CN101589085A - 亲水性聚氨酯(甲基)丙烯酸酯的水凝胶 - Google Patents
亲水性聚氨酯(甲基)丙烯酸酯的水凝胶 Download PDFInfo
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Abstract
本发明涉及使用水溶性氧化还原引发剂由聚氨酯(甲基)丙烯酸酯在水中形成的水凝胶。
Description
本发明涉及使用水溶性氧化还原引发剂由聚氨酯(甲基)丙烯酸酯在水中形成的水凝胶。
特别是在需要保持伤口潮湿的情况中,以合适的伤口接触材料的形式用于伤口医治的水凝胶能够促进伤口愈合(湿伤口治疗)。通常使用基于聚(甲基)丙烯酸酯、聚乙烯基吡咯烷酮或聚乙烯基醇的合成聚合物形成水凝胶。通常,这类水凝胶特别突出的是与活组织良好的相容性。
还已知可通过亲水性异氰酸酯官能预聚物和大量过量的水反应得到的聚氨酯的水凝胶,例如EP-A 426 422、EP-A 455324、WO 9817215、WO 9913923和WO2002060501中所述的。为了避免由于异氰酸酯基团与水反应释放的二氧化碳而起泡,大量过量的水是必需的。相反,这意味着不能获得具有低含量初始加入水(无气泡)的聚氨酯水凝胶。因此,所生产的聚氨酯水凝胶只能向(干)伤口释放水,而只能以非常有限的程度吸收伤口液体。
而且,生产聚氨酯水凝胶的现有技术是慢操作,通常必须使用三种组分,所得凝胶仍然含有大量未结合的多元醇。合成方法通常使用脂族异氰酸酯官能预聚物,该预聚物基于聚乙二醇、聚丙二醇或丙三醇作为多元醇,部分地在促进剂(例如具有伯氨基端基的低聚环氧烷)存在下形成;也就是说,对于快速反应体系必需有三种组分。多元醇的用量要显著超过化学计量比量。因此,所述水凝胶仍然含有过量的多元醇和活化剂。此外,反应速度很慢,通常在90分钟后才达到胶凝点。这类凝胶中抗微生物活性物质可加入的程度至今还没有报导。
还存在通过自由基交联形成的水凝胶。GB-A 2086927描述了半-IPN水凝胶,该水凝胶由过氧化物引发,在较高的温度下通过低分子量聚丙烯酸酯在线型聚氨酯的乙醇溶液存在下发生交联反应形成。然后,除去辅助的溶剂乙醇。
GB-A 2131442描述了低分子量聚烯丙基化合物,GB 2150938描述了甲基丙烯酸羟乙酯和其它单丙烯酸酯作为外部的自由基聚合单体。这些现有技术的参考文献同样涉及在较高温度下使用辅助溶剂如乙醇和过氧化物。
EP-A 351 364描述了由N,N-二甲基丙烯酰胺、含氟聚合物和交联剂与不饱和异氰酸酯反应制备的水凝胶,可能的交联剂包括多元醇,例如聚乙烯醇或三甘醇,所述不饱和异氰酸酯例如是MOI(甲基丙烯酰氧基乙基异氰酸酯)或TMI(α,α-二甲基-3-异丙烯基苄基异氰酸酯)。通过紫外引发剂或自由基引发剂引发交联反应。同样具有上述缺点。而且,身体接触中的紫外交联是危险的(与皮肤、患者和医务人员的护眼镜发生反应)。
US 2005 0271727描述了聚乙烯基醇和交联剂通过氧化还原聚合反应形成的水凝胶,所述交联剂依据Furch等在聚合物(Polymer),(1998)39(10),1977-1982中的描述由HEMA和乙交酯制备,该制备方法成本高且操作麻烦。
因此,需要一种聚氨酯水凝胶,其在需要时仅仅使用少量水就能形成,因此在与伤口接触时能额外地吸收伤口液体。当然,聚氨酯水凝胶仍然应该能够向(干)伤口释放水。如果需要,聚氨酯水凝胶仅仅在伤口或其它身体开放部位(例如,在内窥镜介入的情况中)中形成,所以交联必须在无明显放热的情况下进行。辐射固化(例如,紫外交联)由于高成本和操作麻烦而应该避免使用。所有液体前体和聚氨酯水凝胶本身应该具有良好的生物相容性;应该避免使用有机溶剂。
目前已经发现,摩尔质量至少为2000克/摩尔的亲水性聚氨酯丙烯酸酯的水溶液可通过在10-42℃的温度下利用氧化还原体系交联,所形成的聚氨酯水凝胶的含水量可以在很宽的范围内调节。不一定需要使用有机溶剂或单体丙烯酸酯;获得的聚氨酯水凝胶具有良好的生物相容性。
因此,本发明提供一种制备聚氨酯水凝胶的方法,该方法包括使A)在B)和C)存在下发生自由基交联:
A)具有烯键式不饱和基团的亲水性聚氨酯;
B)水;
C)包含水溶性氧化剂和水溶性还原剂的氧化还原体系,所述氧化剂在氧化还原电势方面能通过形成自由基与水溶性还原剂反应。
可通过该方法获得的水凝胶以及生产聚氨酯水凝胶的方法构成本发明的主题的一部分。
具有烯键式不饱和基团的亲水性聚氨酯可通过多异氰酸酯与羟基官能聚环氧烷反应制得。
以存在的氧化烯(oxalkylene)单元为基准计,这些聚环氧烷的环氧乙烷含量优选至少为50%,更优选至少为60%。
除非另有说明,否则,所有百分数都是重量百分数(此处和下文中)。
特别优选这些聚环氧烷包含环氧乙烷和环氧丙烷的共聚物,其中环氧乙烷含量为50-100%,优选为60-82%,该共聚物从多元醇或胺起始,例如水(看作二醇)、乙二醇、丙二醇、丁二醇、丙三醇、TMP、山梨糖醇、季戊四醇、三乙醇胺、氨或乙二胺。
这些聚环氧烷的摩尔质量优选为Mn=2000-20000克/摩尔,更优选为4000-8500克/摩尔。
OH官能度优选为2-6,更优选为3-6,最优选为3-4。
可用的多异氰酸酯包括例如烯键式不饱和异氰酸酯,例如MOI(异氰酸基乙基甲基丙烯酸酯),TMI(3-异丙烯基-α,α-二甲基苄基异氰酸酯)或烯丙基异氰酸酯。
也可以使用饱和二异氰酸酯或多异氰酸酯代替或补充烯键式不饱和二异氰酸酯或多异氰酸酯,然后通过与除了不饱和基团外还具有至少一个异氰酸酯-活性基团的化合物反应而引入烯键式不饱和基团。
为此,通过以聚环氧烷的OH基为基准计1.6-30倍当量的二异氰酸酯反应来制得预聚物。NCO/OH的比例优选为4∶1至12∶1,更优选为2∶1。
如果合适,在制备过程中可以加入催化剂和/或稳定剂,催化剂例如是胺或锡化合物,稳定剂例如是苯甲酰氯、间苯二甲酰氯、磷酸二丁酯、3-氯丙酸或甲苯磺酸甲酯。
反应温度为20-120℃,优选为60-100℃。
然后可除去过量的未反应的异氰酸酯,优选通过薄膜蒸馏除去。
合适的饱和二异氰酸酯符合通式(I)
OCN-R-NCO(I),
其中R是C4-C22-亚烷基、C5-C22-环亚烷基、C8-C22-芳亚烷基(其中与异氰酸酯基连接的碳原子是sp3杂化的)或C6-C18-芳基。
这类二异氰酸酯的例子是HDI、IPDI、二异氰酸基环己基甲烷、2,2,4-三甲基六亚甲基二异氰酸酯、二异氰酸基甲基环己烷、二异氰酸基甲基三环癸烷、亚二甲苯基二异氰酸酯、四甲基亚二甲苯基二异氰酸酯、降冰片烷二异氰酸酯、环己烷二异氰酸酯、十二烷二异氰酸酯、2,4-TDI、2,6-TDI、2,2-、2,4-或4,4-MDI、4,4’-二异氰酸基-3,3’-二甲基联苯、3,4’-二异氰酸基二苯基醚、1,5-萘二异氰酸酯或它们的混合物。
但是,优选的是上述种类的脂族二异氰酸酯,原因在于,毒物学者通常认为所得聚氨酯的水解产物是安全的。
然后,这样得到的异氰酸酯官能预聚物与除了不饱和基团外还具有至少一个异氰酸酯-活性基团的化合物反应。优选的异氰酸酯-活性基团是氨基或羟基官能团,优选是羟基官能团。
NCO基团与NCO-活性基团的当量比优选为1.5∶1至1.0∶1。必须避免NCO-活性基团过量,否则将留下不饱和单体。在这种化合物不足时,剩余的游离NCO基团在施用前通过与水或单醇(如甲醇、乙醇或异丙醇)反应而除去。
优选的具有烯键式不饱和基团和至少一个异氰酸酯-活性基团的化合物是羟基丙烯酸酯和羟基甲基丙烯酸酯,例如丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、二丙烯酸丙三醇酯、二甲基丙烯酸丙三醇酯、丙三醇单丙烯酸酯单甲基丙烯酸酯、丙三醇单烯丙基醚甲基丙烯酸酯、TMP二丙烯酸酯、TMP二甲基丙烯酸酯、三丙烯酸季戊四醇酯、三甲基丙烯酸季戊四醇酯和它们的任意所需的混合物。
具有烯键式不饱和基团的亲水性聚氨酯的转化反应在20-80℃的温度下、优选在聚合抑制剂和OH-NCO反应催化剂存在下进行,所述聚合抑制剂例如是氢醌、氢醌单烷基醚、二叔丁基甲酚或亚甲基二(叔丁基甲酚),所述催化剂例如是锡化合物或胺。
水溶性氧化剂是能氧化所述水溶性还原剂或其它材料形成自由基的材料。
可用的水溶性氧化剂包括过氧化氢及其无机盐、过氧化物、氢过氧化物,例如叔丁基过氧化氢,过羧酸,例如过乙酸,过苯甲酸,过间氯苯甲酸,一过氧邻苯二甲酸和它们的铵盐、碱金属或碱土金属盐,无机过酸,优选以它们的铵盐或碱金属盐的形式,例如过硼酸,过碳酸,过氧二硫酸,过氧二磷酸,卡罗尔酸(Caro’s acid),过碘酸,高锰酸,高铼酸,卤素或供卤物质,次卤酸(hypohalides),亚氯酸钠,铈(IV)化合物,例如硝酸铈铵,或比在水中最稳定的价态更高的氧化态的金属离子,例如矾(V)化合物,锰(III)盐,铁(III)盐,六氰基(III)高铁酸盐,钴(III)盐,银(I)盐,溴酸钾或过硫酸氢钾制剂(oxone)。优选的是过氧二硫酸铵、过氧二硫酸钠和过氧二硫酸钾。
水溶性还原剂是能还原所述水溶性氧化剂形成自由基的材料。
可用的水溶性还原剂包括抗坏血酸,异抗坏血酸,含邻OH基的化合物,例如丙三醇或糖醇或糖或寡聚糖或多糖,还原性糖,例如葡萄糖,甲醛,乙二醛,乙醛酸,亚硫酸钠,亚硫酸铵,亚硫酸钾或相应的氢亚硫酸盐或亚硫酸氢盐或焦亚硫酸盐,亚硫酸盐-醛加合物,硫代硫酸钠,硫代硫酸钾,硫脲,氢醌,连苯三酚,没食子酸,草酸及其盐,酒石酸及其盐,丙二酸及其盐,甲酸及其盐,乳酸及其盐,水杨醛肟钛(III),次磷酸钠,亚磷酸、亚膦酸或三价膦酸的衍生物,甲苯亚磺酸钠(sodiumtoluenesulphinate),亚磺酸(sulphinous acid)的衍生物,例如Rongalit(甲醛次硫酸钠),连二亚硫酸钠,巯基乙醇,半胱氨酸和含半胱氨酸的肽,半胱氨酸胺,巯基乙酸,3-硫代丙酸,二氧化硫,NADH,碘化物,钴(II)盐或亚乙基硫脲。优选的是抗坏血酸。
除了氧化剂和还原剂外,还可以使用一种或多种活化剂。优选的活化剂是过渡金属盐,该过渡金属盐就象铁一样可以以不均匀的步幅改变其氧化态。铁盐是特别优选的活化剂。
优选的铁盐是铁(II)或铁(III)盐,例如氯化铁(II),硫酸铵铁(II),硫酸铁(II),硫酸铁(III),氯化铁(III),硝酸铁(III),乙酰丙酮铁(II),六氰基(II)高铁酸钾,六氰基(II)高铁酸钠,六氰基(II)高铁酸铵,六氰基(III)高铁酸钾,六氰基(III)高铁酸钠,六氰基(III)高铁酸铵,硝基普色酸钠(sodiumnitroprossate),D葡糖酸铁(II),乳酸铁(II),碘化铁(II),高氯酸铁(II),高氯酸铁(III),四氟硼酸铁(II)或甲苯磺酸铁(III),而且可以加入络合配体,例如次氮基三乙酸或EDTA。
在一个优选的实施方式中,A)使用1.0重量份的亲水性不饱和聚氨酯,B)使用0.2-19重量份水,C)使用以A)和B)的总量为基准计各0.05-5重量%的水溶性氧化剂和水溶性还原剂作为氧化还原体系。
当使用活化剂时,以A)和B)的总量为基准计,加入0.00001-0.01重量%、优选0.0001-0.001重量%的过渡金属盐。
本发明的方法优选通过分别提供氧化剂水溶液和还原剂水溶液来进行。待交联的亲水性聚氨酯已经分散或溶解到这两种溶液中的至少一种中。通过混合这两种溶液来引发交联,如果合适,混合可以在活化剂存在下进行,活化剂可以为溶液状态。
特别优选氧化剂溶液和还原剂溶液都含有溶解或分散形式的亲水性聚氨酯。
在室温以下可以观察到令人满意的形成水凝胶的反应速度。水凝胶的生产优选在5-100℃、更优选10-42℃的温度下进行。
可使用常规混合技术混合这两种溶液。
除了水凝胶的形成剂外,还可以加入WO 2002060501所述的抗菌活性物质,在此情况中优选的是水溶性物质。必须谨慎注意这些物质与氧化剂或还原剂之间可能的相互作用,因为组分之间可能相互破坏,造成产品在施用之前无法长期储存。但是,抗菌活性物质也可以完全或部分地起到氧化剂或还原剂的作用,例如过氧二硫酸盐、过氧化氢、高锰酸盐、银(I)化合物、亚硫酸盐或醛。
还可以加入增稠剂,例如聚乙烯醇,多糖的甲基、羟乙基、羟丙基或羧甲基醚,例如纤维素或淀粉,聚乙烯吡咯烷酮,聚丙烯酸,甲基乙烯基醚-MA共聚物,无机增稠剂,例如二氧化硅,铝硅酸盐或氢氧化铝,多肽,多糖,例如阿拉伯树胶或琼脂,壳聚糖,透明质酸或聚氨酯增稠剂,在此情况中,增稠剂也可以完全或部分地起到还原剂的作用。增稠剂可以预先结合到亲水性氨基甲酸酯丙烯酸酯的水溶液中,或者在反应开始前不久才加入。
例如,本发明的聚氨酯水凝胶可用作伤口接触材料。作为伤口接触材料,聚氨酯水凝胶可通过上述一种或多种组分的交联作用直接形成在皮肤或伤口上,或者施用预制的聚氨酯水凝胶,通常为片状伤口接触材料的形式。
本发明的聚氨酯水凝胶还可用作术后防粘材料(PSA)以防止器官不利地生长合拢。在此特别有利的是,聚氨酯水凝胶是由一种或多种最初为液体的组分制备的,因此尤其在内窥镜介入情况中可以计量加入到体内。在施用后,通过所述交联作用形成聚氨酯水凝胶。
根据聚氨酯多元醇组分的选择,由此生产的聚氨酯水凝胶可以是生物稳定或生物降解的。尤其在用作PSA时,优选施用可生物降解的聚氨酯水凝胶。
可以对人或动物使用。
实施例
实施例1:
将在60℃的由93.75克由TMP(3-官能)起始的环氧乙烷含量为63%、环氧丙烷含量为37%的聚醚、0.0625克亚甲基二-叔丁基甲酚(BKF)和0.0625克DBTL的初始加料与10克甲基丙烯酰氧基乙基异氰酸酯混合,搅拌4小时,在室温下静置4天。
然后,将10克该亲水性氨基甲酸酯丙烯酸酯和0.2克过氧二硫酸铵溶解在40克水中,单独再将另外10克亲水性氨基甲酸酯丙烯酸酯和1克抗坏血酸溶解在40克已经加入了10微升3%氯化铁(II)溶液的水中。然后,通过简单搅拌将两部分合并,5分钟后得到水凝胶。
实施例2:
在2小时内,在80℃时,向200克HDI和1克苯甲酰氯的初始进料中滴加400克由TMP(3-官能)起始的环氧乙烷含量为63%、环氧丙烷含量为37%的聚醚,然后搅拌1小时。然后,通过薄膜蒸馏在130℃和0.1托的条件下蒸馏除去过量的HDI,留下420克NCO含量为2.75%的预聚物。在60℃将153克该预聚物、0.1克BKF和0.1克DBTL与21.4克3-(丙烯酰氧基)-2-羟丙基酯甲基丙烯酸酯(丙三醇单丙烯酸酯单甲基丙烯酸酯)混合,冷却至室温,静置4天。
然后,将10克该亲水性氨基甲酸酯丙烯酸酯和0.2克过氧二硫酸铵溶解在40克水中,单独再将另外10克亲水性氨基甲酸酯丙烯酸酯和1克抗坏血酸溶解在40克已经加入了10微升3%氯化铁(II)溶液的水中。然后,通过简单搅拌将两部分合并,5分钟后得到水凝胶。
实施例3:
向112克六官能山梨糖醇起始的摩尔质量为6740克/摩尔的聚环氧乙烷中加入0.1克BKF和0.1克DBTL,然后加入15克MOI。将该混合物在室温下静置7天。
然后,将10克该亲水性氨基甲酸酯丙烯酸酯和0.2克过氧二硫酸铵溶解在40克水中,单独再将另外10克亲水性氨基甲酸酯丙烯酸酯和1克抗坏血酸溶解在40克已经加入了10微升3%氯化铁(II)溶液的水中。然后,通过简单搅拌将两部分合并,5分钟后得到水凝胶。
实施例4:
在2小时内,在80℃向100克HDI和2克苯甲酰氯的初始进料中滴加1000克四官能乙二胺起始的聚醚,其环氧乙烷含量为75%、环氧丙烷含量为25%,摩尔质量为4800克/摩尔。然后,将混合物在80℃搅拌6小时。然后,通过薄膜蒸馏在130℃除去过量的HDI,得到NCO含量为3.11%的预聚物。将67.5克该预聚物与0.1克BKF、0.1克DBTL和6.5克甲基丙烯酸羟乙酯(HEMA)混合。
然后,将10克该亲水性氨基甲酸酯丙烯酸酯和0.2克过氧二硫酸铵溶解在40克水中,单独再将另外10克亲水性氨基甲酸酯丙烯酸酯和1克抗坏血酸溶解在40克已经加入了10微升3%氯化铁(II)溶液的水中。然后,通过简单搅拌将两部分合并,5分钟后得到水凝胶。
Claims (12)
1.一种制备聚氨酯水凝胶的方法,该方法包括使A)在B)和C)存在下发生自由基交联:
A)具有烯键式不饱和基团的亲水性聚氨酯;
B)水;
C)包含水溶性氧化剂和水溶性还原剂的氧化还原体系,所述氧化剂在氧化还原电势方面能通过形成自由基与水溶性还原剂反应。
2.如权利要求1所述的方法,其特征在于,所述亲水性聚氨酯是基于羟基官能聚环氧烷。
3.如权利要求2所述的方法,其特征在于,以存在的氧化烯单元为基准计,羟基官能聚环氧烷的环氧乙烷含量至少为60%。
4.如权利要求2或3所述的方法,其特征在于,羟基官能聚环氧烷的分子量Mn=2000-20000克/摩尔,OH官能度为2-6。
5.如权利要求2-4中任一项所述的方法,其特征在于,所述亲水性聚氨酯具有丙烯酸酯或甲基丙烯酸酯基团作为烯键式不饱和基团。
6.如权利要求2-5中任一项所述的方法,其特征在于,所述亲水性聚氨酯是基于脂族或脂环族二异氰酸酯。
7.如权利要求2-6中任一项所述的方法,其特征在于,所述氧化还原体系由作为氧化剂的选自过氧二硫酸铵、过氧二硫酸钠和过氧二硫酸钾的至少一种化合物和作为还原剂的抗坏血酸组成。
8.如权利要求2-7中任一项所述的方法,其特征在于,所述铁盐用作活化剂,也用作氧化还原体系。
9.如权利要求2-8中任一项所述的方法,其特征在于,A)使用1.0重量份的亲水性不饱和聚氨酯,B)使用0.2-19重量份的水,C)使用以A)和B)的总量为基准计各0.05-5重量%的水溶性氧化剂和水溶性还原剂作为氧化还原体系。
10.如权利要求2至8中任一项所述的方法,其特征在于,还可以加入抗菌活性组分。
11.通过如权利要求1至10中任一项所述的方法得到的水凝胶。
12.如权利要求11所述的水凝胶在生产用于伤口治疗的接触材料中的应用。
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DE19953445A1 (de) * | 1999-11-06 | 2001-05-17 | Basf Coatings Ag | Selbstvernetzende Polyurethane und Pfropfmischpolymerisate auf Polyurethanbasis sowie ihre Verwendung zur Herstellung von Beschichtungsstoffen, Klebstoffen und Dichtungsmassen |
US20050271727A1 (en) | 2004-06-07 | 2005-12-08 | Callisyn Pharmaceuticals, Inc. | Biodegradable and biocompatible crosslinked polymer hydrogel prepared from PVA and/or PEG macromer mixtures |
CA2596861A1 (en) * | 2005-02-04 | 2006-08-10 | The Procter & Gamble Company | Absorbent structure with improved water-absorbing material |
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- 2007-01-18 DE DE102007002783A patent/DE102007002783A1/de not_active Withdrawn
-
2008
- 2008-01-08 KR KR1020097014948A patent/KR20090104826A/ko not_active Application Discontinuation
- 2008-01-08 CA CA002675605A patent/CA2675605A1/en not_active Abandoned
- 2008-01-08 CN CNA2008800025355A patent/CN101589085A/zh active Pending
- 2008-01-08 RU RU2009131140/04A patent/RU2009131140A/ru not_active Application Discontinuation
- 2008-01-08 JP JP2009545850A patent/JP2010516824A/ja not_active Withdrawn
- 2008-01-08 WO PCT/EP2008/000065 patent/WO2008086954A1/de active Application Filing
- 2008-01-08 BR BRPI0806776-7A patent/BRPI0806776A2/pt not_active IP Right Cessation
- 2008-01-08 EP EP08701008A patent/EP2121792A1/de not_active Withdrawn
- 2008-01-15 US US12/008,939 patent/US7947863B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
---|---|
US20080177213A1 (en) | 2008-07-24 |
BRPI0806776A2 (pt) | 2011-09-13 |
DE102007002783A1 (de) | 2008-08-07 |
WO2008086954A1 (de) | 2008-07-24 |
EP2121792A1 (de) | 2009-11-25 |
KR20090104826A (ko) | 2009-10-06 |
US7947863B2 (en) | 2011-05-24 |
JP2010516824A (ja) | 2010-05-20 |
CA2675605A1 (en) | 2008-07-24 |
RU2009131140A (ru) | 2011-02-27 |
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