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    • 1. 发明申请
    • Polymer Synthesis
    • 聚合物合成
    • US20130046052A1
    • 2013-02-21
    • US13583557
    • 2011-03-08
    • Steven P. ArmesYuting Li
    • Steven P. ArmesYuting Li
    • C08F265/06C09D153/00C08F259/02C08F275/00C08F265/10
    • C08F2/18C08F2/38C08F293/005C08F2438/03
    • A method of preparing a block copolymer of Formula (B) wherein P1 represents a substantially aqueously soluble polymeric component and P2 represents a substantially aqueously insoluble polymeric component, comprises admixing an aqueously soluble polymer macro-chain transfer agent comprising P1 with a monomer (M2) and initiating an aqueous dispersion-type radical addition fragmentation chain transfer (RAFT) polymerisation. (P1) is derived from a monomer (M1) selected from monomers of the Formulae (M1A), (M1B) and/or (M1C) where R1, R10 and R11 represent a substituent of (M1A) or (M1C) which allows P1 to be at least partially aqueously soluble, R2 represents H, CH3 or CN, RS represents one or more substituents of the aromatic ring effective to allow P1 to be at least partially aqueously soluble, and monomer M2 is selected from: where R3 is a substituent of (M2) which allows P2 to be substantially aqueously insoluble, and R4 and R6 independently represent H or methyl.
    • 制备式(B)的嵌段共聚物的方法,其中P1表示基本上是溶解性的聚合物组分,P2表示基本上不溶于水的聚合物组分,包括将包含P1的水溶性聚合物大分子链转移剂与单体(M2)混合, 并引发水分散型自由基加成断裂链转移(RAFT)聚合。 (P1)衍生自选自式(M1A),(M1B)和/或(M1C)的单体的单体(M1),其中R1,R10和R11表示(M1A)或(M1C)的取代基,其允许P1 至少部分是水溶性的,R 2表示H,CH 3或CN,RS表示芳族环的一个或多个取代基,其有效使P1至少部分可溶于水,单体M2选自:其中R 3为取代基 的(M2),其允许P2基本上不溶解,并且R 4和R 6独立地表示H或甲基。
    • 7. 发明申请
    • Synthesis of Reversible Shell Crosslinked Nanostructures
    • 可逆壳交联纳米结构的合成
    • US20080234391A1
    • 2008-09-25
    • US12048680
    • 2008-03-14
    • Charles L. McCormickBrad S. LokitzYuting Li
    • Charles L. McCormickBrad S. LokitzYuting Li
    • A61K47/32C08L53/00
    • C08F293/00A61K9/1075C08F293/005C08F297/02C08F297/026C08F2438/03C08J3/246C08J2353/00C08L53/00C08L2666/02
    • In one aspect, the present invention is directed to a thermally responsive AB diblock copolymer prepared by RAFT polymerization wherein the diblock copolymer comprises poly(N-(3-aminopropyl)methacrylamide hydrochloride)-block-(N-isopropylacrylamide). Nanostructures of the thermally responsive diblock copolymer are formed by molecularly dissolving the diblock copolymer in aqueous solution at room temperature; and increasing the solution temperature to form nanostructures, for example vesicles or micelles. The first RAFT polymerization of an unprotected amino acid based monomer directly in water is also disclosed. The present invention also provides a method of forming shell cross-linked vesicles by adding a RAFT synthesized anionic homopolymer to a solution of the thermally responsive diblock copolymer. A method of forming interpolyelectrolyte complexed micelles or vesicles is also disclosed, the method comprising preparing by sequential aqueous RAFT polymerization a block copolymer comprised of N,N,-dimethyl acrylamide (DMA), N-acryloyl alanine (AAL) and N-isopropyl acrylamide (NIPAM); dissolving the block copolymers into aqueous solution; raising the solution temperature above the lower critical solution temperature of the NIPAM block; allowing the micelle solution to equilibrate; adjusting the pH of the solution to about 5; adding a cationic polymer to the solution; and stirring the solution. The reaction is readily reversed by the addition of a salt solution. In another aspect of the invention a reversible shell cross-linked micelle of a triblock copolymer cross-linked with cystamine is disclosed where a cleaving agent can be added to cleave the micelles. The reaction can be reversed with the addition of tris(2-carboxyethyl)phosphine or dithiothreitol.
    • 一方面,本发明涉及通过RAFT聚合制备的热响应性AB二嵌段共聚物,其中二嵌段共聚物包含聚(N-(3-氨基丙基)甲基丙烯酰胺盐酸盐) - 嵌段 - (N-异丙基丙烯酰胺)。 热响应二嵌段共聚物的纳米结构体是通过在室温下将二嵌段共聚物分子式溶解在水溶液中形成的; 并增加溶液温度以形成纳米结构,例如囊泡或胶束。 还公开了直接在水中的未保护的氨基酸基单体的第一次RAFT聚合。 本发明还提供了通过将RAFT合成的阴离子均聚物加入到热响应的二嵌段共聚物的溶液中来形成壳交联囊泡的方法。 还公开了形成聚电解质络合的胶束或囊泡的方法,该方法包括通过连续水性RAFT聚合制备由N,N, - 二甲基丙烯酰胺(DMA),N-丙烯酰丙氨酸(AAL)和N-异丙基丙烯酰胺 (NIPAM); 将嵌段共聚物溶解在水溶液中; 提高溶液温度高于NIPAM嵌段的较低临界溶解温度; 使胶束溶液平衡; 将溶液的pH调节至约5; 向溶液中加入阳离子聚合物; 并搅拌溶液。 反应容易通过加入盐溶液逆转。 在本发明的另一方面,公开了与胱氨酸交联的三嵌段共聚物的可逆壳交联胶束,其中可加入裂解剂以切割胶束。 反应可以通过加入三(2-羧乙基)膦或二硫苏糖醇来反转。