Advancements in Polymer Science: Synthesis, Characterization, and Biomedical Applications of Homopolymers and Copolymers

Polymer science encompasses a different range of materials critical to industries spanning from packaging to biomedicine. Understanding the synthesis, characterization, and applications of common homopolymers and copolymers is fundamental to advancing polymer research and development. In this comprehensive review, we explore various preparation methods, including free radical, anionic, and cationic polymerization, utilized for synthesizing homopolymers and copolymers. Furthermore, we investigate solvent choices commonly employed for polymer characterization, ranging from neat conditions, polar protic and polar aprotic solvents. We also explored characterization techniques, including Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR), Atomic Force Microscopy (AFM), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA). In addition to industrial applications, we highlight the diverse biological applications of homopolymers, poly(2-hydroxyethyl methacrylate) (pHEMA) and polystyrene, which find its extensive use in biomedicine. By synthesizing and analyzing this wealth of information, this review aims to provide a comprehensive understanding of the synthesis, characterization, and applications of homopolymers and copolymers, with a particular focus on their biological applications. This holistic approach not only contributes to advancements in polymer science and technology but also fosters innovation in biomedicine, ultimately benefiting human health and well-being.

Surface Photografting of Novel Sulfobetaine Copolymers on Silica

A couple of novel sulfobetaine copolymer is developed via Michael-type addition reaction. The comonomers, diamines and maleimide react via Michael reaction through UV irradiation using AIBN as photoinitiator producing polyamine chain. Further, sulfobetaine copolymers were obtained on treatment of the polyamine with sulfopropylating agent, 1,3-propane sultone. These novel sulfobetaine polymers were grafted on silica surface to produce responsive biocompatible surface. This easy straightforward, catalyst free facile protocol for synthesis of polymer grafted surface is useful for developing biomedical devices. Additionally, both the copolymers show fluorescence characteristics.

Nitroxide-Mediated Photo-Controlled/Living Radical Polymerization of Methacrylic Acid

The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.

Synthesis of Branched Polyethylene via Bulky α-Diimine Nickel(II)-Catalyzed Ethylene Chain-Walking Polymerization

The catalysis of olefin polymerization through the chain-walking process is a subject of great interest. In this contribution, the successful synthesis of a Brookhart-type unsymmetrical α-diimine nickel catalyst Ni, which contains both dibenzhydryl and phenyl groups, was determined by X-ray crystallography. The compound has a pseudo-tetrahedral geometry at the Ni center, showing pseudo-C2-symmetry. Upon activation with modified methylaluminoxane (MMAO), Ni1 exhibits high catalytic activity up to 1.02 × 107 g PE (mol Ni h)−1 toward ethylene polymerization, enabling the synthesis of high molecular weight branched polyethylene. The molecular weights and branching densities could be tuned over a very wide range. The polymerization results indicated the possibility of precise microstructure control, depending on the polymerization temperature. The branching densities were decreased with increasing the polymerization temperature.

Non-Thermal Radio Frequency Stimulation of Tubulin Polymerization in Vitro: A Potential Therapy for Cancer Treatment

The use of radio frequency energy is an established technology for certain oncology therapies. Direct inputs of radio frequency (RF) energy as thermal energy are applied to ablate tumors or catalyze secondary reactions in adjunct treatments against certain tumor types. Yet, other applications are being developed which take advantage of properties of RFs that impinge on biological proteins and cells without thermal effects. Here we report a proof-of-concept application of specific, digitally encoded, low power (non-thermal) radio frequency energy in an in vitro preparation of a tubulin polymerization assay. The radio frequency energy signal, designated M2(3), was applied to the tubulin polymerization assay samples during spectrophotometric measurements to assess the effectiveness for enhancing tubulin polymerization. A commercially available taxane (paclitaxel) that promotes tubulin polymerization was used as a control to assess the effectiveness of the M2(3) radio frequency energy signal on tubulin polymerization rates. A low power, specific, digital radio frequency energy signal is capable of promoting tubulin polymerization as effectively as a commercially available taxane.

Elucidation of Acceleration Mechanisms by a Photosensitive Onium Salt for Nitroxide-Mediated Photocontrolled/Living Radical Polymerization

The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.

Evaluation of Rhizobium tropici-Derived Extracellular Polymeric Substances on Selected Soil Properties, Seed Germination, and Growth of Black-Eyed Peas (Vigna unguiculata)

Rhizobium tropici-derived extracellular polymeric substances (EPS) have been used in soils to enhance soil structures and mitigate soil erosions. However, information on their use to improve soil health and fertility indicators, and plant growth is limited. In a greenhouse study, we investigated their effects on some soil health, soil fertility indices, and the growth of black-eyed peas (Vigna unguiculate). Results showed that soils incubated with EPS significantly increased basal soil respiration, soil microbial biomass, permanganate oxidizable carbon (POC), and potentially mineralizable nitrogen (PMN). The EPS shifted microbial populations from bacteria to fungi and Gram (−ve) to Gram ( ve) bacteria. However, it had little or no effects on soil pH, soil organic matter (SOM), and cation exchange capacity (CEC). The EPS decreased soil moisture loss, increased soil aggregate stability, but delayed blacked-eyed peas germinations in the soils. At 0.1% (w/w) concentrations in soils, there was increase in plant root nodulations and vegetative growth. This study was carried out within 40 days of incubating soils with EPS or growing the black-eyed peas in a greenhouse study. The plant growth parameters were taken before flowering and fruiting. Further studies of the effects of incubating soils with the extracellular polymeric substances on plant growth. Soil microbial biomass, microbial diversities, and other soil fertility indices are deemed necessary.

The Continuum Stored Energy for Constitutive Modeling Finite Deformations of Polymeric Materials

With symmetries measured by the Lie group and curvatures revealed by differential geometry, the continuum stored energy function possesses a translational deformation component, a rotational deformation component, and an ellipsoidal volumetric deformation component. The function, originally developed for elastomeric polymers, has been extended to model brittle and ductile polymers. The function fits uniaxial tension testing data for brittle, ductile, and elastomeric polymers, and elucidates deformation mechanisms. A clear distinction in damage modes between brittle and ductile deformations has been captured. The von Mises equivalent stress has been evaluated by the function and the newly discovered break-even stretch. Common practices of constitutive modeling, relevant features of existing models and testing methods, and a new perspective on the finite elasticity-plasticity theory have also been offered.

Preparation of Polymer Composite Particles by Phase Separation Followed by Suspension Polymerization

The novel method for preparing the polymer composite particles has been developed. It was tried to prepare polymer composite particles composed of polystyrene and carbon black with the phase separation method followed by suspension polymerization. In order to prepare the polymer composite particles with the more uniform diameter, the styrene monomer droplets containing carbon black were formed with phase separation emulsification in which ethyl alcohol and water were used as the good solvent and the poor solvent for styrene monomer, respectively. In the experiment, the surfactant species and their concentrations, the pouring velocity of water and the weight ratio of carbon black to styrene monomer were mainly changed. Water was poured at the given pouring velocity into ethyl alcohol in which styrene monomer and an initiator were dissolved and carbon black was dispersed beforehand. The spherical polymer composite particles containing carbon black were prepared with Tween 20 and Tween 80 of nonionic surfactants and the irregular polymer composite particles were prepared with PVA, SDS and Kotamine. The diameters of polymer composite particles increased with the pouring velocity of water and with the weight ratio of carbon black to styrene monomer.

Simple Preparation of Halogen-Substituted <i>α</i>-Diimine Nickel Complexes Immobilized into Clay Interlayer as Catalysts for Ethylene Oligo-/Polymerization

In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene&bull;g-cat–1&bull;h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.

Optimization of Grafted Fibrous Polymer as a Solid Basic Catalyst for Biodiesel Fuel Production

Grafted fibrous polymer with quaternary amine groups could function as a highly-efficient catalyst for biodiesel fuel (BDF) production. In this study, the optimization of grafted fibrous polymer (catalyst) and transesterification conditions for the effective BDF production was attempted through a batch-wise transesterification of triglyceride (TG) with ethanol (EtOH) in the presence of a cosolvent. Trimethylamine was the optimal quaternary amine group for the grafted fibrous catalyst. The optimal degree of grafting of the grafted fibrous catalyst was greater than 170%. The optimal transesterification conditions were as follows: The optimal molar quantity of quaternary amine groups, transesterification temperature, molar ratio of TG and EtOH, and primary alkyl alcohol were 0.8 mmol, 80°C, 1:200, and 1-pentanol, respectively. The grafted fibrous catalyst could be applied to BDF production using natural oils. Furthermore, the grafted fibrous catalyst could be used repeatedly after regeneration involving three sequential processes, i.e., organic acid, alkali, and alcohol treatments, without any significant loss of catalytic activity.

Synthesis of Amine-type Adsorbents with Emulsion Graft Polymerization of 4-hydroxybutyl Acrylate Glycidylether

Radiation induced graft polymerization on polymeric matrix followed by functionalization is widely accepted for the preparation of metal adsorbents. In this paper, a pre-irradiation method was used for emulsion graft polymerization of 4-hydroxybutyl acrylate glycidylether (4-HB) onto polyethylene/polypropylene (PE/PP) nonwoven fabric. The degree of grafting (Dg) which can be calculated by weight increment was determined as a function of reaction time, irradiation dose, and monomer concentration. After 30 kGy irradiation, with 4-HB concentration of 5%, surfactant Span 20 of 0.5% at 40°C for 2 h, the trunk polymer was made grafted at a Dg of 135%. 4-HB-grafted PE/PP nonwoven fabric was modified by ethylenediamine (EDA) in isopropyl alcohol (IPA) as a solvent at 60°C. With a Dg of 135%, the amine group density of the adsorbent is 2.8 mmol/g. The adsorption test was carried out by batch experiment in several metal ion solutions, and the removal ratio from the EDA modified adsorbent of the metal ions is in the order of Cu2+ > Pb2+ > Zn2+ > Ni2+ > Li+. Compared with glycidyl methacrylate (GMA) which is a typical functional monomer for graft polymerization, 4-HB-grafted adsorbent exhibited not only better mechanical property but also higher adsorption capacity of Cu2+ and Pb2+.

SOME REMARKS ON THE POLYMERIZATION REACTION ENGINEERING

In this paper,we overview beifely some of our key projects that had contridubted to modifyprevious author’s conclusions and put forward new viewpoints that are being underinvestigation.The novel ideas worth mentioning are the calculation of the sequence distributionon the copolymerization with a new version of probability suggested,the characterization of stepgrowth polymerization that indicates the MDW may not be continuous in theory,and after all,the Nylon 6 polymerization engineering exploitation where the concept of water activity is usedin place of concentration so as to extend the applicability’of the kinetic model proposed previous-ly.

HOMOPOLYMERS AND COPOLYMERS OF GLYCOLIDE AND LACTIDE

The homopolymerization and copolymerization of glycolide (GA) and lactide (LA) are des-cribed. The resulting polymers are characterized by differential scanning calorimetry (DSC),thermogravimetric analysis (TGA), 300 MHz proton nuclear magnetic resonance spectroscopy(NMR), infrared spectroscopy, and X-ray diffraction. The rheological properties of PGA andPGLA 910 are evaluated by shear experiments. The biodegradation has been studied in vivo. Theresults show that the polyesters can be absorbed by the muscles of rabbits after 60 days.

Influence of Suspension Parameters on Water Absorbency of Starch-g-poly( sodium acrylate) Synthesized by Inverse Suspension Polymerization

Superabsorbents starch grafted sodium polyacrylate was prepared by inverse suspension polymerization, using toluene as the continuous phase, potassium persulfate as the initiator. The effect of suspension parameters, such as volume ratio of continuous phase and dispersed phase, type and dosage of suspending agents, on water absorbency of the starch grafted polymer was studied. Different starch derivatives were also investigated. Superabsorbents made of cationic starch has higher water absorbency than that made of native corn starch.

AQUEOUS STABLE FREE RADICAL POLYMERIZATION PROCESSES

An overview of aqueous polymerizations, which include emulsion, miniemulsion and suspension polymerizations, under stable free radical polymerization (SFRP) conditions is presented. The success of miniemulsion and suspension SFRP polymerizations is contrasted with the difficulties associated with obtaining a stable emulsion polymerization. A recently developed unique microprecipitation technique is referenced as a means of making submicron sized particles that can be used to achieve a stable emulsion SFRP process.

Characterization and coagulation performance of polymeric phosphate ferric sulfate on eutrophic water

Polymeric phosphate ferric sulfate (PPFS),a new improved coagulation reagent,was prepared by polymeric ferric sulfate (PFS),Na2HPO4 and NaOH. The degree of iron polymerisation (Fepol) of PPFS was determined by means of the ferron-timed spectroscopy method. Furthermore,the effect of n(P)/n(Fe),alkalization degree,pH value,and PPFS dosage on the removal rate of eutrophic water turbidity and chl-a and ζ-potential of products were also investigated. The experimental results show that the best n(P)/n(Fe) of flocculation effect in stable product of PFFS is 0.3; the best alkalization degree of flocculation effect is 0.2,while the n(P)/n(Fe) is 0.3. Under the neutral and subalkalic (pH value is 7-8) conditions,PPFS achieves the best processing efficiency. PPFS has more excellent turbidity and higher chlorophyl removal rate by studying treatment eutrophic water in comparison with PFS.

Amphiphilic Block Copolymer for adsorption of Organic Contaminants

In this study, new polymeric adsorbents, 2 types of polystyrene-block-poly (N-isopropylacrylamide) (PSN, structure of hydrophobic core and hydrophilic shell), were developed and applied for removal of organic pollutants from wastewater. Encapsulation of organic pollutants by the polystyrene-block-poly (N-isopropylacrylamide) (PSN) resulted in increasing hydrophobicity of the polystyrene with abundant hydrophobic spaces within the amphiphilic block copolymer. The encapsulation mechanism of BTEX by PSN was investigated and found to be mainly attributable to the Van der Waals interactions between the aromatic ring of BTEX and the hydrophobic core of PSN. Polystyrene-block-poly (N-isopropylacrylamide) showed good potential as a novel and cost effective adsorbent for application to wastewater treatment, which can be simply regenerated and reused using an external temperature changing system.

Graft Copolymerization of N,N-Dimethylacrylamide to Cellulose in Homogeneous Media Using Atom Transfer Radical Polymerization for Hemocompatibility

In homogeneous media, N,N-Dimethylacrylamide (DMA) was grafted copolymerization to cellulose by a metal-catalyzed atom transfer radical polymerization (ATRP) process. First, cellulose was dissolved in DMAc/LiCl system, and it reacted with 2-bromoisobutyloyl bromide (BiBBr) to produce macroinitiator (cell-BiB). Then DMA was polymerized to the cellulose backbone in a homogeneous DMSO solution in presence of the cell-BiB. Characterization with FT-IR, NMR, and GPC measurements showed that there obtained a graft copolymer with cellulose backbone and PDMA side chains (cell-PDMA) in well-defined structure. The proteins adsorption studies showed that the cellulose membranes modified by the as-prepared cell-PDMA copolymer owns good protein adsorption resistancet.