Formation Of Random Copolymers Research Articles

Structure, morphology and crystallization of isodimorphic random copolymers: Copolyesters, copolycarbonates and copolyamides

Random copolymerization is used to prepare new polymeric materials that combine the desirable properties of different homopolymers. The covalent bonds between the comonomers enable miscibility and the formation of random copolymers with specific properties tailored for various applications. The crystallization behavior of random copolymers is intricate, encompassing up to three crystallization modes, i.e., total comonomeric exclusion, isomorphism, and isodimorphism. Isomorphism and isodimorphism allow for crystallization across the entire composition range, resulting in unique and potentially advantageous properties for each composition. These characteristics have garnered significant attention, as evidenced by the multiple publications that have appeared in the last decade.This contribution reviews the progress made in several aspects of isodimorphic copolymers, including new cases and applications. The initial section focuses on the factors influencing the pseudo-eutectic position, which is crucial for understanding the crystallization behavior of these copolymers. Subsequently, advancements in determining the degree of comonomer inclusion are discussed. Another section highlights studies that have raised new questions about the concepts of isodimorphism and isomorphism, particularly their presence in blends and terpolymers. These findings have opened up new avenues for research.In the final part of this review, selected examples are presented to illustrate the relationship between structure and properties in random copolymers. Furthermore, practical applications, such as using random copolymers as hot melt adhesives, are showcased. Despite significant progress in understanding the crystallization modes in random copolymers, this contribution emphasizes that new phenomena continue to emerge, providing further opportunities for exploration and shedding light on novel applications related to these intriguing crystallization modes.

Production of “Green” Thermoplastic Polyurethanes from Decamethylene Sebacate‐co‐Isosorbide Copolymers

AbstractLong‐chain aliphatic copolyesters based on sebacic acid (SA) and isosorbide (IS), of renewable origin, are synthesized by a “green” and sustainable route, without the use of solvents, for the synthesis of polyurethanes (PUs). The polyesters are characterized by size exclusion chromatography (SEC), proton nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogravimetry (TG). ¹H NMR and FTIR analyses confirm the production of copolyesters with the incorporation of IS, while SEC indicates that the addition of IS to copolyesters decreases the molecular weights. The results suggest the formation of random copolymers in the presence of IS, which makes the polymer chains more rigid. The formation of PUs by the reaction of copolyesters with 1,8‐diisocyanatooctane is confirmed by FTIR. Thermal behavior is compatible with thermoplastic processing and use in different biomedical applications.

ТЕРМИЧЕСКОЕ ПОВЕДЕНИЕ СОПОЛИМЕРОВ МАЛЕИМИДА С АЛКИЛМЕТАКРИЛАТАМИ

Copolymers of maleimide with methyl- and allyl methacrylate have been prepared by the method of radical copolymerization in bulk. It was established that, regardless of the composition of the initial monomer mixture, copolymerization proceeded with the formation of random copolymers enriched with acrylate monomer units. Maleimide copolymers have high thermal stability up to 320 °C.

Highly Efficient Modular Construction of Functional Drug Delivery Platform Based on Amphiphilic Biodegradable Polymers via Click Chemistry.

Amphiphilic copolymers with pendant functional groups in polyester segments are widely used in nanomedicine. These enriched functionalities are designed to form covalent conjugates with payloads or provide additional stabilization effects for encapsulated drugs. A general method is successfully developed for the efficient preparation of functional biodegradable PEG-polyester copolymers via click chemistry. Firstly, in the presence of mPEG as initiator, Sn(Oct)2-catalyzed ring-opening polymerization of the α-alkynyl functionalized lactone with D,L-lactide or ε-caprolactone afforded linear mPEG-polyesters bearing multiple pendant alkynyl groups. Kinetic studies indicated the formation of random copolymers. Through copper-catalyzed azide-alkyne cycloaddition reaction, various small azido molecules with different functionalities to polyester segments are efficiently grafted. The molecular weights, polydispersities and grafting efficiencies of azido molecules of these copolymers were investigated by NMR and GPC. Secondly, it is demonstrated that the resulting amphiphilic functional copolymers with low CMC values could self-assemble to form nanoparticles in aqueous media. In addition, the in vitro degradation study and cytotoxicity assays indicated the excellent biodegradability and low cytotoxicity of these copolymers. This work provides a general approach toward the preparation of functional PEG-polyester copolymers in a quite efficient way, which may further facilitate the application of functional PEG-polyesters as drug delivery materials.

Comparative Experimental and Theoretical Study of Mg, Al and Zn Aryloxy Complexes in Copolymerization of Cyclic Esters: The Role of the Metal Coordination in Formation of Random Copolymers.

Homogeneity of copolymers is a general problem of catalytic coordination polymerization. In ring-opening polymerization of cyclic esters, the rational design of the catalyst is generally applied to solve this problem by the equalization of the reactivities of comonomers—however, it often leads to a reduction of catalytic activity. In the present paper, we studied the catalytic behavior of BnOH-activated complexes (BHT)Mg(THF)2nBu (1), (BHT)2AlMe (2) and [(BHT)ZnEt]2 (3), based on 2,6-di-tert-butyl-4-methylphenol (BHT-H) in homo- and copolymerization of L-lactide (lLA) and ε-caprolactone (εCL). Even at 1:5 lLA/εCL ratio Mg complex 1 catalyzed homopolymerization of lLA without involving εCL to the formation of the polymer backbone. On the contrary, Zn complex 3 efficiently catalyzed random lLA/εCL copolymerization; the presence of mono-lactate subunits in the copolymer chain clearly pointed to the transesterification mechanism of copolymer formation. Both epimerization and transesterification side processes were analyzed using the density functional theory (DFT) modeling that confirmed the qualitative difference in catalytic behavior of 1 and 3: Mg and Zn complexes demonstrated different types of preferable coordination on the PLA chain (k2 and k3, respectively) with the result that complex 3 catalyzed controlled εCL ROP/PLA transesterification, providing the formation of lLA/εCL copolymers that contain mono-lactate fragments separated by short oligo(εCL) chains. The best results in the synthesis of random lLA/εCL copolymers were obtained during experiments on transesterification of commercially available PLLA, the applicability of 3/BnOH catalyst in the synthesis of random copolymers of εCL with methyl glycolide, ethyl ethylene phosphonate and ethyl ethylene phosphate was also demonstrated.

Copolymerization of D,L-lactide and ε-caprolactone using tin(II) octanoate as catalysts: an insight into copolymer microstructure

Sn(Oct)2-catalyzed ring-opening copolymerization of D,L-lactide and e-caprolactone in bulk at 130 °C at different D,L-lactide/e-caprolactone has been studied. It was shown that independent on the initial comonomers ratio, the synthesized copolymers are enriched by D,L-lactide at the early stage of reaction indicating the formation of gradient-like copolymer. However, the intensive transesterification reaction both during the polymerization and at the monomer-starved conditions leads to the redistribution of the monomer sequences and formation of the random copolymer. The synthesized copolymers are characterized by high polydispersity (Đ > 2.0), which raises when the reaction mixture was kept under monomer-starved conditions that confirms the occurrence of transesterification. The formation of random copolymer is confirmed by single Tg value, which gradually increased with the increase of the amount of D,L-lactide in the copolymer from –48.6 °C to 33.3 °C for D,L-lactide/e-caprolactone ratio in copolymer of 20:80 and 90:10 mol/mol, respectively.

DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates.

Catalytic ring-opening polymerization (ROP) of cyclic esters (lactides, lactones) and cyclic ethylene phosphates is an effective way to process materials with regulated hydrophilicity and controlled biodegradability. Random copolymers of cyclic monomers of different chemical nature are highly attractive due to their high variability of characteristics. Aryloxy-alkoxy complexes of non-toxic metals such as derivatives of 2,6-di-tert-butyl-4-methylphenoxy magnesium (BHT-Mg) complexes are effective coordination catalysts for homopolymerization of all types of traditional ROP monomers. In the present paper, we report the results of density functional theory (DFT) modeling of BHT-Mg-catalyzed copolymerization for lactone/lactide, lactone/ethylene phosphate and lactide/ethylene phosphate mixtures. ε-Caprolactone (ε-CL), l-lactide (l-LA) and methyl ethylene phosphate (MeOEP) were used as examples of monomers in DFT simulations by the Gaussian-09 program package with the B3PW91/DGTZVP basis set. Both binuclear and mononuclear reaction mechanistic concepts have been applied for the calculations of the reaction profiles. The results of calculations predict the possibility of the formation of random copolymers based on l-LA/MeOEP, and substantial hindrance of copolymerization for ε-CL/l-LA and ε-CL/MeOEP pairs. From the mechanistic point of view, the formation of highly stable five-membered chelate by the products of l-LA ring-opening and high donor properties of phosphates are the key factors that rule the reactions. The results of DFT modeling have been confirmed by copolymerization experiments.

Design and Synthesis of Aromatic Polyesters Bearing Pendant Clickable Maleimide Groups

ABSTRACTA bisphenol bearing pendant maleimide group, namely, N‐maleimidoethyl‐3, 3‐bis(4‐hydroxyphenyl)‐1‐isobenzopyrrolidone (PPH‐MA) was synthesized starting from phenolphthalein. Aromatic (co)polyesters bearing pendant maleimide groups were synthesized from PPH‐MA and aromatic diacid chlorides, namely, isophthaloyl chloride (IPC), terephthaloyl chloride (TPC), and 50:50 mol % mixture of IPC and TPC by low temperature solution polycondensation technique. Copolyesters were also synthesized by polycondensation of different molar proportions of PPH‐MA and bisphenol A with IPC. Inherent viscosities and number‐average molecular weights of aromatic (co)polyesters were in the range of 0.52–0.97 dL/g and 20,200–32,800 g/mol, respectively indicating formation of medium to reasonably high‐molecular‐weight polymers. 13C NMR spectral analysis of copolyesters revealed the formation of random copolymers. The 10% weight loss temperature of (co)polyesters was found in the range 470–484 °C, indicating their good thermal stability. A selected aromatic polyester bearing pendant maleimide groups was chemically modified via thiol‐maleimide Michael addition reaction with two representative thiol compounds, namely, 4‐chlorothiophenol and 1‐adamantanethiol to yield post‐modified polymers in a quantitative manner. Additionally, it was demonstrated that polyester containing pendant maleimide groups could be used to form insoluble crosslinked gel in the presence of a multifunctional thiol crosslinker. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 630–640

Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride and alkyl methacrylates

Radical copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with methyl methacrylate and allyl methacrylate in the bulk and methanol solution in the presence of azobis-isobutyric acid dinitryle at 70–90°C has been studied. Copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with methyl methacrylate or allyl methacrylate in the bulk proceeds with formation of random copolymers enriched in methacrylate units; in the copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidiny chloride with methyl methacrylate in methanol, the copolymerization constants of the monomers become close. The kinetic parameters of the reaction have been studied, the relative activities of the monomers have been determined. It has been found that 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride is copolymerized with allyl methacrylate or methylmethacrylate to form pyrrolidinium structures in the cyclolinear polymer chain. At high degrees of conversion of the copolymerization of 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride with allyl methacrylate, the viscosity increases and the side polymer chains are crosslinked by “allyl bonds” to form insoluble copolymers, swelling in benzene and DMSO.

Ferrocene-Containing Multifunctional Polyethers: Monomer Sequence Monitoring via Quantitative 13C NMR Spectroscopy in Bulk

Ferrocenyl glycidyl ether (fcGE) and allyl glycidyl ether (AGE) are copolymerized via living anionic ring-opening polymerization to generate polyfunctional copolymers with molecular weights up to 40 300 g/mol and low molecular weight dispersities (Mw/Mn < 1.18). Copolymerizations were carried out in bulk at 100 °C and unexpectedly found to proceed without any isomerization of the allyl double bonds. The copolymerization behavior of fcGE and AGE was monitored by in situ quantitative 13C NMR kinetic measurements in bulk, evidencing the formation of random copolymers under these conditions, showing no gradient of comonomer incorporation. The redox-active behavior of the copolymers and homopolymers of fcGE was studied by cyclic voltammetry (CV). In order to demonstrate possible postmodification reactions, the random copolymers were modified with N-acetyl-l-cysteine methyl ester via a thiol–ene addition. All polymers have furthermore been characterized by 1H NMR spectroscopy, DOSY 1H NMR spectroscopy, size exc...

On the interrelationship of transreaction with viscoelastic properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) blends in the presence of nanoclay

An attempt was made to explore the effects of the interchange reactions on the viscoelastic behavior of binary blends based on poly(ethylene terephthalate) (PET)/poly(ethylene naphthalate) (PEN) and their nanocomposites. It was seen that with an increase in the number of extrusion runs and mixing temperature, the extent of reaction (X) and degree of randomness (RD) both increased, whereas the average sequence block lengths values were decreased. On the contrary, the blend composition did not play a significant role on X and RD values. Addition of nanoclay inhibited the transreactions in PET/PEN blends. The absence of crystallization peaks implied that the crystalline structure was destroyed as a result of blending and an amorphous system was created possibly due to the transreactions simultaneously with the formation of random copolymers inhibiting the crystallization process. The rheological investigations showed that the addition of PEN into the PEN/PET blends enhanced the storage modulus, loss modulus, and complex viscosity. The viscosity upswing observed at low‐frequency region in the case of nanocomposite systems evidently confirmed the occurrence of transreactions. Nonetheless, a significant increment in the viscoelastic properties was perceived in the presence of nanoclay corroborating the proper nanoclay distribution throughout the PET/PEN blend system. POLYM. ENG. SCI., 53:2556–2567, 2013. © 2013 Society of Plastics Engineers

Synthesis of poly[3‐(methacryloylamino) propyl trimethylammonium chloride‐co‐methacrylic acid] copolymer hydrogels for controlled indomethacin delivery

AbstractStimulus responsive hydrogels are being considered as one of the most exciting biomaterials of current generation. A novel hydrogel based on poly 3‐[(methacryoylamino) propyl trimethylammonium chloride‐co‐methacrylic acid] (PMAPTACMAAc) copolymer was synthesized by free radical aqueous copolymerization. The water uptake of the hydrogels was investigated as a function of temperature and pH. The in vitro release properties of the PMAPTACMAAc hydrogels were analyzed under simulated body fluid (pH 7.4) by loading indomethacin (IND) as a model drug. The XRD study of the hydrogel revealed the amorphous nature of the copolymer and provided evidence that crystalline IND was entrapped in the hydrogel matrix. The DSC study showed the presence of single glass transition temperature in the thermogram which indicated the formation of random copolymers. The prepared hydrogels showed typical polyampholyte behavior and swelling was affected by the monomer feed ratios in the hydrogels. The morphological study on the hydrogels showed the three dimensional (3D) porous nature of the PMAPTACMAAc‐5 gel with pore size ranging from 10 to 40 μm. The kinetics of the cumulative IND release shows that the gel follows a non‐Fickian release mechanism. In vitro cytotoxicity of the hydrogel (PMAPTACMAAc‐5 gel) on RAW 264.7 murine macrophages showed that the hydrogel was biocompatible and not toxic as the viability was maintained. The hydrogel with a 90 : 10 feed ratio of MAAc and MAPTAC was better than the other developed formulations. The results suggest that the hydrogels could be employed as a sustained release formulation for targeted delivery of IND, for example to the colon. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Synthesis and Characterization of Copolymers of Methyl Methacrylate and 2-Ethoxyethyl Methacrylate

The free-radical initiated copolymerizations of methyl methacrylate (MMA) with 2-ethoxyethyl methacrylate (2-EOEMA) were carried out using 2,2-azo-bisisobutyronitrile (AIBN) as the initiator in 1,4-dioxane solutions. The co- polymer products were characterized by IR, 1 H-NMR, and 13 C-NMR spectroscopic techniques. The reactivity ratios of the monomers were computed by the Fineman-Rose (F-R) and Kelen-Tudos (K-T) methods at lower conversion, using the IR data. The results are in good agreement with each other and the mean reactivity ratios for MMA/EOEMA copolymers are r1=0.8436, r2= 0.7751, and r1r2 = 0.6614. The reactivity ratios indicate the formation of random copolymers, which have been supported by the azeotropic composition evaluations. The distribution of monomer sequence along the copolymer chain has been calculated using a statistical method based on the reactivity ratios. The probability of finding the mean sequence lengths of 2-EOEMA and MMA units has also been evaluated.

Structure formation of random isotactic copolymers of propylene and 1-hexene or 1-octene at rapid cooling

The effect of variation the cooling rate in a wide range between 10−2 and 103Ks−1 on solidification the relaxed melt of random isotactic copolymers of propylene with low amount of 1-hexene or 1-octene has been studied. Emphasis has been placed on the structure formation at rapid cooling and an evaluation of the conditions required to permit crystallization, mesophase formation, or suppression of any ordering. The presence of low amount of either 1-hexene or 1-octene co-units in the propylene chain decreases drastically the critical cooling rate required for suppression of crystallization from about 150–200Ks−1 in the homopolymer to about only 10Ks−1 in the copolymers; increasing the cooling rate beyond these limits allowed mesophase formation or even generation of fully amorphous samples. The study of the kinetics of formation of specific structures is completed by a complementary analysis of the X-ray structure, morphology and superstructure of the ordered phase. The hindrance of non-isothermal crystallization and mesophase formation of random copolymers of propylene with 1-hexene or 1-octene is compared with that in propylene–1-butene copolymers; addition of only 2–3mol% 1-hexene or 1-octene into the propylene chain leads to even larger hindrance of the ordering process than the addition of more than 10mol% 1-butene.

A Ruthenium-Catalyzed Hydrosilane-Induced Polymerization of 3-Alkyl-3-hydroxymethyloxetane Derivatives: Facile Access to Functionalized Polyoxetanes by Virtue of Organosilyl Groups

Abstract Ring-opening polymerization of 3-alkyl-3-alkoxymethyl- or 3-alkyl-3-siloxymethyloxetanes is catalyzed by a triruthenium cluster, [Ru3{μ3-(η2,η3,η5-C12H8)}(CO)7], in the presence of trialkylsilanes, providing a novel accessible method for functionalized polyoxetanes of Mn = 103–105. Oxetanes having alkoxy-, fluoroalkoxy-, triethyleneglycoloxy-, and trialkylsiloxy functions undergo polymerization and copolymerization. Consumption rates of two monomers in the copolymerization of 3-benzyloxymethyl- and 3-trimethylsiloxymethyl-3-alkyloxetanes are almost the same, indicating formation of random copolymers. The organosilyl group in the polymer and copolymers with siloxymethyl side chains is converted to CH2OH or CH2OCOR groups by hydrolysis or silyl/acyl exchange. These protocols give the way to access polymers or copolymers bearing OH and OCOR side chains. A ruthenium-catalyzed reaction of 3-ethyl-3-hydroxymethyloxetane with trialkylsilanes results in dehydrogenative silylation to give 3-ethyl-3-siloxymethyloxetane, which is followed by ring-opening polymerization. Combination of tandem dehydrogenative silylation/ring-opening polymerization/the silyl/acyl exchange realizes one-pot synthesis of polymers with CH2OCOR side chains from 3-ethyl-3-hydroxymethyloxetane. DSC analyses of the formed polymers provided Tg and Tm data, which are a good example showing that the polymer properties are controlled by appropriate selection of functional groups at the side chain.

Synthesis, Characterization, Reactivity Ratio and Photo Crosslinking Properties of the Copolymer of 4-Cinnamoyl Phenyl Methacrylate with Butyl Methacrylate

Copolymers of 4-cinnamoyl phenyl methacrylate (4-CPMA) and n-butyl methacrylate (BMA) were prepared in a methyl ethyl ketone (MEK) solution with benzoyl peroxide (BPO) as an initiator at 70°C. They were characterized with UV, IR, 1H-NMR, 13C-NMR, TGA, DSC and gel permeation chromatography. Copolymers were prepared by using different feed ratio of monomers. The monomer reactivity ratios determined by the method of Kelen-Tudos (K-T) were r1 (CPMA) = 2.32, r2 (BMA) = 0.56. The glass transition temperature of the copolymer shows a single Tg indicating the formation of random copolymer for all of the monomer feed composition. Thermogravimetric analysis in air has shown that the initial decomposition temperature of the copolymer was above 220°C. The photocrosslinking properties of the copolymer were examined by UV irradiation with polymer film.

Enzymatic Preparation of Novel Thermoplastic di-Block Copolyesters Containing Poly[(R)-3-hydroxybutyrate] and Poly(ϵ-Caprolactone) Blocks via Ring-Opening Polymerization

Enzymatic modification of a microbial polyester was achieved by the ring-opening polymerization of epsilon-caprolactone (CL) with low-molecular weight telechelic hydroxylated poly[( R)-3-hydroxybutyrate] (PHB-diol) as initiator and Novozym 435 (immobilized Candida antarctica Lipase B) as catalyst in anhydrous 1,4-dioxane or toluene. The ring-opening polymerization was investigated at different conditions with two different types of PHB-diols: PHB-diol(P), containing a primary OH and a secondary OH end groups, and PHB-diol(M), consisting of 91% PHB-diol(P) and 9% PHB-diol containing two secondary OH end groups. The reactions were followed by GPC analyses of the resulting polymers at different time points, and the optimal conditions were established to be 70 degrees C at a weight ratio of CL/enzyme/solvent of 8:1:24. The ring-opening polymerization of CL with PHB-diol(M) (Mn of 2380, NMR) at the molar ratio of 50:1 under the optimal conditions in 1,4-dioxane gave the corresponding poly[HB(56 wt %)-co-CL(44 wt %)] with Mn (NMR) of 3900 in 66% yield. Polymerization of CL and PHB-diol(P) ( Mn of 2010, NMR) at the same condition in toluene gave the corresponding poly[HB(28 wt %)-co-CL(72 wt %)] with Mn (NMR) of 7100 in 86% yield. Both polymers were characterized by (1)H and (13)C NMR and IR analyses as di-block copolyesters containing a PHB block with a secondary OH end group and a poly(epsilon-caprolactone) (PCL) block with a primary OH end group. NMR analyses and control experiments suggested no formation of random copolymers and no change of the PHB block during the reaction. The enzymatic ring-opening polymerization was selectively initiated by the primary OH group of PHB-diol, whereas the secondary OH group remained as an end group in the final polymers. The thermal properties of the di-block poly(HB-co-CL)s were analyzed by DSC, with excellent T g values for the elastomer domain: poly[HB(56 wt %)- co-CL(44 wt %)] with M n (NMR) of 3900 demonstrated a T g of -57 degrees C, Tm of 145, 123, and 53 degrees C; and poly[HB(28wt%)-co-CL(72wt%)] with Mn (NMR) of 7100 gave a Tg of -60 degrees C, Tm of 147 and 50 degrees C. Thus, the selective enzymatic ring-opening polymerization with PHB-diol as macro-initiator provides a new method for the preparation of PHB-based block copolymers as biomaterials with good thermoplastic properties and novel structures containing functional end groups.

Self-Assembly of Methacrylic Nanostructured Copolymers Containing Polyhedral Oligomeric Silsesquioxanes

AbstractTwo hybrid copolymer series obtained by free-radical copolymerization of methacrylcyclohexyl Polyhedral oligomeric silsesquioxane (POSS) with butyl methacrylate or 2-ethylhexylmethacrylate were characterized by 1H-NMR spectroscopy, gel permeation chromatography (GPC), X-rays Diffraction (XRD), differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Reactivity ratios were calculated by low yield composition data suggesting the formation of random copolymers with low probability of poly-POSS sequences. XRD studies showed the crystallization behaviour of the inorganic phase independently on the POSS content; however sample processing by solvent casting effectively hindered the copolymer self-assembling ability. DSC suggests the formation of polyphasic structures with Tg increasing with POSS content, and with endothermal peaks occurring at higher temperature. Finally TGA shows an improved thermal stability of hybrid copolymers with char yield correlated to the level of inorganic phase.

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

AbstractThis article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, 1H‐NMR, and 13C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single Tg, indicating the formation of random copolymers. A slight deviation of the Tg for the copolymers and its complexes can be observed. The copolymer Tg is higher than the Tg value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Design of random copolymers with statistically controlled monomer sequence distributions via Monte Carlo simulations

We use Monte Carlo simulations to model the formation of random copolymers with tunable monomer sequence distributions. Our scheme is based on the original idea proposed a few years ago by Khokhlov and Khalatur [Physica A 249, 253 (1998); Phys. Rev. Lett. 82, 3456 (1999)], who showed that the distribution of species B in A-B random copolymers can be regulated by (a) adjusting the coil size of a homopolymer A and (b) chemically modifying ("coloring") monomers that reside at (or close to) the periphery of the coil with species B. In contrast to Khokhlov and Khalatur's work, who modeled the polymer modification by performing the coloring instantaneously, we let the chemical coloring reaction progress over time using computer simulations. We show that similar to Khokhlov and Khalatur's work, the blockiness (i.e., number of consecutive monomers) of the B species along the A-B copolymer increases with increasing degree of collapse of the parent homopolymer A. A simple analysis of the A-B monomer sequences in the copolymers reveals that monomer sequence distributions in homopolymers "colored" under collapsed conformations possess certain degrees of self-similarity, while there is no correlation found among the monomer sequence distributions formed by coloring homopolymers with expanded conformations.