CN1339955A - 聚醛与多种物质相互作用形成的凝胶 - Google Patents
聚醛与多种物质相互作用形成的凝胶 Download PDFInfo
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- CN1339955A CN1339955A CN00803712A CN00803712A CN1339955A CN 1339955 A CN1339955 A CN 1339955A CN 00803712 A CN00803712 A CN 00803712A CN 00803712 A CN00803712 A CN 00803712A CN 1339955 A CN1339955 A CN 1339955A
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- gel
- hydrophilic
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- polyacetals
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Classifications
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及在先技术的需要,提供了一种不可逆的、亲水的凝胶,可与敷料复合物、皮肤相容性复合物、伤口填塞物、创伤敷料、烧伤敷料、含药敷料、干膜、化妆面膜和化妆包裹敷料结合。本发明的凝胶是由亲水聚醛和从聚酰胺、聚胺、聚醇中选出来的聚合物组成的共混物。
Description
本发明所属技术领域
本发明属于稳定、不可逆的亲水凝胶领域，特别是聚酰胺、聚胺或聚醇与亲水的聚醛的共混物，可应用于各种敷料，包括在化妆品上的应用。
与本发明相关的背景技术
已知聚乙烯基吡咯烷酮(PVP)与聚氨酯混合后生产出亲水的共混物，它能用于创伤敷料和化妆。例如，美国专利5,156,601披露了一种敷料，它含有一种发粘的聚氨酯胶、聚(N-乙烯基内酰胺)如含有一定程度开环的吡咯烷酮基团的聚乙烯基吡咯烷酮。美国专利5,420,197描述了由聚(N-乙烯基内酰胺)，如含有一定开环程度的吡咯烷酮基团的聚乙烯基吡咯烷酮和聚氨基葡糖形成的亲水凝胶。其它文献还有美国专利5,135,755和5,206,322等。
虽然一些亲水凝胶可以在创伤敷料和其他一些皮肤相容性材料上应用，但很多已知的亲水凝胶是可逆的，有冷流趋向，所以还是需要在敷料、植入物和皮肤复合物中用不可逆、不冷流的凝胶。
发明目的
本发明的目的就是提供有亲水和吸收特征，不存在冷流的凝胶，以作为敷料复合物和皮肤相容性复合物。
还有一个目的是不需昂贵的设备和/或工艺就可以制作凝胶。
另一个目的是提供能用于各种产品，如洞腔敷料、含药贴、面膜和创口伤敷料的聚醛和聚(醇、胺、酰胺)组成的凝胶。发明简述
本发明解决了在先技术的不足，提供了能结合敷料复合物、皮肤相容性复合物、创伤包扎材料、创伤敷料、烧伤敷料、药物释放敷料、干膜、化妆面膜和化妆用敷料的不可逆的、亲水的凝胶。本发明中的凝胶是由一种亲水的聚醛和一种从聚酰胺、聚胺、聚醇中选出来的聚合物组成的共混物。
在本发明制备凝胶中很有用的亲水聚醛，包括丙烯醛、乙烯基缩甲醛、戊二醛及其混合物的均聚物、共聚物和三元共聚物，但不限于此。本发明中制备凝胶用到的聚酰胺包括丙烯酰胺、N-乙烯基酰胺、N-乙烯基缩甲醛及其混合物的均聚物、共聚物和三元共聚物，但不限于此。本发明中制备凝胶用到的聚胺包括1，2-乙二胺、烯丙胺、乙烯基吡啶、N-乙烯基缩甲醛、聚氨基葡糖、乙烯胺及其混合物的均聚物、共聚物和三元共聚物，但不限于此。本发明中用到的聚醇包括水解聚乙烯醇、烯丙醇、纤维素、乙二醇、环氧乙烷及其混合物的均聚物、共聚物和三元共聚物。
优选的是，凝胶含有至少一种可以从凝胶中释放出来的组分，优选的可释放组分是一种香料或一种具备生物功能或治疗身体功能的材料。
本发明的敷料复合物有与皮肤自粘合、易于剥离的优点。制备的凝胶作为本发明的一个成果，即使在热水中也是稳定的，能吸收多倍的水，能恰好在身体需要的部位释放药剂。最重要的是，本发明的凝胶产品有防冷流的独特性能。
本发明在先前技术基础上所作出的其他改进，从下面对本发明的优选实施例阐述中可以得到理解。对这些描述应理解为不限定本发明的范围，仅仅提供本发明中优选形式的操作实施例，本发明的范围不受此限制，而是按照下面权利要求的范围。发明详述
本发明是一种用于敷料复合物、伤口填塞物、创伤敷料、烧伤敷料、含药敷料、干膜、化妆面膜敷料和化妆包裹敷料的不可逆的亲水凝胶，本发明中稳定、不可逆、亲水的凝胶是由两种组分组成的共混物，一种组分是亲水的聚醛，另一种是聚酰胺、聚胺，或聚醇。
亲水的聚醛由单体醛接枝到聚(N-乙烯基内酰胺)而成，单体醛包括丙烯醛，乙烯基缩甲醛和戊醛，但不限于此，这些组分均可买到，例如可以从Aldrich化学公司买到。
单体形式的丙烯醛是非常活跃的，毒性相当大。但当接枝到生物相容的聚合物长链，如聚乙烯基吡咯烷酮(PVP)或聚乙二醇(PEG)时，就得到亲水的、高反应活性且无毒的大分子聚醛。
除了聚乙烯基吡咯烷酮，其它N-乙烯基内酰胺的均聚物、共聚物和三元共聚物也能用于本发明中亲水的聚醛的制备。
本处聚(N-乙烯基内酰胺)的概念可以理解为N-乙烯基内酰胺，如N-乙烯基吡咯烷酮、N-乙烯基己内酰胺等等的均聚物、共聚物和三元共聚物，除此之外，还有少量的(例如重量百分比大于约20％)的一种或其它几种可共聚的N-乙烯基内酰胺的乙烯基单体的均聚物、共聚物和三元共聚物，但不限于此。聚(N-乙烯基内酰胺)的共聚物或三元共聚物可以由乙烯基吡咯烷酮等N-乙烯基内酰胺单体与含乙烯基官能团，如丙烯酸基、羟烷基丙烯酸基、甲基丙烯酸基的单体、丙烯酸或甲基丙烯酸、丙烯酰胺共聚而成。在聚乙烯基内酰胺均聚物中，优选的是聚乙烯基吡咯烷酮(PVP)均聚物。在聚(N-乙烯基内酰胺)共聚物中，优选的是乙烯基吡咯烷酮与丙烯酰胺的共聚物。适用的聚(N-乙烯基内酰胺)三元共聚物，是由乙烯基吡咯烷酮、乙烯基己内酰胺和丙烯酸二甲氨基乙基酯共聚而成的，但不限于此。各种聚乙烯基吡咯烷酮都可买到。
内酰胺可以认为是由一种氨基酸通过-COOH与-NH2反应脱水成环而成的。所以，内酰胺环中含有-NH-CO-，N-乙烯基内酰胺中，环上的N原子上连接一个乙烯基，这种单体可以通过乙烯基进行聚合。
意外地发现，当单体醛接枝到聚(N-乙烯基内酰胺)上获得亲水性大分子的聚醛，与承载醇、酰胺、胺等官能体的聚合物混合时，一种亲水的、不可逆的、无游离醛的凝胶就形成了。“亲水”的概念指的是有结合或吸收水而导致溶胀和形成凝胶的强烈倾向。而用到“不可逆凝胶”概念指的是材料在加热、辐射或温和的化学条件下不会破坏结构的完整性，如琼脂和聚丙烯酰胺凝胶等。
已经惊人地发现，本发明中的亲水的、不可逆凝胶有着很有价值的抗冷流的特性。
“冷流”指室温下的蠕变。塑料由于其粘弹性，经过一段时间的负荷，比制备后同一负荷立刻松弛掉要有更大的变形。这种变形的程度在持续负荷和升高温度的情况下更大。蠕变即是在低于弹性极限的应力的持续作用下而出现的永久变形。这种变形，无论应力作用多长时间，只要负荷松弛掉都会部分回复(初级蠕变)和部分不能回复(二次蠕变)。这里“冷流”指的是本发明中不可逆凝胶，由于重力超时作用而使结构变得松散。
承载醇、酰胺、胺等官能体的聚合物指的是聚醇、聚酰胺、聚胺，也包括天然聚醇、聚酰胺、聚胺，但不限于此。本发明中，与聚醛反应生成亲水、不可逆凝胶的聚醇，包括水解聚醋酸乙烯酯，纤维素，烯丙醇、乙二醇、环氧乙烷及混合物的聚合物，但不限于此。
有用的聚酰胺包括可以买到的丙烯酰胺、N-乙烯基内酰胺、N-乙烯基缩甲醛及其混合物的聚合物，但不限于此。
在本发明中制备凝胶中用到的聚胺包括可以买到的1，2-乙二胺、烯丙基胺、乙烯基吡啶和聚氨基葡糖的聚合物，但不限于此。
为制得凝胶，一种聚(N-乙烯基内酰胺)的水溶液与可聚合的醛混合后形成亲水的聚醛水溶液。聚(N-乙烯基内酰胺)的水溶液中，含有重量比约5％到约50％的聚(N-乙烯基内酰胺)。得到的亲水聚醛水溶液中，含有重量比约5％到约50％的聚醛。然后将得到的聚醛与聚胺水溶液混合，聚醇或聚酰胺的重量比为约12∶1到约1∶1，制得的混合物含有聚醛、聚酰胺、聚胺、聚醇等聚合物的总含量在混合物中的重量约1％至50％，最好是5％至15％。
聚胺水溶液含有重量比约为5％至约50％的聚胺。聚酰胺水溶液含有重量比约为5％至约50％的聚酰胺。聚醇水溶液含有重量比约为5％至约50％的聚醇。
得到的混合物允许在10秒至2小时内固化，直到形成亲水的、不可逆的凝胶，固化的时间和温度不是很严格。为方便起见，可以在环境温度下固化，但升高温度可以缩短时间。凝胶指发粘、半固体、果冻状物。本发明中的凝胶，即使在沸水或醇中也是稳定的、不可逆的、不可溶的。凝胶是亲水的，能吸收多倍于它本身重量的水，至少也可以吸它重量100％的水。这里的“发粘”指的是接触时有粘的感觉，或能一定程度凝胶能与皮肤相粘，而当希望揭掉时又容易揭掉。
凝胶机理的本质尚不清楚，但我们不打算囿于理论，相信聚醛加入到承载着胺、酰胺和胺等官能体的聚合物组分中后，会通过聚酰胺、聚胺或聚醇中的离子键相互连接成网而产生分散的共价交联。
很多不同类型的添加材料可以结合于本发明的凝胶中，包括有机盐、低浓度的无机盐、醇、胺、聚合物栅格(polymer lattices)、填料、表面活性剂、颜料、染料、香料等等，只要不干扰凝胶的形成。这些材料很多都可从凝胶中直接释放。
本发明中的凝胶特别适合作为各种对人和动物有治疗作用的、可释放生物活性物质的载体。适于结合于本发明凝胶中的生物活性材料包括荷尔蒙制剂、催眠药、镇静药、解热药剂、消炎药剂、局部麻醉药、解挛药、抗溃疡药剂、抗病毒药、抗真菌药、拟交感神经功能药剂、心血管药剂、抗肿瘤药剂等等，加入的生物活性物质量应按照药剂活性量加入。
作为生物活性添加剂特别优选的有硝化甘油、东莨菪碱、毛果芸香碱、酒石酸麦角酰胺、苯丙醇胺、茶碱，抗菌药如四环素、新霉素、土霉素、三氯生(tricolsan)、头孢唑林钠、磺胺嘧啶银，以及水杨酸盐类如甲基水杨酸盐和水杨酸，烟酸盐类如甲基烟酸盐；辣椒碱、苯佐卡因、α-醇酸、维生素和生物稳定剂。
当凝胶用于化妆制品时，可以加水合剂如吡咯烷羧酸钠、多元醇和聚合物。作为亲水的目的，通过亲水凝胶可以吸收大量的水，为皮肤提供润湿功能。
如上所述的水溶性和不溶于水的添加剂，可以在凝胶制备前混在水溶液中，也可以在制备凝胶过程中与聚(N-乙烯基内酰胺)的水溶液共混或与聚胺、聚酰胺或聚醇的水溶液相混。优选的是，在聚乙烯基吡咯烷酮与载有胺、酰胺或醇官能体的聚合物混和前，把水溶性组分与聚乙烯基吡咯烷酮混合。不溶于水的组分也可以通过加入表面活性剂进行乳化从而加入聚(N-乙烯基内酰胺)或聚胺、聚酰胺或聚醇中，或者在聚(N-乙烯基内酰胺)与聚胺、聚酰胺或聚醇混合后，在凝胶制备的同时，把添加剂混入凝胶中。添加剂也可以通过喷涂、浸渍、刷涂或滚压等方式置于凝胶敷料的表面。
凝胶可以用于制作吸附剂、伤口包裹、填充物或敷料、皮肤面膜或覆盖物(wraps)、药物释放药膏、植入物和干膜制品。
当凝胶可以用于制作伤口填塞物，或伤口敷料时，它有利于提供具备如下所希望敷料的性能，如(1)生物相容性，(2)能适应创伤洞腔(3)与创伤不粘到一起(4)能吸收渗出液(5)能从伤口完整揭除(6)当吸收渗出液膨胀时能保持物理完整性(7)不很粘，容易处理。
当用作皮肤水合膜(skin-hydrating mask)时，凝胶有优良的水合能力，其优点是不含乙醇，并且容易且干净地清除。
当用作植入物时，凝胶在诸如热和有水的条件下，能良好地保持物理完整性，由于其生物相容性，也是一种优良的可选植入物材料。
当制成干膜用作皮肤掩蔽物(skin mask)时，它是一种柔软的、清洁的、浸水后能附着在皮肤上的亲水膜，膜能固定活泼的吸湿剂和其它组分贴近皮肤，有助于它们的释放。当经过一段时间后，可容易地揭掉膜，而不会留下残余物。
本发明中的成品，可以直接包装在模子里；或作成干膜形式；或作成两组分体系，在使用前混合；也可以采用一种基材，在上面覆盖防粘衬层以防止凝胶自粘，粘到皮肤之前去掉防粘衬层。
基材可以实现几种功能，包括增强、提供气体和液体阻挡层、帮助空气渗入、提供对凝胶和治疗面的保护，等等。对本领域技术人员来说，熟知应如何选择基材以提供所期望的性能。可用的基材包括聚合物织物、胶原膜、纺织品、无纺织物及其混合物，但不限于此。优选的基材可以是聚氨酯或聚酯膜、可拉伸的材料、防粘衬层及具有混合物性能的材料。
可以用任何已知方法或技术，把本发明凝胶涂敷或施加于衬材或基材。凝胶可以结合或粘附到各种基材或衬材上，如树脂、金属箔片、天然的纺织品或无纺织物、合成纤维等等。提供气体或液体阻挡功能的衬材可以是聚合物膜，如聚氨酯膜。也可以用聚酯、聚乙烯醇或聚氯乙烯制成的膜作成。当凝胶有阻挡层基材时，这样的结构特别适用于创伤和烧伤敷料。能保持湿度并吸收过量的渗出物以促进治疗，细菌能被阻挡在创伤或烧伤部位之外，可以在凝胶中加入抗微生物的药剂以防止感染。为使用方便，衬材上的凝胶可用硅烷膜或聚乙烯防粘衬覆盖。
凝胶可以涂到衬材上，使凝胶全部或部分占据衬材的表面。如果凝胶占据衬材的部分表面，衬材上没有涂凝胶的地方就可以另外加胶粘剂。凝胶也可以含有增粘剂如多酸、聚醇和聚胺等，这些材料有助于提高粘度。这种类型的敷料放到皮肤上，另加的皮肤胶粘剂使皮肤与之能完全贴合，仅仅有吸收能力的凝胶接触创伤处。当有吸收能力的凝胶由于吸满了渗出物而实际上失去了粘附力时，另加的胶粘剂能使敷料仍有附着力。在一个优选实施例中，采用这种方式制备敷料：把独立的两片凝胶片置于两块独立的基材上，在一个片的表面施加生物活性材料的溶液，然后把两片压到一起，使具有生物活性的材料夹在两凝胶片之间。
在另一实施例中，有一种用于化妆制品和化妆包裹敷料的，具皮肤相容性组分的凝胶。还有一个实施例，凝胶用于化妆品如面膜和指甲套。该凝胶都有水合功能，有或没有基材，加入其他组分以增强化妆效果。用作化妆凝胶的成套用具，可以包括一种成品凝胶或两种成分：聚(N-乙烯基内酰胺)组分，以及乙醇、胺、酰胺官能体的载体作用聚合物。其它的化妆品制剂如水合剂、香料等也可添加于凝胶成品或两种组分中的任一种。混合组分后再使用。该凝胶的优点在于使用后易于地揭掉。化妆品的概念应该理解为用于加强或改善人体外表的制品。
进一步在另一个实施例中，香料可以混入凝胶中。当凝胶在一种合适的开口容器中保持湿润时，香料缓慢地释放，例如一种空气清新剂。
下面的实施例是为了阐明本发明，但不能限制本发明。在下面的实施例中，制成的不可逆、亲水的、无游离醛的凝胶，能用于创伤、烧伤敷料，植入物或化妆品。
优选实施例的详细描述
实施例1
准备三个独立的，装有搅拌、回流冷凝器和温度计的250毫升的圆底烧瓶，(1)在第一个烧瓶中加入10％的聚乙烯基吡咯烷酮(Kollidon 90F，-BASF)溶液99.0克；(2)在第二个烧瓶中加入10％的聚乙二醇溶液99.0克，并且(3)在第三个烧瓶中加入10％的聚乙二胺溶液99.0克。一边搅拌，一边把溶液升温至60℃，每个烧瓶中加入0.5克水溶性引发剂(Wako V-50，Dock树脂公司)，每个烧瓶中的溶液搅拌30分钟。然后在每个烧瓶中加入0.5克由Aldrich化学品公司生产的可聚合的丙烯醛，溶液加热到75℃，在搅拌下反应6小时。当与聚醇、聚胺或聚酰胺混合时，烧瓶中的聚乙烯基吡咯烷酮、聚乙二醇和聚乙二胺就形成了亲水的，不可逆的凝胶，没有检测到游离醛。
实施例2
在装有搅拌器、回流冷凝器和温度计的250毫升的圆底烧瓶中，加入25％的PEG溶液(Carbowax，Fischer公司)99.0克，一边搅拌，一边把溶液升温至60℃，加入0.5克水溶性引发剂(过氧化氢，Aldrich化学品公司)，将溶液搅拌30分钟，然后加入0.5克可聚合的醛(由Aldrich化学品公司生产的丙烯醛)，加热到75℃，在搅拌下反应6小时。当PEG与聚醇、聚胺或聚酰胺混合后，就形成了亲水的，不可逆的凝胶，没有检测到游离醛。
实施例3
在装有搅拌器、回流冷凝器和温度计的250毫升的圆底烧瓶中，加入10％的聚乙烯基吡咯烷酮溶液(Kollidon 90F，BASF)99.4克。一边搅拌，一边把溶液升温至60℃，加入0.5克水溶性引发剂(过硫酸钠，Aldrich化学品公司)，溶液搅拌30分钟溶液，然后加入0.1克由Aldrich化学品公司生产的可聚合的丙烯醛，加热到75℃，在搅拌下反应6小时。当聚乙烯基吡咯烷酮与聚醇、聚胺或聚酰胺混合后，就形成了亲水的，不可逆的凝胶，没有检测到游离醛。
实施例4
在装有搅拌器、回流冷凝器和温度计的250毫升的圆底烧瓶中，加入乙烯基吡咯烷酮(Aldrich化学品公司)20克和79克水，一边搅拌，一边把溶液升温至60℃，加入0.5克水溶性引发剂(WakoV-50)，溶液搅拌10分钟，然后加入0.1克由Aldrich化学品公司生产的可聚合的丙烯醛，加热到75℃，在搅拌下反应6小时。当与聚醇、聚胺或聚酰胺混合后，聚乙烯基吡咯烷酮形成了亲水的，不可逆的凝胶，没有检测到游离醛。
实施例5
在一个装有50克如实施例1所描述的聚合物的烧杯中，在搅拌条件下加入3克乳酸，混合完全后，在搅拌下加入47克由BASF生产的聚胺的50％的溶液，得到的凝胶是发粘的、柔软的，加入了1.5％的乳酸，能用作化妆品。
实施例6
在一个装有50克如实施例3所描述的聚乙烯基吡咯烷酮的烧杯中，搅拌下加入50克稀释的聚氨基葡糖溶液。得到的凝胶在130℃下不可逆，柔韧且不太粘伤口。当把此凝胶放入室温下的过量水或盐水溶液中时，它吸收水，几天后也不会溶解或分解。发现这种凝胶能在水或盐水中吸收它自重1,020％的水。因为这种凝胶发粘，但不粘伤口，可用作创伤或烧伤敷料。
实施例7
把按实施例5制作的一部分凝胶进行干燥，制成一种薄的柔软的膜，室温下在水中浸泡，在溶胀过程中膜能吸收150％的水。
对工艺熟悉的人对本发明的各种调整和变化亦非常熟悉，但这些并不背离本发明的范围和宗旨。即便本发明是与其适宜的特殊实施例一起阐述的，应该明了的是，权利要求的发明不应该被不适当地限制在这些特殊实施例里。确实，对那些对工艺熟悉的人来说，对所描述的实施本发明模式的各种调整已经非常熟悉。这些调整都在随后所附的权利要求范围内。
Claims (20)
1.一种稳定、不可逆、亲水的凝胶，是由一种亲水的聚醛和一种从聚胺、聚酰胺、聚醇及其混合物组成的组中选出的聚合物的共混物组成的。
2.根据权利要求1所述的聚胺、所述的聚酰胺、所述的聚醇是天然聚合物。
3.根据权利要求1所述的亲水的聚醛包括丙烯醛、乙烯基缩甲醛、戊二醛及其混合物的均聚物、共聚物或三元共聚物。
4.根据权利要求1所述的聚酰胺，包括源于丙烯酰胺、N-乙烯基内酰胺、N-乙烯基缩甲醛及其混合物组成的组的均聚物、共聚物或三元共聚物。
5.根据权利要求1所述的聚胺，包括源于1，2-乙二胺、烯丙胺、乙烯基吡啶、聚氨基葡糖及其混合物组成的组的均聚物、共聚物或三元共聚物。
6.根据权利要求1所述的聚醇包括源于水解聚乙烯醇、烯丙基醇、纤维素、乙二醇、环氧乙烷及其混合物组成的组的均聚物，共聚物或三元共聚物。
7.根据权利要求1所述的凝胶，其中所述亲水凝胶包括组成重量比为聚醛∶聚酰胺，聚醛∶聚胺，或聚醛∶聚醇等由约12∶1至约1∶1。
8.根据权利要求1所述的凝胶，其中所述亲水凝胶是在总聚合物浓度重量百分比为约5％至50％的聚醛、聚胺、聚酰胺和聚醇水溶液中制备的。
9.根据权利要求8所述凝胶，其中所述水溶液包括水或一种水与醇的混合物。
10.根据权利要求1所述的凝胶，进一步包括至少一种基材，选自由聚合物膜、胶原膜、纺织物、无纺织物及其混合物组成的组。
11.根据权利要求1所述的凝胶，进一步包括至少一种基材，选自由聚氨酯膜、聚酯膜、可伸展的材料、防粘衬及其混合物组成的组。
12.根据权利要求1所述的凝胶，其中所述亲水凝胶，进一步包括至少一种添加剂，选自由表面活性剂、香料、生物活性物质及其混合物组成的组。
13.根据权利要求1所述的凝胶，其中所述添加剂能从所述凝胶中释放出来。
14.根据权利要求1所述的凝胶，其中所述亲水凝胶进一步包括至少一种添加剂，选自由硝化甘油、东莨菪碱、毛果芸香碱、酒石酸麦角酰胺、苯丙醇胺、茶碱、四环素、新霉素、土霉素、三氯生、头孢唑林钠、磺胺嘧啶银，水杨酸盐类、烟酸盐类、辣椒碱、苯佐卡因、α-醇酸、维生素和生物稳定剂及其混合物组成的组。
15.根据权利要求1所述的凝胶的产品形式，选自由敷料复合物、皮肤相容复合物、伤口填塞物、创伤敷料、烧伤敷料、含药敷料、干膜、化妆面膜和化妆包裹敷料组成的组。
16.根据权利要求15所述的凝胶形式是没有基材的伤口填塞物、植入物或洞腔敷料。
17.用于制作不可逆的、适度发粘的、亲水的凝胶的方法，包括以下几个步骤(i)制作共混物：把溶有聚醛的均聚物或共聚物的水溶液与聚胺、聚醇或聚酰胺的水溶液按重量比为12∶1至1∶1的比例混合好，总的聚合物含量超过混合物的5％；并且(ii)允许步骤(i)所述混合物固化直到生成亲水的凝胶。
18.根据权利要求17所述的方法，进一步包括在步骤(i)所述混合物中加入生物活性物质。
19.根据权利要求18所述的生物活性材料是一种抗微生物制剂。
20.根据权利要求17所述的方法，其中步骤(i)所述的混合物制作敷料的方法是，把独立的两块凝胶片施于两块独立的基材上，在一个片的表面加入生物活性材料的溶液，然后把凝胶片压到一起，使所述具有生物活性物质夹在两片之间。
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| US09/248,591 | 1999-02-11 | ||
| US09/248,591 US6121375A (en) | 1999-02-11 | 1999-02-11 | Gels formed by the interaction of poly(aldehyde) with various substances |
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| EP (1) | EP1164991B1 (zh) |
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| KR (1) | KR20010102071A (zh) |
| CN (1) | CN1339955A (zh) |
| AT (1) | ATE446069T1 (zh) |
| AU (1) | AU761930B2 (zh) |
| BR (1) | BR0008129A (zh) |
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| DE (1) | DE60043185D1 (zh) |
| HU (1) | HUP0105366A2 (zh) |
| ID (1) | ID30281A (zh) |
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| MX (1) | MXPA01008099A (zh) |
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| NZ (1) | NZ513492A (zh) |
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| SK (1) | SK11362001A3 (zh) |
| TR (1) | TR200102333T2 (zh) |
| UA (1) | UA73933C2 (zh) |
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| US20100015231A1 (en) * | 2008-07-17 | 2010-01-21 | E.I. Du Pont De Nemours And Company | Low swell, long-lived hydrogel sealant |
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| US9044529B2 (en) * | 2008-11-19 | 2015-06-02 | Actamax Surgical Materials, Llc | Hydrogel tissue adhesive formed from aminated polysaccharide and aldehyde-functionalized multi-arm polyether |
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| WO2011002956A1 (en) | 2009-07-02 | 2011-01-06 | E. I. Du Pont De Nemours And Company | Aldehyde-functionalized polysaccharides |
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| US8796242B2 (en) | 2009-07-02 | 2014-08-05 | Actamax Surgical Materials, Llc | Hydrogel tissue adhesive for medical use |
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| US8859705B2 (en) | 2012-11-19 | 2014-10-14 | Actamax Surgical Materials Llc | Hydrogel tissue adhesive having decreased gelation time and decreased degradation time |
| CN104277111B (zh) * | 2013-07-08 | 2020-06-12 | 百瑞全球有限公司 | 用于制备固定化蛋白质、多肽或寡肽的复合载体、制法及用途 |
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| RU2613112C2 (ru) * | 2015-04-20 | 2017-03-15 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Раневое покрытие на основе хитозана (варианты) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105982830A (zh) * | 2015-01-29 | 2016-10-05 | 于杰 | 功能面膜 |
| CN104839198A (zh) * | 2015-03-20 | 2015-08-19 | 山西省农业科学院植物保护研究所 | 一种用于防治桃小食心虫的温敏型农药缓释剂 |
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| US6365664B1 (en) | 2002-04-02 |
| HUP0105366A2 (hu) | 2002-04-29 |
| RU2225185C2 (ru) | 2004-03-10 |
| EP1164991B1 (en) | 2009-10-21 |
| JP2002536118A (ja) | 2002-10-29 |
| AU761930B2 (en) | 2003-06-12 |
| UA73933C2 (en) | 2005-10-17 |
| CA2359872C (en) | 2008-10-07 |
| TR200102333T2 (tr) | 2002-05-21 |
| DE60043185D1 (de) | 2009-12-03 |
| NO20013913L (no) | 2001-10-10 |
| AU2609100A (en) | 2000-08-29 |
| EP1164991A1 (en) | 2002-01-02 |
| IL144775A (en) | 2006-10-31 |
| EP1164991A4 (en) | 2006-07-19 |
| MXPA01008099A (es) | 2002-04-24 |
| NZ513492A (en) | 2002-11-26 |
| WO2000047149A1 (en) | 2000-08-17 |
| NO322419B1 (no) | 2006-10-02 |
| IS6045A (is) | 2001-08-09 |
| CA2359872A1 (en) | 2000-08-17 |
| KR20010102071A (ko) | 2001-11-15 |
| SK11362001A3 (sk) | 2002-04-04 |
| ATE446069T1 (de) | 2009-11-15 |
| PL349812A1 (en) | 2002-09-09 |
| CZ20013008A3 (cs) | 2002-02-13 |
| US6121375A (en) | 2000-09-19 |
| BR0008129A (pt) | 2002-02-05 |
| NO20013913D0 (no) | 2001-08-10 |
| ID30281A (id) | 2001-11-15 |
| IL144775A0 (en) | 2002-06-30 |
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