Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide),PEG-b-(PNIPAM)_2,were successfully synthesized through atom transfer radical polymerization(ATRP).A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly(ethylene glycol) monomethyl ether(PEG).The copolymers were obtained via the ATRP of N-isopropylacrylamide(NIPAM) at 30℃with CuCl/Me_6TREN as a catalyst system and DMF/H_2O(v/v = 3:1) mixture as solvent.The resulting copo...     

酶促缩聚和原子转移自由基聚合法合成AB型两亲性嵌段共聚物

Novozyme-435催化10-羟基癸酸进行自缩聚反应得到线性聚酯, 端基分别是羟基(—OH)和羧基(—COOH), 在三乙胺催化下, 分别用α-溴代丙酰溴和三甲基氯硅烷(TMSCL)进行端基官能化生成一个单官能度的大分子引发剂, 在CuCl/2,2'-联吡啶(bpy)催化体系中, 引发甲基丙烯酸环氧丙酯(GMA)的原子转移自由基反应(ATRP), 得到聚(10-羟基癸酸酯)/聚甲基丙烯酸环氧丙酯(PHDA-b-PGMA) AB 型两亲性嵌段共聚物, 其结构及分子量(分布)通过核磁共振和凝胶渗透色谱(GPC)确证. 此AB型两亲性嵌段共聚物在水溶液中能自组装形成纳米粒子, 用原子力显微镜(AFM)观察粒子的形状和大小.     

Synthesis and characterization of poly(phenylene oxide) graft copolymers by atom transfer radical polymerizations

A series of comb-like poly(phenylene oxide)s (PPO) graft copolymers with controlled grafting density and length of grafts were synthesized by atom transfer radical polymerization (ATRP). The α-bromo-poly(2,6-dimethyl-1,4-phenylene oxide)s (BPPO) were used as macroinitiators to polymerize vinyl monomers and the graft copolymers carrying polystyrene (PS), poly(p-acetoxystyrene) (PAS), and poly(methyl methacrylate) (PMMA) as side chains were synthesized and characterized by NMR, FTIR, GPC, DSC and TGA. The composition-dependent glass-transition temperatures (T_g) of PPO-g-PS exhibited good correlation with theoretical curve in Couchman equations except for the cases of low PS content (<40 mol%) copolymers in which a positive deviation was observed due to enhanced molecular interactions. The increase in monomer/initiator ratio led to the increase of degree of polymerization and the decrease of polydispersity. Despite the immiscibility nature between PPO and PMMA, the PPO-g-PMMA exhibited enhanced compatibilization as apparent single T_g in a wide temperature window throughout various compositions revealing an efficient segmental mixing on a molecular scale due to grafting structure.     

Synthesis and characterization of H-type amphiphilic liquid crystalline block copolymers by ATRP

H-type amphiphilic liquid crystalline block copolymers containing azobenzene were synthesized by atom transfer radical polymerization （ATRP）. Macroinitiators prepared by the esterification between poly（ethylene oxide） （PEG） and 2,2-dichloroacetyl chloride were utilized to initiate the polymerization of 6-[4-（4-ethoxyphenylazo）phenoxy]hexyl rnethacrylate （M6C）. The resulting macroinitiators and block copolymers were characterized by ^1H NMR, gel permeation chromatography （GPC）. Polarizing optical microscopy （POM） and differential scanning calorimetry （DSC） preliminarily revealed the liquid crystalline property of these block copolymers. This series of liquid crystalline block copolymers are promising in some areas, such as optical data storage, optical switch, and molecular devices.     

Optimization of the synthesis of poly(octadecyl acrylate) by atom transfer radical polymerization and the preparation of all comblike amphiphilic diblock copolymers

The atom transfer radical polymerization of octadecyl acrylate (ODA) has been investigated and optimized to produce polymers with predetermined molecular weights and narrow polydispersities (<1.2). The poor solubility of the catalytic system formed with conventional ligands such as the N‐(n‐propyl)‐2‐pyridylmethanimine and 2,2′‐bipyridine with Cu(I)Br in nonpolar reaction conditions gave poor control over molecular weight characteristics in ODA polymerizations. The use of N‐(n‐octyl)‐2‐pyridylmethanimine in combination with Cu(I)Br yielded a more soluble catalyst that improved control over the polymerization. The products from the polymerizations were further improved when an initiator, octadecyl 2‐bromo‐2‐methyl‐propanoate, similar in structure to the monomer, was used. Together, these modifications produced polymerizations that showed true controlled character as well as products with predetermined molecular weights and narrow polydispersities. Diblock copolymers of PODA were prepared with methyl methacrylate (MMA) and olig(oethylene glycol) methyl ether methacrylate (OEGMA). The PODA‐block‐POEGMA copolymers are the first examples of all comblike amphiphilic block copolymers. One of PODA‐block‐POEGMA copolymer samples has been shown to self‐assemble as micelles in a dilute aqueous solution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1129–1143, 2005     

A versatile synthesis of poly(lauryl acrylate) using N-(n-octyl)-2-pyridylmethanimine in copper mediated living radical polymerization

A facile synthesis of poly(lauryl acrylate) has been achieved by atom transfer radical polymerization using benzyl-2-bromoisobutyrate, copper (I) bromide, and N-(n-octyl)-2-pyridylmethanimine (OPMI). The latter was of great interest as its synthesis was very easy to carry out and as it allowed the reaction mixture to be homogeneous, which was essential for the control of the reaction. The polymerization was controlled under these conditions and was optimized with the addition of copper (II) bromide as deactivator. We proved that the synthesis of poly(lauryl acrylates) with well defined molecular weights and narrow polydispersities was possible using a ligand which does not require difficult synthesis and purification. We also showed the ability of pyridylmethanimine ligands to control ATRP of an acrylate derivative. Best results were obtained at 130 °C in xylene for [Initiator]₀/[Cu(I)Br]₀/[Cu(II)Br₂]₀/[OPMI]/[lauryl acrylate] equal to 1/1/0.05/2.2/181, respectively (M_n = 19,942, DPI = 1.28).     

Synthesis of AB diblock copolymers by atom-transfer radical polymerization (ATRP) and living polymerization of alpha-amino acid-N-carboxyanhydrides

The synthesis of poly(methyl acrylate)-block-poly(gamma-benzyl-L-glutamate) (PMA-b-PBLG) diblock copolymers, using atom-transfer radical polymerization (ATRP) of methyl acrylate and living polymerization of gamma-benzyl-L-glutamate-N-carboxyanhydride (Glu-NCA) is described. Amido-amidate nickelacycle end groups were incorporated onto amino-terminated poly(methyl acrylates), and the resulting complexes were successfully used as macroinitiators for the growth of polypeptide segments. This method allows the controlled preparation of polypeptide-block-poly(methyl acrylate) diblock architectures with control over polypeptide chain length and without the formation of homopolypeptide contaminants.     

Synthesis of hyperbranched-linear star block copolymers by atom transfer radical polymerization of styrene using hyperbranched poly(siloxysilane) (HBPS) macroinitiator

Hyperbranched-linear star block copolymers, hyperbranched poly(siloxysilane)-block-polystyrene (HBPS-b-PSt), were prepared by atom transfer radical polymerization (ATRP) of styrene in xylene, using bromoester-terminated HBPS (HBPS-Br (P3), M_n = 7500, M_w/M_n = 1.76) as a macroinitiator. The number-average molecular weights of the obtained polymers (M_n) were in the range of 21,800-60,000 and molecular weight distributions were unimodal throughout the reaction (M_w/M_n = 1.28-1.40). These polymers showed 5 wt.% decomposition temperature (T_d5) over 300 °C. The DSC thermograms of the resulting polymers indicated two glass transition temperatures (T_g). The T_g of HBPS segment shifted to higher value while the T_g of PSt segment shifted to lower value compared with those of the homopolymers. Preliminary physical characterization related to the solution viscosity of the resulting block copolymers is also reported.     

Preparation of block copolymers of polystyrene and poly (t‐butyl acrylate) of various molecular weights and architectures by atom transfer radical polymerization

Block copolymers of polystyrene and poly(t‐butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine catalyst system and had predictable molecular weights based on the degree of polymerization, as calculated from the initial ratio of monomer to initiator. The final polydispersities were low (1.10 < M_w /M_n < 1.3) for all the homopolymers and block copolymers. Polymers of various chain architectures were prepared, ranging from linear AB diblocks to three‐armed stars composed of AB diblocks on each arm. The key to controlled synthesis with this catalyst system was the choice of the solvent, temperature, and concentrations of catalyst and deactivator. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2274–2283, 2000     

Self-assembled polypeptide-block-poly(vinylpyrrolidone) as prospective drug-delivery systems

Poly(β-benzyl-l-aspartate)-block-poly(vinylpyrrolidone) diblock copolymers (PAsp(OBzl)-b-PVP) having both hydrophobic and hydrophilic segments of various lengths were synthesized by a combination of ATRP and ROP. These amphiphilic diblock copolymers formed polymeric micelles consisting of a hydrophobic PAsp(OBzl) core and a hydrophilic PVP shell in aqueous solution. The block copolymer was characterized using ¹H NMR and gel permeation chromatography (GPC) analysis. Due to its core–shell structure, this block polymer forms unimolecular micelles in aqueous solutions. The micelle properties of PAsp(OBzl)-b-PVP diblock copolymer were extensively studied by dynamic light scattering (DLS), fluorescence spectroscopy, and transmission electron microscopy (TEM). PAsp(OBzl)-b-PVP copolymers displayed the lowest CMC and demonstrated little cytotoxicity when exposed to SW-1990 pancreatic cancer cells. In order to assess its application in biomedical area, the anti-inflammation drug prednisone acetate was loaded as the model drug in the polymeric nanoparticles. In vitro release behavior of prednisone acetate was investigated, which showed a dramatic responsive fast/slow switching behavior according to the pH-responsive structural changes of a micelle core structure. All of theses features are quite feasible for utilizing it as a novel intelligent drug-delivery system.     

Direct synthesis of amphiphilic block copolymers, consisting of poly(methyl methacrylate) and poly(sodium styrene sulfonate) blocks through atom transfer radical polymerization

Amphiphilic block copolymers of methyl methacrylate (MMA) and sodium styrene sulfonate (SSNa) were successfully synthesized via direct atom transfer radical polymerization (ATRP) of SSNa. First, poly(sodium styrene sulfonate) (PSSNa) or poly(methyl methacrylate) (PMMA) macroinitiators were prepared using proper ATRP systems for each case. In some cases, functional initiators, which allow further reactions, were used. The macroinitiators were characterized and further used to synthesize PSSNa/PMMA block copolymers, by using proper solvent combinations, such as N,N-dimethylformamide/water or methanol/water at appropriate volume ratios, in order to ensure solubility of the synthesized amphiphilic copolymers. The molecular weight of the copolymers was determined by gel permeation chromatography, using water as eluent. By using a combination of analytical techniques like ¹H NMR, FTIR and thermogravimetry, the chemical structure and the actual copolymer composition were determined. Since, the block copolymers were soluble in water, forming hydrophilic/hydrophobic domains in aqueous solution, their micellization behavior was further studied by pyrene fluorescence probing.     

利用酶促开环聚合和原子转移自由基聚合方法合成AB型嵌段共聚物

我们用端基官能化方法实现两种聚合反应的结合, 成功地制备了AB型双嵌段共聚物PCL-b-PSt和BAB型三嵌段共聚物PSt-b-PCL-b-PSt. 本文利用上述方法, 将酶促开环聚合和原子转移自由基聚合有机地结合起来, 合成了AB型嵌段共聚物-聚己内酯/聚甲基丙烯酸环氧丙酯(PCL-b-PGMA. 此嵌段共聚物具有良好的生物相容性, 在现代生物领域具有广泛的应用前景.     

Tailor‐made poly(ethyl acrylate) by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of ethyl acrylate (EA) was carried out using different initiators, CuBr or CuCl as catalyst in combination with different ligands e.g., 2,2′‐bipyridine (bpy) and N,N,N′,N″N″‐pentamethyl diethylenetriamine (PMDETA). Use of PMDETA as ligand resulted in faster polymerization rate (95% conversion in 15 min) than those using bipyridine (～58% conversion in 10.5 h). This is due to the lower reduction potential of copper‐amine than that of copper‐bpy complex, resulting in higher rates of activation of dormant halides. Use of ethylene carbonate as solvent lead to faster polymerization rate and better control in polymerization when compared with p‐xylene as solvent. The reaction temperature had a positive effect on polymerization rate and the optimum reaction temperature was found to be 90 °C. An apparent enthalpy of activation of ～85 kJ/mol was determined for the ATRP of ethyl acrylate, corresponding to an enthalpy of equilibrium of ～64 kJ/mol. By judicious choice of the reaction parameters it was possible to tailor the end group of the final polymer. MALDI‐TOF‐MS analysis and the chain extension experiment of poly(ethyl acrylate) (PEA) prepared using bpy as ligand showed the presence of ? Br as the end group. On the contrary, when PMDETA was used as the ligand, the mass spectra analysis showed hydrogen terminated polymer as the major species towards the end of polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1661–1669, 2007     

Synthesis of bis-allyloxy functionalized polystyrene and poly (methyl methacrylate) macromonomers using a new ATRP initiator

A new bis-allyloxy functionalized ATRP initiator, viz, 4,4-bis (4-(allyloxy) phenyl) pentyl-2-bromo-2-methylpropanoate was synthesized starting from commercially available 4,4-bis (4-hydroxyphenyl) pentanoic acid. Atom transfer radical polymerization of styrene in bulk and that of methyl methacrylate in anisole using CuBr/N,N,N′,N′,N″-pentamethyldiethylenetriamine system was carried out. The kinetic study of styrene polymerization showed controlled polymerization behavior. Bis-allyloxy functionalized well-defined polystyrene (M_n^GPC: 13,600–28,250, PDI: 1.07–1.09) and poly (methyl methacrylate) (M_n^GPC: 10,100–18,450, PDI: 1.23–1.34) macromonomers were obtained. The presence of allyloxy functionality was confirmed by ¹H NMR spectroscopy. The reactivity of allyloxy functionality was demonstrated by carrying out organic reactions such as addition of bromine and hydrosilylation on polystyrene macromonomer. Polystyrene macromonomer with bis-allyloxy functionality was transformed into bis-epoxy functionalized polystyrene macromonomer using 3-chloroperoxybenzoic acid.     

SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION(ATRP)*

Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH_2CH_2OCOCCl_3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH_2CH_2OCOCCl_3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH_2CH_2OCOCCl_3 (PS-Cl_3) or P(S-b-B)-CH_2CH_2O-COCCl_3 (PSB-Cl_3) was used as the macroinitiator in thepolymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared bythe integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl_3 and the P(S-b-MMA) were identified by FTIR and ~1H-NMR spectrum, respectively. A new way to design blockcopolymers (the combination of LAP and ATRP) was developed.     

ATRP法合成两亲的含氟柱状刷PBIEM-g-(PAA-b-PFA)

以聚甲基丙烯酸[2-(2-溴异丁酰氧)]乙酯(PBIEM)为大分子引发剂,采用接出(grafting from)原子转移自由基聚合(ATRP)技术合成了以聚丙烯酸叔丁酯-b-聚含氟丙烯酸酯为侧链的柱状分子刷PBIEM-g-(PtBA-b-PFA).通过GPC,1H-NMR和FTIR对PBIEM-g-(PtBA-b-PFA)组成和结构进行了表征,证实ATRP过程中没有发生分子间或分子内偶合反应,制备得到可控性好的含氟嵌段共聚物刷.利用大分子链中叔丁酯基团的水解反应生成两亲的含氟柱状刷PBIEM-g-(PAA-b-PFA),原子力显微镜可直接观察到PBIEM-g-(PAA-b-PFA)特征的核壳型柱状结构,得到聚合物刷的整体长度为ln=54~72 nm.     

Synthesis of poly(isobornyl acrylate) containing copolymers by atom transfer radical polymerization

For the first time, a detailed study of the atom transfer radical polymerization of isobornyl acrylate (iBA) is reported. On the basis of these results, well‐defined PiBA‐containing block copolymers were synthesized, focussing on the preparation of amphiphilic poly(acrylic acid) (PAA) containing block copolymers. The precursor monomers 1‐ethoxyethyl acrylate (EEA) as well as tert‐butyl acrylate have been used to synthesize the PAA‐segments of the PiBA‐b‐PAA block copolymers. Finally, the synthesis of “block‐like” copolymers of PiBA and PEEA via a one‐pot procedure was investigated. By optimizing the copper and ligand concentration, and choosing the appropriate solvent, a controlled polymerization behaviour was obtained in all cases, as evidenced by a detailed kinetic analysis, GPC, NMR, and MALDI‐TOF data. Thermogravimetric analysis confirmed the quantitative transformation of the precursor polymer PEEA to the corresponding PAA‐containing copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1649–1661, 2008     

Synthesis and MALDI-TOF-MS of PS-PMA and PMA-PS block copolymers

The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique.     

Controlled/“living” atom transfer radical polymerization of methyl methacrylate in the synthesis of triblock copolymers from a poly(oxyethylene) macroinitiator

Atom transfer radical polymerization of methyl methacrylate initiated by a poly(oxyethylene) macroinitiator by the esterification of PEG 1500 with 2-chloro propionyl chloride was synthesized. These polymerization proceeds both in bulk and solution with a quantitative initiation efficiency, leading to A-B-A triblock copolymers. The macroinitiators and their block copolymers were characterized by FT-IR, FT-NMR and GPC analyses. In bulk polymerization, the kinetic study showed that the relationship between ln[M]₀/[M] vs time was linear showing that there is a constant concentration of active species throughout the polymerization and follow the first order kinetics with respect to monomer. Moreover, the experimental molecular weight of the block copolymers increased linearly with the monomer conversion and the polydispersity index remained between 1.3 and 1.5 throughout the polymerization. No formation of homo poly(methyl methacrylate) could also be detected, and all this confirms that the bulk polymerization proceeds in a controlled/“living” manner.     

原子转移自由基聚合制备聚(甲基丙烯酸甲酯-b-苯乙烯)时单体聚合顺序对嵌段效率的影响

采用原子转移自由基聚合研究了聚（ 甲基丙烯酸甲酯 ｂ 苯乙烯） 嵌段共聚物的合成,实验结果表明,当先进行甲基丙烯酸甲酯的聚合,然后再进行苯乙烯的聚合时,得到了完全的嵌段共聚物;反之,如果改变单体的聚合顺序,则嵌段效率很低．用聚合物末端Ｃ—Ｘ（Ｘ＝ Ｃｌ,Ｂｒ） 键的断裂能对实验结果进行了解释．