CN115215988A - 多功能聚氨酯及其制备方法与应用 - Google Patents

多功能聚氨酯及其制备方法与应用 Download PDF

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CN115215988A
CN115215988A CN202210981613.2A CN202210981613A CN115215988A CN 115215988 A CN115215988 A CN 115215988A CN 202210981613 A CN202210981613 A CN 202210981613A CN 115215988 A CN115215988 A CN 115215988A
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张茂兰
曾国明
杨爽
丁慧
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Chongqing University of Science and Technology
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Abstract

本发明属于高分子材料技术领域，具体涉及一种多功能聚氨酯及其制备方法与应用。该多功能聚氨酯以二异氰酸酯、多元醇、HEP、荧光抗生素、单宁酸和DMPA为原料，利用缩聚反应原理制备而成。制备方法为：将多元醇、DMPA、HEP、荧光抗生素、二异氰酸酯和催化剂混合；充分溶解后，在氮气气氛下进行反应，制得聚氨酯预聚体；随后将单宁酸的丙酮溶液滴加入聚氨酯预聚体溶液中，并补加三乙胺，透析，冷冻干燥制得多功能聚氨酯。本专利提供的新型多功能聚氨酯兼具黏附性、pH响应性、荧光性和抗菌性，因此可作为敷料用于皮肤损伤修复领域，作为成像剂应用到体内诊断及治疗领域，甚至潜在地应用于药物控释领域。

Description

多功能聚氨酯及其制备方法与应用
技术领域
本发明属于高分子材料技术领域，具体涉及一种多功能聚氨酯及其制备方法与应用。
背景技术
聚氨酯(PU)是一种可设计性高、应用范围广、生物相容性较好的高分子材料，不仅自身具有优异的韧性和耐磨性能，而且PU的分子设计自由度很大，通过设计可以获得相当多的材料，这些材料有诸多不同的物理化学特性和机械特性。目前PU作为生物材料方面的研究，大多与生物相容性和血液相容性有关，利用PU独特的化学特性，对其进行扩链优化使PU材料在生物医学应用领域有很大的应用价值。
在生物医学应用领域，单一材料的性能已难以满足现有需求，限制了其在医疗领域的更广阔的应用，多功能材料早已成为人们研究的热点。PU的化学结构较复杂，它的合成需要具有三种典型的组成成分：扩链剂、二异氰酸酯和多元醇(低分子量聚合物)。荧光抗生素包含内在荧光抗生素及荧光基团与不同种类抗生素所形成的缀合物。其可帮助阐明抗生素的MOA，检测环境中的抗生素，追踪生物体内的抗生素摄取及检测细菌感染等。单宁酸(TA)是一种天然的多酚类化合物，能够与多种聚合物通过氢键、离子键或者疏水作用形成络合物，能够与多种金属离子配位，通过多重相互作用在形成一种理想的粘附单元。由于分子量从几百到几千的TA都含有大量的酚羟基，因此TA在聚氨酯合成中常常作为扩链剂或交联剂来使用，例如Satyarat等充分利用了TA多酚羟基的结构，合成并制备了超支化水性聚氨酯(WHPU)，该水性聚氨酯不仅具有良好的力学性能，而且具备一定的抗氧化能力和微生物降解性。
基于此，本专利结合聚氨酯的优点，采用单宁酸、姜黄素、1,4-双(2-羟乙基)哌嗪(HEP)对聚氨酯进行优化，制备出一种兼具荧光、pH缓冲、抗菌和粘附性能的多功能聚氨酯。
发明内容
本发明的目的之一在于提供一种用于制备多功能聚氨酯的组合物。
为实现上述目的，本发明采用以下技术方案：
用于制备多功能聚氨酯的组合物，所述组合物由二异氰酸酯及其衍生物、多元醇、2,2’-双(羟甲基)丙酸(DMPA)、1,4-双(2-羟乙基)哌嗪(HEP)、荧光抗生素和单宁酸(TA)组成；所述二异氰酸酯的物质的量为其他组分物质的量的总和。
进一步，所述组合物由二异氰酸酯及其衍生物、多元醇、DMPA、HEP、荧光抗生素和单宁酸按摩尔比为5.5-7：2：1：1：1：0.5-2组成。
进一步，所述多元醇为聚酯类二元醇、羟基封端的聚酰亚胺中的任一种或多种。
进一步，所述荧光抗生素为喹诺酮类荧光抗生素、大环内酯类荧光抗生素、氨基糖苷类荧光抗生素、磺胺类荧光抗生素、恶唑烷酮类荧光抗生素、天然荧光抗生素中的任一种或多种。
进一步，所述天然荧光抗生素为姜黄素。
进一步，所述二异氰酸酯及其衍生物为六亚甲基二异氰酸酯。
进一步，所述组合物由六亚甲基二异氰酸酯、羟基封端的聚酰亚胺、DMPA、HEP、姜黄素和单宁酸组成，其摩尔比为5.5-7：2：1：1：1：0.5-2。
进一步，所述组合物由六亚甲基二异氰酸酯、羟基封端的聚酰亚胺、DMPA、HEP、姜黄素和单宁酸组成，其摩尔比为5.5：2：1：1：1：0.5。
进一步，所述组合物由六亚甲基二异氰酸酯、羟基封端的聚酰亚胺、DMPA、HEP、姜黄素和单宁酸组成，其摩尔比为6：2：1：1：1：1。
进一步，所述组合物由六亚甲基二异氰酸酯、羟基封端的聚酰亚胺、DMPA、HEP、姜黄素和单宁酸组成，其摩尔比为7：2：1：1：1：2。
本发明的目的之二在于提供一种多功能聚氨酯，该多功能聚氨酯以TA作为扩链剂，并成功聚合TA和姜黄素，使得该多功能聚氨酯兼具黏附性、荧光性和抗菌性。
为实现上述目的，本发明采用以下技术方案：
一种多功能聚氨酯，所述多功能聚氨酯含有所述用于制备多功能聚氨酯的组合物。
TA作为聚氨酯的扩链剂的报道鲜有，而本专利用TA作为PU的扩链剂，将TA加入待聚合的PU中，使PU二次扩链，以此赋予PU生物相容性、药理活性和抗菌能力。同时，在预聚体二次扩链之前加入荧光抗生素，赋予PU荧光特性的同时，增加其抑菌性。因为姜黄素等荧光抗生素能在肿瘤发生部位聚集，其具有较快的全身清除率，避免了治疗后较长的避光时间及皮肤的光敏反应，并且具有良好的抗细菌，抗真菌，抗氧化，抗炎和抗癌等生物活性。本专利成功聚合TA和姜黄素，使本品多功能聚氨酯具有一定的抑菌性能，其抗炎、抗氧化、抗癌性能还处于研究中。
本发明专利的多功能聚氨酯主要用于生物医学方面，而人体内各种体液的pH值具有十分重要的意义，为保证机体的各种功能活动可以正常进行，需要控制pH值在一狭小范围内，因此本专利引入非离子两性缓冲物HEP，以优化该聚氨酯的pH缓冲性。
本发明的目的之三在于提供一种多功能聚氨酯的制备方法。
为实现上述目的，本发明采用以下技术方案：
多功能聚氨酯的制备方法，具体包括以下步骤：
S1：将所述多元醇、所述DMPA、所述HEP、所述荧光抗生素、所述二异氰酸酯及其衍生物、丙酮和异辛酸亚锡混合并充分溶解，得混合溶液1；
S2：将S1所得混合溶液1在氮气气氛下进行反应，制得聚氨酯预聚体；
S3：将单宁酸的丙酮溶液滴加入S2制得的聚氨酯预聚体溶液中，加入三乙胺调节pH值为碱性，制得所述多功能聚氨酯。
进一步，所述异辛酸亚锡为催化剂。
进一步，所述异辛酸亚锡用量占原料的比重为1/100～1/1000。
进一步，S2中，反应温度为70-80℃，反应时间为3-10小时。
进一步，S3中，补加三乙胺后，反应温度为60-75℃搅拌10min-2h，并进行透析，冷冻干燥得到所述多功能聚氨酯。
进一步，所述多元醇为羟基封端的聚酰亚胺。
进一步，所述羟基封端的聚酰亚胺为均苯四甲酸酐(PMDA)与氨基封端的聚乙二醇/乙二胺/己二胺等二胺类化合物反应制得的酸酐封端的聚合物，并加入乙醇胺进行羟基封端。
进一步，所述均苯四甲酸酐的物质的量大于氨基封端的聚乙二醇/乙二胺/己二胺等二胺类化合物，所述乙醇胺的物质的量大于均苯四甲酸酐和氨基封端的聚乙二醇/乙二胺/己二胺等二胺类化合物的物质的量之差。
更进一步，所述均苯四甲酸酐、所述聚乙二醇、所述乙醇胺的摩尔比优选为1.1：1：0.2。
进一步，所述羟基封端的聚酰亚胺的制备方法具体为：
(1)向圆底烧瓶中按比例加入ATPEG和PMDA，再加入溶剂N-甲基吡咯烷酮(NMP)，使其充分溶解；
(2)充氮气，抽真空，随后在40℃条件下加热8-10h；
(3)之后，向烧瓶中加入乙醇胺，接冷凝管，氮气气氛下进行梯度升温加热，40℃加热4-8h，120℃加热1-4h，150℃加热1-4h，180℃加热1-4h，最后200℃加热1-2h；
(4)制备完成后对材料进行透析，使用MD为1000的透析袋，用二次水透析2天，之后冷冻干燥，得到产物PAPI。
进一步，所述多功能聚氨酯在制备抗菌敷料中的应用。
进一步，所述多功能聚氨酯在制备用于疾病诊断的成像剂中的应用。
进一步，所述多功能聚氨酯在制备控释药物中的应用，所述多功能聚氨酯用于维持生物的正常pH值。
进一步，所述多功能聚氨酯在污水处理中的应用，采用所述多功能聚氨酯吸附污水中的重金属离子。
本发明的有益效果在于：
1.本专利以单宁酸作为扩链剂，单宁酸通过氢键、离子键、疏水缔合作用等多种化学键和分子间作用发挥络合和交联作用对聚氨酯进行二次扩链处理，增加聚氨酯的粘附性及抗菌性，使其可用做敷料等医学领域。
2.本专利在聚氨酯的合成过程中加入了荧光抗生素，使本品聚氨酯具有荧光特性和抗菌性，使聚合物可以作为成像剂应用到体内诊断及治疗领域。
3.本专利在聚合物合成中加入具有pH响应性的HEP，增强材料的pH缓冲性，对材料维持生物的正常pH值和正常生理环境起到重要作用，可潜在地应用于药物控释领域。
附图说明
图1为红外光谱分析图；
图2为pH缓冲性结果图；
图3为荧光测试图；
图4为抑菌测试结果；
图5为粘附性测试图；
具体实施方式
下面将结合具体的实施例对本发明的技术方案进行更进一步地清楚、完整地描述。显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部实施例。因此，基于本发明中的实施例，本领域技术人员在没有付出创造性劳动前提下所获得的其他所有实施例都属于本发明的保护范围。
实施例1.PAPI的制备方法
PAPI是均苯四甲酸酐(PMDA)与聚乙二醇(ATPEG)反应制备酸酐封端的聚合物，随后加入乙醇胺进行羟基封端；材料比例：n(PMDA):n(ATPED):n(乙醇胺)＝1.1:1:0.2，制备方法具体如下：
(1)向圆底烧瓶中按比例加入ATPEG和PMDA，再加入溶剂N-甲基吡咯烷酮(NMP)，使其充分溶解；
(2)充氮气，抽真空，随后在40℃条件下加热8h；
(3)8h后，向烧瓶中加入乙醇胺，接冷凝管，氮气气氛下进行梯度升温加热，40℃加热4h，120℃加热3h，150℃加热4h，180℃加热2h，最后200℃加热1h；
(4)制备完成后对材料进行透析，使用MD为1000的透析袋，用二次水透析2天，之后冷冻干燥，得到产物PAPI。
实施例2.多功能聚氨酯PU-TA(P1)
Figure BDA0003799245740000051
实施例3.多功能聚氨酯PU-TA(P2)
Figure BDA0003799245740000052
实施例4.多功能聚氨酯PU-TA(P3)
Figure BDA0003799245740000053
实施例5.多功能聚氨酯PU-TA的制备方法
(1)按比例将适量PAPI、DMPA、HEP、HDI、姜黄素，催化剂异辛酸亚锡和适量丙酮加入到圆底烧瓶中；
(2)待溶解之后，加上冷凝管，氮气气氛下，75℃条件下反应6小时，得到PU预聚体；
(3)按照摩尔比将单宁酸的丙酮溶液滴加入PU预聚体溶液中，并添加三乙胺调节pH值至碱性，然后升温至60℃搅拌5-10min后，将材料进行透析，冷冻干燥得到多功能聚氨酯。
实施例6.PU-TA表征
1.本发明通过红外光谱分析(FT-IR)对实施例4制得的PU-TA聚合物的结构进行分析，结果如图1所示，3428cm-1处为姜黄素和TA中的酚羟基OH和氨基甲酸酯键中NH伸缩振动吸收峰，2870cm-1处为PAPI链段中CH伸缩振动吸收峰，1770cm-1为DMPA中游离羧酸的C＝O伸缩振动峰，1719cm-1处为氨基甲酸酯键和TA中酯键的C＝O伸缩振动吸收峰，1628cm-1为芳香部分C＝C伸缩振动峰，1040cm-1处为C-O-C振动峰，由此表明PU-TA多功能聚氨酯制备成功。
2.实施例4制得的PU-TA的pH缓冲性：HEP是一种非离子两性缓冲液，在pH6.8-8.2范围内有较强的缓冲能力，优化了聚氨酯的pH缓冲性。本发明通过酸碱滴定实验方法确定PU-TA的pH缓冲性。先将pH均调节至2.3左右，随着NaOH的滴加，明显可以看出PU组的pH变化斜率小于水，水几乎没有缓冲能力，详见图2。曲线的斜率越小表示对pH的缓冲能力越强。同时考察发现，TA的含量对多功能聚氨酯的pH缓冲性也有影响，TA含量的越高，pH缓冲性越明显。
3.实施例4制得的PU-TA的荧光测试：在化学性质上，姜黄素本身具有优质稳定的荧光特性，如图3所示，本发明通过通过荧光分光光度计检测了多功能聚氨酯的荧光激发光谱和荧光发射光谱，发现姜黄素聚合成功，使多功能聚氨酯具备较高的荧光性能，增加了多功能聚氨酯的荧光追踪功能，但是TA的含量对吸光度和荧光值也有所影响，TA含量的越高，荧光值越大。
4.实施例2、3制得的PU-TA的抑菌测试：在生物性能上，TA本身具有一定的抑菌作用，再者姜黄素可通过细菌群体感应调节系统抑制细菌毒力因子，抑制细菌生物膜形成，防止细菌粘附于宿主受体，成功聚合TA和姜黄素是该多功能聚氨酯具有一定的抑菌性能的原因。本发明通过抑菌圈实验验证制得的多功能聚氨酯对细菌的抑制作用，结果如图4所示，制得的多功能聚氨酯对金黄色葡萄球菌表现出了较好的的抗菌性能，且其抗菌性能可以通过调整多功能聚氨酯中的原料比例进行调节；图4中，PU1和PU2分别为实施例2和3制得的PU-TA。
5.实施例3制得的PU-TA的粘附性：在物理性质上，TA能够通过多重相互作用在多结合位点与高分子复合或者是交联，并且它还能够与金属配位形成TA-金属的网络结构，因此，TA在聚氨酯合成中可形成一种理想的粘附单元，使多功能聚氨酯的粘附性增强，同时也赋予了该多功能聚氨酯吸附金属离子的能力，可用于污水中的重金属离子吸附。如图5所示，本专利制得的多功能聚氨酯具有较好的粘附性。

Claims (12)

1.用于制备多功能聚氨酯的组合物，其特征在于，所述组合物由二异氰酸酯及其衍生物、多元醇、DMPA、HEP、荧光抗生素和单宁酸组成；所述二异氰酸酯的物质的量为其他组分物质的量的总和。
2.根据权利要求1所述的组合物，其特征在于，所述组合物由二异氰酸酯及其衍生物、多元醇、DMPA、HEP、荧光抗生素和单宁酸按摩尔比为5.5-7：2：1：1：1：0.5-2组成。
3.根据权利要求2所述的组合物，其特征在于，所述多元醇为聚酯类二元醇、羟基封端的聚酰亚胺中的任一种或多种。
4.根据权利要求2所述的组合物，其特征在于，所述荧光抗生素为喹诺酮类荧光抗生素、大环内酯类荧光抗生素、氨基糖苷类荧光抗生素、磺胺类荧光抗生素、恶唑烷酮类荧光抗生素、天然荧光抗生素中的任一种或多种。
5.根据权利要求4所述的组合物，其特征在于，所述天然荧光抗生素为姜黄素。
6.根据权利要求2所述的组合物，其特征在于，所述二异氰酸酯及其衍生物为六亚甲基二异氰酸酯。
7.一种多功能聚氨酯，其特征在于，所述多功能聚氨酯含有权利要求1-6任一所述的用于制备多功能聚氨酯的组合物。
8.权利要求7所述的多功能聚氨酯的制备方法，其特征在于，具体包括以下步骤：
S1：将所述多元醇、所述DMPA、所述HEP、所述荧光抗生素、所述二异氰酸酯及其衍生物、丙酮和异辛酸亚锡混合并充分溶解，得混合溶液1；
S2：将S1所得混合溶液1在氮气气氛下进行反应，制得聚氨酯预聚体；
S3：将单宁酸的丙酮溶液滴加入S2制得的聚氨酯预聚体溶液中，加入三乙胺调节pH值为碱性，制得所述多功能聚氨酯。
9.权利要求7所述的多功能聚氨酯在制备抗菌辅料中的应用。
10.权利要求7所述的多功能聚氨酯在制备用于疾病诊断的成像剂中的应用。
11.权利要求7所述的多功能聚氨酯在制备控释药物中的应用，其特征在于，所述多功能聚氨酯用于维持生物的正常pH值。
12.权利要求7所述的多功能聚氨酯在污水处理中的应用，其特征在于，采用所述多功能聚氨酯吸附污水中的重金属离子。
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