Amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate)-g-poly(ε-caprolactone) graft copolymers: synthesis and characterisation

Amphiphilic poly(N,N-dimethylamino-2-ethyl methacrylate)-g-poly(ε-caprolactone) graft copolymers (PDMAEMA-g-PCL) with various compositions and molecular weights were synthesised via a fully controlled three-step strategy. First, poly(ε-caprolactone) macromonomers (PCLMA) were prepared by ring-opening polymerization (ROP) of ε-caprolactone (CL) initiated by aluminum triisopropoxide (Al(OⁱPr)₃), followed in a second step by quantitative esterification of PCL hydroxy end-groups with a methacrylic acid derivative. Finally, the controlled copolymerization of PCLMA and N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) was carried out by atom transfer radical polymerisation (ATRP) in THF at 60 °C using CuBr ligated with 1,1,4,7,10,10, hexamethyl triethylenetetramine and ethyl 2-bromoisobutyrate as catalyst and initiator, respectively. Furthermore, PDMAEMA-g-PCL graft copolymers were reacted with methyl iodide to convert the pendant tertiary amines into quaternary ammonium iodides increasing accordingly their water solubility. Some preliminary experiments was further carried out by tensiometry and dynamic light scattering in order to shed so light on the tensioactive behaviour of these amphiphilic graft copolymers (with protonated amines or quaternary ammonium cations).     

Effect of microwave energy on chain propagation of poly(ε-caprolactone) in benzoic acid-initiated ring opening polymerization of ε-caprolactone

Microwave-assisted ring opening polymerization of ε-caprolactone (ε-CL) initiated by benzoic acid was investigated. The molar ratio of ε-CL to benzoic acid was 5, 15 and 25. The mixtures of ε-CL/benzoic acid were heated under microwave irradiation and the temperatures were self-regulated to equilibrium from 204 to 240 °C with microwave power ranging from 340 to 680 W. The polymer chain propagated fast between 160 and 230 °C, within which the higher the temperature, the faster the propagation. However, when the temperature was over 230 °C, the resultant poly-(ε-caprolactone) (PCL) degraded. The advantage of microwave-assisted polymerization was that the propagation of PCL chain was significantly enhanced but the formation of growing center at the beginning stage of the polymerization was greatly inhibited. With this metal-free method, PCL with weight-average molar mass (M_w) over 4×10⁴ g/mol was prepared.     

Macromlecular engineering of polylactones and polylactides. XVI. On the way to the synthesis of ω-aliphatic primary amine poly (ϵ-caprolactone) and polylactides

Since bromides are well-known precursors of primary amines, diethylaluminum 12 bromo-1-dodecyl oxide has been prepared and used as an initiator for the ring-opening polymerization of ?-caprolactone and L-lactide. Uner strictly controlled conditions, the end-functionalization of the polyesters in quantitative and the bromo end-group is easily converted into an azide group whatever the polymeric backbone. The subsequent reduction of the azide into the expected primary amine has been investigated by catalytic transfer hydrogenation (CTH) in DMF and by hydrolysis in the presence of triphenylphosphine in THF, respectively.The hydrolysis reaction (PΦ₃/H₂O) is perturbed by a coupling reaction, which involves a protonate secondary amine and leads to a twofold increase in the polyester molecular weight. The CTH method gives rise to the expected ω-NH₂ poly (?-caprolactone), in contrast to polylactide which seems to be unstable toward the nascent amine end group. Whatever the polarity of the medium (DMF or THF), aminolysis of polylactides is observed to occur and leads to the formation of an internal amide. © 1994 John Wiley & Sons, Inc.     

END GROUP TRANSFORMATION OF POLYMERS PREPARED BY ATRP,SUBSTITUTION TO AZIDES

Polystyrenes, polyacrylates and poly(methyl methacrylate) prepared by atom transfer radical polymerization (ATRP) have predictable molecular weights, low polydispersities and well-defined halogen end groups. The halogen end groups have been substituted by other functionalities such as azides and amines. In order to predict the feasibility and selectivity of nucleophilic substitution reactions, the reactivities of the end groups of the different polymers were studied. First, model studies with benzyl halide (BzX), 1-phenylethyl halide (1-PEX), methyl 2-halopropionate (MXP), ethyl 2-bromoisobutyrate (EBiB) and 2-halopropionitrile (2-XPN) were performed. The models compounds were dissolved in DMF and after adding sodium azide (1.1 eq.), the reaction mixtures were stirred at 25°C. The relative magnitude of the rate constants for the reactions with the chlorinated substrates were found to be BzCl > MClP > 1-PECl ≈ 2-ClPN:22 > 6 > 1. Increased substitution at the carbon center decreased the rate of reaction, benzyl chloride reacted 22 times faster than 1-phenylethyl chloride. The brominated substrates reacted very fast. The rate constant of 1-PEBr, determined by competition experiments, was 4.5 times higher than the rate constant of benzyl chloride. Based on these results, the bromine end groups of different polymers were substituted under reaction conditions simular to those used for the model reactions. The end-functionalized polymers were characterized by ¹H-NMR, IR and MALDI-TOFMS.     

Effects of the polymerization temperature on the structure,morphology and conductivity of polyaniline prepared with ammonium peroxodisulfate

Polyaniline (PANI) samples were prepared by the oxidation of aniline with ammonium peroxodisulfate in a reaction vessel placed in a bath thermostated to particular temperature, T_b, from −20 °C to 40 °C. Temperature–time profiles of reaction mixtures were monitored except for the reaction at −20 °C that proceeded in the solid state. The temperature regime was found to influence the molecular structure, morphology, crystallinity and electrical conductivity of PANI. The increase in T_b results in an increased content of meanwhile unspecified structure defects in the formed PANI chains (the presence of attached self-doping groups is improbable), decreased crystallinity, toughness and compactness of PANI microparticles and increased steepness of the temperature dependence of PANI conductivity. The PANI prepared in the solid-state polymerization at −20 °C shows, besides a rather high crystallinity, the unusually high position of the quinonoid band maximum: 643 nm, which suggests a high regularity of its chains. A correlation between the temperature dependence of PANI conductivity at low temperatures (range from 13 to 318 K) on one hand and the temperature regime of PANI preparation on the other hand, is reported for the first time. The dependences obtained only poorly meet the variable random hopping model.     

Poly(aryl ether amide)s

A general method for the preparation of poly(aryl ether amide)s has been developed where the generation of an aryl ether linkage is the polymer-forming reaction. The amide linkage was found to be sufficiently electron-withdrawing to activate halo-substituents towards nucleophilic aromatic substitution analogous to conventional activating groups (i.e., sulfone, ketone, etc.). Model reactions demonstrated that the amide-activated displacement occurred with high selectivity in near quantitative yield and was judged suitable as a polymer-forming reaction. Appropriately fluoro-substituted amides were prepared and subjected to displacement polymerization with bisphenoxides in a N-methyl-2-pyrrolidone (NMP)/N-cyclohexyl-2-pyrrolidone (CHP) solvent mixture. High molecular weight polymers with glass transition temperatures in the 200–225°C range were obtained. © 1993 John Wiley & Sons, Inc.     

Ring-opening polymerization of ε-caprolactone initiated by diphenylzinc

In the present work the polymerization of ε-caprolactone (ε-CL) using Ph₂Zn as initiator is reported. The effects of reaction temperature, molar ratio of monomer/initiator and reaction time on the yield and the molecular weight are investigated. The temperature is varied between 20 and 120 °C and the molar ratio of monomer to initiator between 200 and 800 mol/mol. The results indicate that the Ph₂Zn induces the polymerization of ε-CL to high conversion and produces polymer with high molecular weight at temperatures around 40-60 °C.     

Synthesis of PCL–graft–PS by combination of ROP, ATRP, and click chemistry

Poly(ε-caprolactone)–graft–polystyrenes were successfully synthesized by grafting an azide end-functionalized polystyrene onto a PCL backbone with multiple pendant alkyne moieties using a “click” chemistry reaction. Both precursors, the PCL backbone and the PS side chains, were prepared separately by two different living/controlled mechanisms, ring-opening polymerisation and ATRP, respectively. Molecular weights, polydispersity indexes, and chemical compositions of the backbone and branches were controlled. The subsequent copper-catalysed Huisgen 1,3-dipolar cycloaddition of PS onto PCL was achieved at room temperature with high conversion. However, a bimodal molecular weight distribution was observed in size exclusion chromatography due to the presence of unreacted PS. Nevertheless, crude product was purified by selective fractionation in cyclohexane to achieve pure graft copolymers.     

New organic-inorganic nanohybrids via ring opening polymerization of (di)lactones initiated by functionalized polyhedral oligomeric silsesquioxane

The synthesis of new organic-inorganic materials were investigated. Poly(ε-caprolactone) and poly(l, l-lactide) covalently end-capped by a polyhedral oligomeric silsesquioxane (POSS) moiety, leading to new nanohybrid materials, were successfully prepared by coordination-insertion ring opening polymerization (ROP) of ε-caprolactone (ε-CL) and l,l-lactide (l,l-LA) respectively. The reaction was initiated from the primary amine available on aminopropylheptakis(isobutyl)POSS nanoparticles and catalyzed by tin(II) 2-ethylhexanoate (tin octoate, Sn(oct)₂). The covalent grafting of the polyester chains onto the POSS “nanocages” was assessed by selective fractionation experiment, Fourier transform infrared spectroscopy (FTIR) and further confirmed by proton nuclear magnetic resonance (¹H NMR). The polymerization proved to be well controlled as attested by the quite narrow polydispersity indices as determined by size exclusion chromatography (SEC). Furthermore, well-defined semi-crystalline poly(ε-caprolactone)-b-polylactide block copolymer carrying such POSS nanoparticle at one end was successfully synthesized attesting for the very efficient control over the polymerization reaction.     

Remarkable effect of hydrogen-bonding interaction on stereospecificity in the radical polymerization of N-vinylacetamide

Radical polymerization of N-vinylacetamide (NVA) in toluene at low temperatures was investigated. It was found that the addition of Lewis bases or alcohol compounds significantly influenced stereospecificity in NVA polymerization. For example, syndiotacticity increased from 25% to 34% by adding tri-n-butyl phosphate at −40 °C. Mono-alcohol compounds increased heterotacticity and heterotactic poly(NVA) with mr triad content of 58% was obtained at −40 °C in the presence of 1,1,1,3,3,3-hexafluoro-2-propanol. Furthermore, isotactic poly(NVA) with mm triad = 49% was obtained at −60 °C in the presence of diethyl l-tartrate. The NMR analysis demonstrated that complex formation between NVA monomer and the added agents, through hydrogen-bonding interaction, played an important role to induce the stereospecificity.     

Synthesis, characterization and degradability of the comb-type poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone)-g-poly(l-lactide)

The novel comb-type biodegradable graft copolymers based on ε-caprolactone and l-lactide were synthesized. Firstly, 2-oxepane-1,5-dione (OPD) was synthesized by the Baeyer-Villiger oxidation of 1,4-cyclohexanedione, and was subsequently copolymerized with ε-caprolactone (CL) to produce poly(2-oxepane-1,5-dione-co-ε-caprolactone) (POCL) catalyzed by stannous(II) 2-ethylhexanoate in toluene. Then, POCL was converted into poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone) (PHCL) using sodium borohydride as reductant. Finally, poly(4-hydroxyl-ε-caprolactone-co-ε-caprolactone)-g-poly(l-lactide) (PHCL-g-PLLA) were prepared successfully by bulk ring-opening polymerization of l-lactide using PHCL as a macro-initiator. All the copolymers have been characterized by ¹H and ¹³C NMR, DSC, and GPC. Compared with the random copolymer of poly(CL-co-LA), the elongation is highly increased. And the thermal analysis showed that the crystallization rate of the PCL backbone in the graft copolymers was greatly reduced compared to the PCL homopolymer. The hydrolytic degradation of the copolymer was much faster in a phosphate buffer (pH = 7.4) at 37 °C, which is confirmed by the weight loss and change of intrinsic viscosity.     

Melt block copolymerization of ϵ-caprolactone and L-lactide

AB block copolymers of ϵ-caprolactone and (L )-lactide could be prepared by ring-opening polymerization in the melt at 110°C using stannous octoate as a catalyst and ethanol as an initiator provided ϵ-caprolactone was polymerized first. Ethanol initiated the polymerization of ϵ-caprolactone producing a polymer with ϵ-caprolactone derived hydroxyl end groups which after addition of L -lactide in the second step of the polymerization initiated the ring-opening copolymerization of L -lactide. The number-average molecular weights of the poly(ϵ-caprolactone) blocks varied from 1.5 to 5.2 × 10³, while those of the poly(L -lactide) blocks ranged from 17.4 to 49.7 × 10³. The polydispersities of the block copolymers varied from 1.16 to 1.27. The number-average molecular weights of the polymers were controlled by the monomer/hydroxyl group ratio, and were independent on the monomer/stannous octoate ratio within the range of experimental conditions studied. When L -lactide was polymerized first, followed by copolymerization of ϵ-caprolactone, random copolymers were obtained. The formation of random copolymers was attributed to the occurrence of transesterification reactions. These side reactions were caused by the ϵ-caprolactone derived hydroxyl end groups generated during the copolymerization of ϵ-caprolactone with pre-polymers of L -lactide. The polymerization proceeds through an ester alcoholysis reaction mechanism, in which the stannous octoate activated ester groups of the monomers react with hydroxyl groups. © 1997 John Wiley & Sons, Inc.     

Synthesis, characterization and degradability of the novel aliphatic polyester bearing pendant N-isopropylamide functional groups

The synthesis, characterization, and degradability of the novel aliphatic polyester bearing pendant N-isopropylamide functional group are reported for the first time. 2-(N-Isopropyl-2-carbamoylethyl)cyclohexanone (CCH) was first synthesized by the Michael reaction of N-isopropylacrylamide with cyclohexanone and was subsequently converted into 6-(N-isopropyl-2-carbamoylethyl)-?-caprolactone (CCL) by the Baeyer-Villiger oxidation reaction using 3-chloroperoxybenzoic acid (mCPBA) as the oxidant. Finally, the novel functionalized poly(?-caprolactone) bearing the pendant N-isopropylamide functional groups, poly(6-(N-isopropyl-2-carbamoylethyl)-?-caprolactone-co-?-caprolactone)s (poly(CCL-co-CL)), were carried out successfully by bulk ring-opening polymerization of CCL and ?-CL initiated by Sn(Oct)₂. Poly(CCL-co-CL) were characterized by ¹H NMR, ¹³C NMR, SEC and DSC. The copolymer containing 9.1 mol% CCL formed flexible films and was used to study its degradability. A phosphate buffer (pH = 7.4) with temperature 37 °C was adopted to proceed the degrading study all through. Compared with poly(?-caprolactone), the hydrolytic degradation of poly(CCL-co-CL) was much faster, which is confirmed by the weight loss and change of intrinsic viscosity.     

Temperature effect of electrochemically roughened gold substrates on polymerization electrocatalysis of polypyrrole

In this work, electrochemical methods were used to prepare complexes with Au and Cl species on bulk Au substrates. Then the electrochemically roughened Au substrates were further heat-treated at different temperatures. The effect of temperatures used in heat treatments between 25 and 100 °C on electrocatalytical polymerization of polypyrrole (PPy) formed on the prepared gold substrates was first investigated. The result indicates that the optimally electrocatalytical capability of the heat-treated Au substrate for PPy polymerization is at 75 °C. Moreover, the autopolymerized PPy on the roughened Au substrate treated at 75 °C demonstrates the highest oxidation level and oxidation degree of 0.32 and 0.50, respectively. Primary results indicate that complexes with positively charged Au act as oxidants, and perchlorate and chloride ions act as dopants for the oxidation-polymerization of PPy.     

Postpolymerization modification of poly(pentafluorophenyl methacrylate): Synthesis of a diverse water‐soluble polymer library

This article explores the feasibility of poly(pentafluorophenyl methacrylate) (PPFMA) prepared by reversible addition fragmentation chain transfer (RAFT) polymerization as a platform for the preparation of diverse libraries of functional polymers via postpolymerization modification with primary amines. Experiments with a broad range of functional amines and PPFMA precursors of different molecular weights indicated that the postpolymerization modification reaction proceeds with good to excellent conversion for a diverse variety of functional amines and is essentially independent of the PPFMA precursor molecular weight. The RAFT end group, which was well preserved throughout the polymerization, is cleaved during postpolymerization modification to generate a thiol end group that provides possibilities for further orthogonal chain‐end modification reactions. The degree of postpolymerization modification can be controlled by varying the relative amount of primary amine that is used and random polymethacrylamide copolymers can be prepared via a one‐pot/two‐step sequential addition procedure. Cytotoxicity experiments revealed that the postpolymerization modification strategy does not lead to any additional toxicity compared with the corresponding polymer obtained via direct polymerization, which makes this approach also of interest for the synthesis of biologically active polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4332–4345, 2009     

谷胱甘肽端基修饰聚己内酯的合成及在水溶液中的聚集行为

用开环聚合法合成了端基分别为巯基和马来酰亚胺基团的聚己内酯,利用马来酰亚胺与巯基的迈克尔加成反应和巯基之间的偶联反应,合成了两种端基为谷胱甘肽的聚己内酯(GS-PCL和GSS-PCL),利用核磁共振氢谱和凝胶渗透色谱表征了两亲性聚己内酯的结构.研究了这两种聚己内酯在水中的聚集行为,发现这两种聚已内酯都可在一定pH值下聚集形成球形胶束,胶束的形态、大小等受pH影响;同时,由GSS-PCL形成的聚集体还表现出氧化还原敏感性.     

Two highly stable and selective solid phase microextraction fibers coated with crown ether functionalized ionic liquids by different sol–gel reaction approaches

In this work, two novel crown ether functionalized ionic liquid (FIL)-based solid phase microextraction (SPME) fibers were prepared by sol–gel technology using the synthesized 1-(trimethoxysily)propyl 3-(6′-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([TMSP(Benzo15C5)HIM][N(SO₂CF₃)₂]) and 1-allyl-3-(6′-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([A(Benzo15C5)HIM][N(SO₂CF₃)₂]) as selective stationary phases. Owing to the introduction of trimethoxysilypropyl to the imidazole cation, the [TMSP(Benzo15C5)HIM][N(SO₂CF₃)₂] could be chemically bonded to the formed sol–gel silica substrate through the hydrolysis and polycondensation reaction. Similarly, the [A(Benzo15C5)HIM][N(SO₂CF₃)₂] was able to participate in the formation of the organic–inorganic copolymer coatings through the free radical crosslinking reaction. These two fibers were determined to have “bubble-like” surface characteristics analogous to a previously prepared [A(Benzo15C5)HIM][PF₆]-based fiber. Their thermal stabilities were much higher than that of the [A(Benzo15C5)HIM][PF₆]-based coating. They were capable of withstanding temperatures as high as 400 °C without evident loss of the crown ether FILs. They also had strong solvent, acid and alkali resistance, good coating preparation reproducibility and high selectivity for medium polar to polar compounds. The high selectivity of these two fibers could be attributed to the strong ion-dipole, hydrogen bonding and π–π interactions provided by the synergetic effect of ILs and benzo-15-crown-5 functionalities. Moreover, the selectivity of these two fibers was rather different although the structures of these two crown ether FILs were very similar. This is maybe because the relative contents of the crown ether FILs chemically bonded to the organic–inorganic copolymer coatings were quite different when prepared by different sol–gel reaction approaches.     

Soluble poly(amide imide)s containing oligoether spacers

A diimide-diacid with oligoether spacer was synthesized from the condensation reaction of trimellitic anhydride with 1,8-diamino-3,6-dioxaoctane. Soluble poly(amide imide)s containing flexible groups were prepared through polycondensation reactions of diimide-diacid with different diamines via direct Yamazaki method. The poly(amide imide)s showed improved solubilty in polar aprotic solvents due to the presence of ether and alkyl flexible groups. According to the differential scanning calorimetry analysis, the glass transition temperatures of the polymers were in the range of 119-157 °C. According to thermogravimetric analysis, the temperatures for 10% weight losses were in the range of 348-387 °C that showed good thermal stabilities for these polymers.     

Amphiphilic Biodegradable Poly(ϵ-caprolactone)-Poly(ethylene glycol) – Poly(ϵ-caprolactone) Triblock Copolymer Synthesis by Maghnite-H+ as a Green Catalyst

Amphiphilic biodegradable (PCL-PEG-PCL) triblock copolymers have been successfully prepared by the ring opening polymerization of ?-caprolactone (CL) in the presence of poly(ethylene glycol) (PEG) at 80°C employing Maghnite-H⁺ a non-toxic Montmorillonite clay as catalyst. Maghnite-H⁺ reacts as a solid source of protons to induce ?-caprolactone polymerization. The triblock architecture, molecular weight and thermal properties of the copolymers were characterized by NMR spectra, GPC and DSC analyses. The effect of Maghnite-H⁺ proportion and PEGs on the rate of copolymerization and on average molecular weight of resulting copolymers was studied. A cationic mechanism for the copolymerization reaction was proposed.     

Automated determination of aliphatic primary amines in wastewater by simultaneous derivatization and headspace solid-phase microextraction followed by gas chromatography–tandem mass spectrometry

This paper presents a fully automated method for determining ten primary amines in wastewater at ng/L levels. The method is based on simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) followed by gas chromatography coupled to ion trap tandem mass spectrometry (GC–IT-MS–MS). The influence of main factors on the efficiency of derivatization and of HS-SPME is described in detail and optimized by a central composite design. For all species, the highest enrichment factors were achieved using a 85 μm polyacrylate (PA) fiber exposed in the headspace of stirred water samples (750 rpm) at pH 12, containing 360 g/L of NaCl, at 40 °C for 15 min. Under optimized conditions, the proposed method achieved detection limits ranging from 10 to 100 ng/L (except for cyclohexylamine). The optimized method was then used to determine the presence of primary amines in various types of wastewater samples, such as influent and effluent wastewater from municipal and industrial wastewater treatment plants (WWTPs) and a potable water treatment plant. Although the analysis of these samples revealed the presence of up to 1500 μg/L of certain primary amines in influent industrial wastewater, the concentration of these compounds in the effluent and in municipal and potable water was substantially lower, at low μg/L levels. The new derivatization–HS-SPME–GC–IT-MS–MS method is suitable for the fast, reliable and inexpensive determination of primary amines in wastewater in an automated procedure.