CN105482105A - 一种可降解主链季铵盐型聚阳离子及其制备方法 - Google Patents

一种可降解主链季铵盐型聚阳离子及其制备方法 Download PDF

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CN105482105A
CN105482105A CN201510960608.3A CN201510960608A CN105482105A CN 105482105 A CN105482105 A CN 105482105A CN 201510960608 A CN201510960608 A CN 201510960608A CN 105482105 A CN105482105 A CN 105482105A
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游正伟
王少飞
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National Dong Hwa University
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    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
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    • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids

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Abstract

本发明涉及一种可降解主链季铵盐型聚阳离子及其制备方法，所述阳离子结构式为制备方法包括：将等摩尔量的1,2-双(氯乙酰氧基)乙烷和N,N,Nˊ,Nˊ-四甲基-1,4-丁二胺加入到容器中，加入甲醇或乙醇，将容器密封，室温下搅拌反应，静置，固液分离，得到的固体进行沉淀纯化，真空干燥，即得。本发明能制备可降解的主链季铵盐型聚阳离子，有望在生物医学领域有进一步的应用。本发明的制备方法条件温和，简单高效。

Description

一种可降解主链季铵盐型聚阳离子及其制备方法
技术领域
本发明属于聚阳离子及其制备方法领域，特别涉及一种可降解主链季铵盐型聚阳离子及其制备方法。
背景技术
在自然界中，阳离子多肽在基因表达，调控DNA响应及组织蛋白的生成过程中起着重要的作用(Gf.chromatin.Science.1978；271:115.)，如调控人体内生理活动(GanzT.Chemistry-Ringsofdestruction.Nature.2001；412:392-3.)，控制生长因子的稳定和活性(FahamS,HilemanRE,FrommJR,LinhardtRJ,ReesDC.Heparinstructureandinteractionswithbasicfibroblastgrowthfactor.Science.1996；271:1116-20.)。合成聚阳离子在生物医学领域也有广泛的应用。比如在基因治疗上，PEI(聚醚酰亚胺)是人工合成的最著名的基因载体之一(PackDW,HoffmanAS,PunS,StaytonPS.Designanddevelopmentofpolymersforgenedelivery.NatRevDrugDiscov.2005；4:581-93.NguyenDN,GreenJJ,ChanJM,LongerR,AndersonDG.PolymericMaterialsforGeneDeliveryandDNAVaccination.AdvMater.2009；21:847-67.)。近来Wang(ZernBJ,ChuHH,OsunkoyaAO,GaoJ,WangYD.ABiocompatibleArginine-BasedPolycation.AdvFunctMater.2011；21:434-40.)等发展了基于精氨酸的聚阳离子，生物学实验结果表明具有良好的生物相容性，利用其和肝素结合，可以有效控制生长因子的缓释(ChuHH,JohnsonNR,MasonNS,WangYD.A[polycation:heparin]complexreleasesgrowthfactorswithenhancedbioactivity.JControlRelease.2011；150:157-63.ChuHH,GaoJ,ChenCW,HuardJ,WangYD.Injectablefibroblastgrowthfactor-2coacervateforpersistentangiogenesis.PNatlAcadSciUSA.2011；108:13444-9.)。
季铵盐型聚合物是另外一种重要的聚阳离子，它们具有良好的表面活性和杀菌灭藻的功能，得到了广泛的研究和应用(刘才林，胡小亮，任先艳.XK一2C双季铵盐阳离子型乳化剂的合成及在乳化沥青中的应用.西南科技大学学报.2010；25:17-20。刘慷慨，高保娇，李蕾.可聚合双季铵盐阳离子表面活性剂.石油化工.2006；35:1082-5.黄涛，游毅.多疏水链阳离子二聚表面活性剂的合成.合成化学.2005；13:480-2.)。近年来材料的可降解性越来越受到人们的关注。特别是基于生物医药领域的应用比如组织工程、药物缓释等，材料的可降解性是关键的特性之一。而目前已经发展的聚阳离子中可降解的相对较少，特别是对于聚季铵盐，多数为不可降解的。
发明内容
本发明所要解决的技术问题是提供一种可降解主链季铵盐型聚阳离子及其制备方法，该聚阳离子具有良好的降解性，有望在生物医学领域有进一步的应用，制备方法条件温和，效率高。
本发明的一种可降解主链季铵盐型聚阳离子，结构式为：
其中，n＝3～300。
本发明的一种可降解主链季铵盐型聚阳离子的制备方法，包括：氮气氛围下，将等摩尔量的1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺加入到容器中，加入甲醇或乙醇，将容器密封，室温下搅拌4～72h，静置，固液分离，得到的固体进行沉淀纯化，真空干燥，得到可降解主链季铵盐型聚阳离子，反应式为：
其中，1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺的质量之和与甲醇或乙醇的比例为1g：1ml—1g：10ml。
所述容器经过无水无氧处理。
所述搅拌的时间为18h。
所述搅拌结束后，溶液变成白色乳浊液。
所述真空干燥的条件为室温条件下，用隔膜泵抽24h。
所述真空干燥得到的是白色粉末状产物。
所述沉淀纯化为甲醇为良溶剂，四氢呋喃为不良溶剂对固体进行沉淀纯化三次。
所述1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺的质量之和与甲醇或乙醇的比例为1g：1ml—1g：5ml。
1,2-双(氯乙酰氧基)乙烷，购于TCI；N,N,N',N'-四甲基-1,4-丁二胺(98％)，购于SIGMA；甲醇(HPLC)、四氢呋喃(THF，AR)购于永华化学科技(江苏)有限公司。
本发明的可降解的聚季铵盐，为生物医学等领域的应用提供新的聚阳离子材料。通过反应单体的筛选，及反应过程的设计，一步法合成了一种主链型季铵盐聚合物，并对其结构及热学性质进行了表征。本发明的关键是选择了1,2-双(氯乙酰氧基)乙烷作为单体，其上α位羰基增强了碳氯键对应的碳的缺电子性，从而提高了反应的活性，在不需要催化剂情况下，室温高效地制备了目标产物。同时，2-双(氯乙酰氧基)乙烷为一个二酯，从而使合成的聚阳离子主链为聚酯结构，具有良好的降解性，有望在生物医学领域有进一步的应用。
本发明同样适用于其它类似结构的制备。比如其它的二元胺，其它的二元氯乙酸酯，或者二α-氯代酮等碳氯键被旁边其它的吸电子基团(比如羰基，硝基，氰基，氟烷基，砜基，亚砜基)所活化的底物。
有益效果
(1)本发明的可降解主链季铵盐型聚阳离子具有良好的降解性，有望在生物医学领域有进一步的应用；
(2)本发明的制备方法条件温和，简单高效。
附图说明
图1为实施例1中物质表征图；A和B为N,N,N',N'-四甲基-1,4-丁二胺及产物聚季铵盐的核磁谱图；C为产物聚季铵盐的碳谱图；D为产物聚季铵盐的红外谱图；
图2为实施例1中产物聚季铵盐的热重曲线。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
把100ml三口烧瓶做无水无氧处理，将其转移至手套箱中，氮气氛围下，加入等摩尔量的1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺。然后根据反应药品的质量，向反应瓶中注入一定体积的甲醇(每1克单体加入3ml甲醇)。加料完成后，将反应体系进行密封，转移出手套箱，在室温下搅拌18小时，溶液变成白色乳浊液。静置反应体系，将固液分离，并以甲醇为良溶剂，四氢呋喃为不良溶剂对所得固体进行沉淀纯化三次，真空干燥，得到白色粉末状产物。
对本实施例中得到的产物进行性能表征。1HNMR和13CNMR谱图由BrukeAM-400(400MHz)型核磁共振仪测定，氘代甲醇(CH3OD)为溶剂，TMS作内标。采用KBr压片法制作样品，将KBr和季铵盐型聚阳离子放在玛瑙研钵中研磨充分，制作压片，将所做的试样在Nicolet380FT-IR傅里叶变换红外光谱仪上表征。
采用美国TA仪器公司生产的Discovery型热重分析仪对样品进行测试。从室温开始加热到400℃，升温速率10℃/min。
图1(A)及(B)中所示为N,N,N',N'-四甲基-1,4-丁二胺及产物聚季铵盐的核磁谱图，对原料N,N,N',N'-四甲基-1,4-丁二胺来说，δ2.26(b)是-N(CH3)2中甲基的峰，δ2.36(a)是N-CH2-CH2-CH2-CH2-N中和氮直接相连的亚甲基的峰，δ1.51(c)是N-CH2-CH2-CH2-CH2-N中当中两个亚甲基的峰，在产物的核磁数据中，这三个位置的峰都消失了，对应的氢的信号都移向低场，相应的化学位移分别为δ3.35，δ3.72，δ1.91。这是由于生成了带正电性的季铵盐结构，对周围的氢具有吸电子作用，这有力地证实了门秀金反应的发生。碳谱数据如图1C示：13CNMR(100.6MHz,CH3OD)δ165.07,67.61,67.50,64.39,53.45,19.19，碳谱数据也进一步确认了产物的分子结构。图1(D)所示为产物红外谱图，在3000cm-1附近有C-H键形成的伸缩振动吸收峰，在1750cm-1附近有明显的C＝O键形成的吸收峰，在1500-1400cm-1有C-H键弯曲振动形成的吸收峰，在1400-1000cm-1内有C-N键及C-O键形成的吸收峰。进一步确认了产物的分子结构。
季铵盐型聚阳离子的热稳定性通过(TGA)进行表征。TGA实验显示(图2)，季铵盐型聚阳离子失重1％的温度为183.9℃，说明它在室温和人体温度下，都具有良好的稳定性，能够在比较广的温度范围内使用。
原料1,2-双(氯乙酰氧基)乙烷为固体，能够在常见溶剂诸如四氢呋喃，氯仿，丙酮里都有良好的溶解性，而产物在常见有机溶剂如四氢呋喃，氯仿，丙酮等中都不溶。而是在溶解于水和大极性的溶剂比如甲醇、乙醇等。进一步证实了其离子化的结构。我们选用正己烷，乙醚，四氢呋喃，氯仿，丙酮，乙酸乙酯，二甲基甲酰胺(DMF)，乙醇，甲醇，水作为溶剂，对产物进行溶解性测试，测试结果如下表所示：
表1季铵盐型聚阳离子在不同溶剂中的溶解性能
溶剂 正己烷 乙醚 四氢呋喃 氯仿 丙酮
溶解性 - - - - -
溶剂 乙酸乙酯 DMF 乙醇 甲醇 水
溶解性 - - + + +
结果表明，其有较高的热降解温度，有良好的水溶性。进而从分子结构上说，其为聚酯，从而具有可降解性。本发明的门秀金(Menschutkin)反应，通过选用活化的底物，可以在室温下，高效地进行，其基本理念，可以应用于类似的各种二元醇对应的α氯代乙酸酯和各种二元仲胺的门秀金反应中，从而制备出一系列的可降解的聚阳离子，有望为生物医学提供新材料。

Claims (5)

1.一种可降解主链季铵盐型聚阳离子，结构式为：
其中，n＝3～300。
2.一种可降解主链季铵盐型聚阳离子的制备方法，包括：将等摩尔量的1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺加入到容器中，加入甲醇或乙醇，将容器密封，室温下搅拌4～72h，静置，固液分离，得到的固体进行沉淀纯化，真空干燥，得到可降解主链季铵盐型聚阳离子；其中，1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺的质量之和与甲醇或乙醇的比例为1g：1ml—1g：10ml。
3.根据权利要求2所述的一种可降解主链季铵盐型聚阳离子的制备方法，其特征在于，所述搅拌的时间为18h。
4.根据权利要求2所述的一种可降解主链季铵盐型聚阳离子的制备方法，其特征在于，所述沉淀纯化为甲醇为良溶剂，四氢呋喃为不良溶剂对固体进行沉淀纯化三次。
5.根据权利要求2所述的一种可降解主链季铵盐型聚阳离子的制备方法，其特征在于，所述1,2-双(氯乙酰氧基)乙烷和N,N,N',N'-四甲基-1,4-丁二胺的质量之和与甲醇或乙醇的比例为1g：1ml—1g：5ml。
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* Cited by examiner, † Cited by third party
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WO2019116163A1 (en) * 2017-12-12 2019-06-20 International Business Machines Corporation Hydrophilic polymers with antimicrobial functionalities
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US10667514B2 (en) 2017-12-12 2020-06-02 International Business Machines Corporation Antimicrobial ionene compositions with a variety of functional groups
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US10743537B2 (en) 2017-12-12 2020-08-18 International Business Machines Corporation Monomer compositions with antimicrobial functionality
US10836864B2 (en) 2017-12-12 2020-11-17 International Business Machines Corporation Chemical compositions with antimicrobial functionality
CN116410464A (zh) * 2023-04-14 2023-07-11 湖南大学 可点击化学修饰的主链阳离子聚合物及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5653602A (en) * 1979-10-07 1981-05-13 Chiyoda Kagaku Kenkyusho:Kk Removing agent for slime
WO2011006011A2 (en) * 2009-07-08 2011-01-13 Virginia Tech Intellectual Properties Inc. Theranostic polycation beacons comprising oligoethyleneamine repeating units and lanthanide chelates
CN102807510A (zh) * 2012-07-06 2012-12-05 华南理工大学 含季铵盐结构的抗菌性甲基丙烯酸酯单体及其制法和应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5653602A (en) * 1979-10-07 1981-05-13 Chiyoda Kagaku Kenkyusho:Kk Removing agent for slime
WO2011006011A2 (en) * 2009-07-08 2011-01-13 Virginia Tech Intellectual Properties Inc. Theranostic polycation beacons comprising oligoethyleneamine repeating units and lanthanide chelates
CN102807510A (zh) * 2012-07-06 2012-12-05 华南理工大学 含季铵盐结构的抗菌性甲基丙烯酸酯单体及其制法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张文艺 等: "水溶性聚季铵盐制备及其异养菌杀菌性能", 《过程工程学报》 *

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WO2019116163A1 (en) * 2017-12-12 2019-06-20 International Business Machines Corporation Hydrophilic polymers with antimicrobial functionalities
US10653142B2 (en) 2017-12-12 2020-05-19 International Business Machines Corporation Polymers with antimicrobial functionalities
US10667514B2 (en) 2017-12-12 2020-06-02 International Business Machines Corporation Antimicrobial ionene compositions with a variety of functional groups
US10687528B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Antimicrobial polymers with enhanced functionalities
US10687530B2 (en) 2017-12-12 2020-06-23 International Business Machines Corporation Hydrophilic polymers with antimicrobial functionalities
US10595527B2 (en) 2017-12-12 2020-03-24 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US10836864B2 (en) 2017-12-12 2020-11-17 International Business Machines Corporation Chemical compositions with antimicrobial functionality
US11525036B2 (en) 2017-12-12 2022-12-13 International Business Machines Corporation Chemical compositions with antimicrobial functionality
US11058110B2 (en) 2017-12-12 2021-07-13 International Business Machines Corporation Polymers with antimicrobial functionalities
US11006628B2 (en) 2017-12-12 2021-05-18 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US11617367B2 (en) 2017-12-12 2023-04-04 International Business Machines Corporation Antimicrobial polymers capable of supramolecular assembly
US11723363B2 (en) 2017-12-12 2023-08-15 International Business Machines Corporation Polymers with antimicrobial functionalities
CN116410464A (zh) * 2023-04-14 2023-07-11 湖南大学 可点击化学修饰的主链阳离子聚合物及其制备方法

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