结果表明,要求保护的本发明可有效地控制聚合时间。
表1
可聚材料 引发剂(重量%) 固化时间(秒)
氰基丙烯酸2-辛酯 无 >240
氰基丙烯酸2-辛酯 0.01%吐温20 45
氰基丙烯酸2-辛酯 0.05%吐温20 30
氰基丙烯酸2-辛酯 0.15%吐温20 20
氰基丙烯酸2-异丙氧基乙酯 无 >240
氰基丙烯酸2-异丙氧基乙酯 2.5%吐温20 50
氰基丙烯酸2-异丙氧基乙酯 5.0%吐温20 <40
2-亚甲基丙二酸二甲酯 无 >150
2-亚甲基丙二酸二甲酯 2.5%四丁基溴化铵 50
Claims (24)
1.用于涂敷来自涂敷器的可聚或可交联材料的涂敷器尖头,它包含该材料的聚合或交联引发剂。
2.如权利要求1所述的涂敷器尖头,其特征在于,所述涂敷器尖头包含容纳所述引发剂的吸收性或吸附性材料中的至少一种。
3.如权利要求1所述的涂敷器尖头,其特征在于,所述尖头与涂敷器连成整体。
4.如权利要求3所述的涂敷器尖头,其特征在于,所述涂敷器是注射器、软质圆筒、管、吸移管或点眼药器。
5.如权利要求1所述的涂敷器尖头,其特征在于,所述涂敷器尖头包含多个部分,所述部分的至少一个包含所述引发剂。
6.如权利要求1所述的涂敷器尖头,其特征在于,所述引发剂包含洗涤剂组合物。
7.如权利要求1所述的涂敷器尖头,其特征在于,所述引发剂含至少一种选自表面活性剂和乳化剂的成分。
8.如权利要求1所述的涂敷器尖头,其特征在于,所述引发剂是聚氧乙烯山梨糖醇酐脂肪酸酯类表面活性剂。
9.制备用于涂敷可聚或可交联材料的涂敷器尖头的方法,包括:
将所述材料的聚合或交联引发剂涂敷至涂敷器尖头的至少一部分上。
10.如权利要求9所述的方法,其特征在于,可通过在形成所述尖头之前将所述引发剂与用来形成该尖头的材料混合来将所述引发剂涂敷至所述尖头上。
11.如权利要求9所述的方法,其特征在于,通过将所述涂敷器尖头浸渍在含所述引发剂的液体介质中或用含所述引发剂的液体介质喷洒所述涂敷器尖头来涂敷所述引发剂。
12.如权利要求11所述的方法,其特征在于,然后将所述涂敷器尖头干燥,使所述液体介质蒸发或挥发。
13.如权利要求9所述的方法,其特征在于,所述材料含至少一种选自游离基试剂、稳定剂、甲醛清除剂、pH调节剂、增塑剂、粘度调节剂、催化剂和着色剂的成分。
14.如权利要求9所述的方法,其特征在于所述材料是粘合剂。
15.如权利要求13所述的方法,其特征在于,所述材料是取代的烯烃。
16.如权利要求15所述的方法,其特征在于,所述取代的烯烃是氰基丙烯酸酯。
17.将可聚或可交联材料涂敷至底材上的方法,包括:将所述材料通过包含该材料的聚合或交联引发剂的涂敷器尖头涂敷至所述底材上。
18.如权利要求17所述的方法,其特征在于,所述材料在涂敷过程中与所述引发剂接触,从而引发所述材料聚合或交联。
19.如权利要求17所述的方法,其特征在于,所述引发剂与所述材料共溶出。
20.涂敷来自涂敷器的可聚或可交联材料的装置,它包含在固体载体上的该材料的聚合或交联引发剂。
21.如权利要求20所述的装置,其特征在于,所述固体载体包含部分所述涂敷器。
22.如权利要求20所述的装置,其特征在于,它包含容器器体和涂敷器尖头,所述涂敷器尖头包含所述固体载体。
23.如权利要求22所述的装置,其特征在于,所述材料位于所述容器器体中,在涂敷之前与所述尖头不接触。
24.如权利要求17所述的装置,其特征在于,所述材料封入容纳在柔性涂敷器内的易碎的小瓶中。
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US08/488,411 US5928611A (en) | 1995-06-07 | 1995-06-07 | Impregnated applicator tip |
US08/488,411 | 1995-06-07 |
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CN1186503A true CN1186503A (zh) | 1998-07-01 |
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CN96194452A Pending CN1186503A (zh) | 1995-06-07 | 1996-06-05 | 浸渍涂敷器尖头 |
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US (4) | US5928611A (zh) |
EP (1) | EP0832137B1 (zh) |
JP (1) | JP3558647B2 (zh) |
CN (1) | CN1186503A (zh) |
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CA (1) | CA2221260A1 (zh) |
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-
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-
1996
- 1996-06-05 AU AU62626/96A patent/AU701219B2/en not_active Ceased
- 1996-06-05 PT PT96921390T patent/PT832137E/pt unknown
- 1996-06-05 DE DE69619235T patent/DE69619235T2/de not_active Expired - Lifetime
- 1996-06-05 CN CN96194452A patent/CN1186503A/zh active Pending
- 1996-06-05 JP JP50186697A patent/JP3558647B2/ja not_active Expired - Lifetime
- 1996-06-05 EP EP96921390A patent/EP0832137B1/en not_active Expired - Lifetime
- 1996-06-05 WO PCT/US1996/009575 patent/WO1996040797A1/en active IP Right Grant
- 1996-06-05 AT AT96921390T patent/ATE213254T1/de not_active IP Right Cessation
- 1996-06-05 BR BR9608540A patent/BR9608540A/pt not_active IP Right Cessation
- 1996-06-05 ES ES96921390T patent/ES2172664T3/es not_active Expired - Lifetime
- 1996-06-05 CA CA002221260A patent/CA2221260A1/en not_active Abandoned
- 1996-06-05 DK DK96921390T patent/DK0832137T3/da active
-
1998
- 1998-12-29 US US09/221,997 patent/US6099807A/en not_active Expired - Lifetime
-
2000
- 2000-02-17 US US09/506,255 patent/US6322852B1/en not_active Expired - Lifetime
-
2001
- 2001-09-14 US US09/951,609 patent/US6376019B1/en not_active Expired - Lifetime
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ATE213254T1 (de) | 2002-02-15 |
EP0832137B1 (en) | 2002-02-13 |
CA2221260A1 (en) | 1996-12-19 |
AU6262696A (en) | 1996-12-30 |
AU701219B2 (en) | 1999-01-21 |
US5928611A (en) | 1999-07-27 |
BR9608540A (pt) | 1999-07-06 |
DE69619235D1 (de) | 2002-03-21 |
US6099807A (en) | 2000-08-08 |
US6376019B1 (en) | 2002-04-23 |
EP0832137A1 (en) | 1998-04-01 |
DE69619235T2 (de) | 2002-10-31 |
JP3558647B2 (ja) | 2004-08-25 |
WO1996040797A1 (en) | 1996-12-19 |
PT832137E (pt) | 2002-07-31 |
US6322852B1 (en) | 2001-11-27 |
ES2172664T3 (es) | 2002-10-01 |
EP0832137A4 (en) | 2000-08-23 |
JPH11511776A (ja) | 1999-10-12 |
DK0832137T3 (da) | 2002-05-27 |
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