Crystallinity Of Copolymers Research Articles

Preparation of a Novel Branched Polyamide 6 (PA6) via Co-Polymerization of ε-Caprolactam and α-Amino-ε-Caprolactam

In this study, a novel branched polyamide 6 has been synthesized via the hydrolytic ring-opening co-polymerization of ε-caprolactam (CPL) and α-Amino-ε-caprolactam (ACL). The NMR characterization proves the existence of a branched chain structure. The rheological test determines that there is a remarkable increase in the melt index (MFR), zero shear rate viscosity, and storage modulus in the low-frequency region. The shear-thinning phenomenon becomes more obvious. The thermal properties tested by differential scanning calorimetry (DSC) show that the melting point and crystallinity of co-polymers decrease with the incorporation of ACL. However, the crystal structure of the samples only exhibits a slight change. When the ACL content in the feed is 1 wt%, the tensile strength and fracture elongation rate of the co-polymers show a significant enhancement.

Boron-Catalyzed C1 Copolymerization of Arsonium and Sulfoxonium Ylides toward Unrepresented Structures and Fluorescence Properties.

The first synthesis of well-defined poly(methylene-co-1,1-diphenylpropenenylene) (C1-co-C1'), equivalent to poly(ethylene-co-diphenylbutadiene) copolymers was accomplished by C1 copolymerization of novel diphenylpropenyl triphenyl arsonium ylides (Ph2AY) and dimethylsulfoxonium methylide (Me2SY) using B-thexylborepane as initiator. All polymerization conditions, including feed ratio, temperature, and reaction time, were optimized. A series of photoluminescent poly(ethylene-co-diphenylbutadiene)s were synthesized at different feed ratios, opening a new synthetic horizon for poly(ethylene-co-disubstitutedbutadiene) copolymers. Notably, a new C1 segment, arising from a double bond rearrangement, was confirmed by NMR, resulting in an unprecedented two-monomer three-structure random terpolymer. An unexpected red-shift phenomenon in the fluorescence spectra was observed with increasing the ratio of Ph2AY in the copolymer. This shift is attributed to the aggregation of diphenylbutadiene segment, similar to through-space conjugation (TSC), likely induced by a decrease in the crystallinity of copolymers. Furthermore, another disubstituted allylic triphenyl arsonium ylides, (E)-2-phenylbutenyl triphenyl arsonium ylide (MePhAY) was also synthesized and investigated. These additional compounds expand the knowledge and the potential applications of such copolymerization techniques in advanced materials.

Boron‐Catalyzed C1 Copolymerization of Arsonium and Sulfoxonium Ylides toward Unrepresented Structures and Fluorescence Properties

AbstractThe first synthesis of well‐defined poly(methylene‐co‐1,1‐diphenylpropenenylene) (C1‐co‐C1’), equivalent to poly(ethylene‐co‐diphenylbutadiene) copolymers was accomplished by C1 copolymerization of novel diphenylpropenyl triphenyl arsonium ylides (Ph2AY) and dimethylsulfoxonium methylide (Me2SY) using B‐thexylborepane as initiator. All polymerization conditions, including feed ratio, temperature, and reaction time, were optimized. A series of photoluminescent poly(ethylene‐co‐diphenylbutadiene)s were synthesized at different feed ratios, opening a new synthetic horizon for poly(ethylene‐co‐disubstitutedbutadiene) copolymers. Notably, a new C1 segment, arising from a double bond rearrangement, was confirmed by NMR, resulting in an unprecedented two‐monomer three‐structure random terpolymer. An unexpected red‐shift phenomenon in the fluorescence spectra was observed with increasing the ratio of Ph2AY in the copolymer. This shift is attributed to the aggregation of diphenylbutadiene segment, similar to through‐space conjugation (TSC), likely induced by a decrease in the crystallinity of copolymers. Furthermore, another disubstituted allylic triphenyl arsonium ylides, (E)‐2‐phenylbutenyl triphenyl arsonium ylide (MePhAY) was also synthesized and investigated. These additional compounds expand the knowledge and the potential applications of such copolymerization techniques in advanced materials.

Insights into Factors Affecting Ethylene-Vinyl Acetate Copolymer Crystallinity in Islatravir Implant.

Islatravir, a highly potent nucleoside reverse transcriptase translocation inhibitor (NRTTI) for the treatment of HIV, has great potential to be formulated as ethylene-vinyl acetate (EVA) copolymer-based implants via hot melt extrusion. The crystallinity of EVA determines its physical and rheological properties and may impact the drug-eluting implant performance. Herein, we describe the systematic analysis of factors affecting the EVA crystallinity in islatravir implants. Differential scanning calorimetry (DSC) on EVA and solid-state NMR revealed drug loading promoted EVA crystallization, whereas BaSO4 loading had negligible impact on EVA crystallinity. The sterilization through γ-irradiation appeared to significantly impact the EVA crystallinity and surface characteristics of the implants. Furthermore, DSC analysis of thin implant slices prepared with an ultramicrotome indicated that the surface layer of the implant was more crystalline than the core. These findings provide critical insights into factors affecting the crystallinity, mechanical properties, and physicochemical properties of the EVA polymer matrix of extruded islatravir implants.

Collagen-decorated electrospun scaffolds of unsaturated copolyesters for bone tissue regeneration.

Many efforts have been devoted to bone tissue to regenerate damaged tissues, and the development of new biocompatible materials that match the biological, mechanical, and chemical features required for this application is crucial. Herein, a collagen-decorated scaffold was prepared via electrospinning using a synthesized unsaturated copolyester (poly(globalide-co-pentadecalactone)), followed by two coupling reactions: thiol-ene functionalization with cysteine and further conjugation via EDC/NHS chemistry with collagen, aiming to design a bone tissue regeneration device with improved hydrophilicity and cell viability. Comonomer ratios were varied, affecting the copolymer's thermal and chemical properties and highlighting the tunable features of this copolyester. Functionalization with cysteine created new carboxyl and amine groups needed for bioconjugation with collagen, which is responsible for providing biological and structural integrity to the extra-cellular matrix. Bioconjugation with collagen turned the scaffold highly hydrophilic, decreasing its contact angle from 107 ± 2° to 0°, decreasing the copolymer crystallinity by 71%, and improving cell viability by 85% compared with the raw scaffold, thus promoting cell growth and proliferation. The highly efficient and biosafe strategy to conjugate polymers and proteins created a promising device for bone repair in tissue engineering.

Sensitive room-temperature phosphorescence for luminometric and visual monitoring of the dynamic evolution of acrylate–vinylidene chloride copolymers

Unlike fluorescence, room-temperature phosphorescence (RTP) has never been utilized to monitor the dynamic variation of polymer. In the present study, acrylate-vinylidene chloride (VDC) copolymers were doped with a good RTP molecule, N-hydroxyethyl 4-bromo-1,8-naphthalimide (HBN). During the maturation process, marked RTP-intensity enhancement of HBN was observed due to the crystallinity increase of copolymers, verified by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). For ensuring the more efficient RTP emission of HBN, copolymers with a higher content of crystallizable VDC segments and a more polar acrylate comonomer, i.e. methyl acrylate (MA) were preferred. According to the RTP characterizations, the following deductions could be obtained: (1) Maturation for 8–9 days at room temperature was needed for the copolymers with a high VDC content to ensure the complete crystallization; (2) Raising the maturation temperature to 50 and 70 °C not only accelerated the crystallization rate, but also increased the crystallinity of copolymers; (3) RTP method was more sensitive to the slight crystallinity variation than XRD and FTIR. Moreover, the dynamic maturation processes of acrylate-VDC copolymers could be also visually monitored through contacting with certain organic solvents that led to the emission color transition from orange to blue.

Synthesis of Poly(Hexamethylene Succinate-Co-Ethylene Succinate) Copolymers With Different Physical Properties and Enzymatic Hydrolyzability by Regulating the Ratio of Monomer.

Poly(hexylene succinate) (PHS), poly(ethylene succinate) (PES), and their random copolyesters, poly(hexylene succinate-co-ethylene succinate) ((P(HS-co-ES)), were synthesized by melting polycondensation. Simply varying the ratios of HS/ES afforded control over the copolymer crystallinity, thermal and mechanical properties, wettability, and enzymatic hydrolyzability as shown by X-ray diffraction (XRD), differential scanning calorimetry (DSC), tensile tests, and water contact angle (WCA) measurements. The enzymatic hydrolysis rates of all prepared copolyesters were higher than those of the corresponding homopolyesters. The hydrolysis rates were affected by crystallinity, melting temperature, and hydrophobicity of the copolyesters, and therefore, the degradation rates could be tuned along with the ES content. The library of copolymers prepared here with tunable degradation rates, ranging from HS-enriched to ES-enriched copolyesters, is promising for a variety of different applications. The P(HS-co-ES51) copolyester that did not fully degrade is particularly promising for use in long-term storage applications, whereas P(HS-co-ES13) and P(HS-co-ES76) that rapidly degrade are good for use in very short-term applications.

High methanol resistance semi-crystalline sulfonated poly(ether ketone) proton exchange membrane for direct methanol fuel cell

Three new sulfonated and semi-crystalline poly(ether ketone)-type copolymers (Cr-SPEK) with densely sulfonated microblock of different length are synthesized and evaluated as proton exchange membranes. The relationship between molecular structure of copolymers, microscopic morphology and macroscopic performance of membranes are studied: The increase in the length of the hydrophilic sulfonated microblock facilitates constructing well-connected ionic transport channels, which improves the proton conduction of Cr-SPEK membranes. And expanding the size of hydrophobic poly(ether ketone) (PEK) block promotes higher crystallinity of copolymers, resulting in enhancing dimensional stability, mechanical tensile, oxidation stability and methanol resistance of Cr-SPEK membranes. The tCr-SPEK membrane with longest hydrophilic microblock and maximum crystallinity (15.2%) exhibits best comprehensive performance. The proton conductivity and swelling ratio of the tCr-SPEK membrane measured under fully hydrated state at 80 °C are 146.7 mS cm−1 and 11.9%, respectively. And the methanol permeability of tCr-SPEK membrane is only 1.1 × 10−7 cm2 s−1, which is nearly one-sixteenth of that of Nafion 117 membrane. The single cell performance of tCr-SPEK membrane in direct methanol fuel cells (DMFCs) continuously grows with the higher concentration of methanol solution until 12 M. Therefore, the tCr-SPEK membrane represents great potential for application in DMFCs.

Enzymatic Catalysis in Favor of Blocky Structure and Higher Crystallinity of Poly(Butylene Succinate)-Co-(Dilinoleic Succinate) (PBS-DLS) Copolymers of Variable Segmental Composition.

To systematically investigate the synthesis of poly(butylene succinate)-co-(dilinoleic succinate) (PBS-DLS) copolymers and to enrich the library of polyesters synthesized via a sustainable route, we conducted a two-step polycondensation using fully biobased monomers such as diethyl succinate (DS), 1,4-butanediol (1,4-BD) and dilinoleic diol (DLD) in diphenyl ether, using Candida Antarctica lipase B (CAL-B) as biocatalyst. A series of PBS-DLS copolyesters with a 90-10, 70-30 and 50-50 wt% of hard (PBS) to soft (DLS) segments ratio were compared to their counterparts, which were synthesized using heterogenous titanium dioxide/silicon dioxide (TiO2/SiO2) catalyst. Chemical structure and molecular characteristics of resulting copolymers were assessed using nuclear magnetic spectroscopy (1H- and 13C-NMR) and gel permeation chromatography (GPC), whereas thermal and thermomechanical properties as well as crystallization behavior were investigated by differential scanning microscopy (DSC), dynamic mechanical thermal analysis (DMTA), digital holographic microscopy (DHM) and X-ray diffraction (XRD). The obtained results showed that, depending on the type of catalyst, we can control parameters related to blockiness and crystallinity of copolymers. Materials synthesized using CAL-B catalysts possess more blocky segmental distribution and higher crystallinity in contrast to materials synthesized using heterogenous catalysts, as revealed by DSC, XRD and DHM measurements.

Effect of Crystallinity on the Properties of Polycaprolactone Nanoparticles Containing the Dual FLAP/mPEGS-1 Inhibitor BRP-187.

Seven polycaprolactones (PCL) with constant hydrophobicity but a varying degree of crystallinity prepared from the constitutional isomers ε-caprolactone (εCL) and δ-caprolactone (δCL) were utilized to formulate nanoparticles (NPs). The aim was to investigate the effect of the crystallinity of the bulk polymers on the enzymatic degradation of the particles. Furthermore, their efficiency to encapsulate the hydrophobic anti-inflammatory drug BRP-187 and the final in vitro performance of the resulting NPs were evaluated. Initially, high-throughput nanoprecipitation was employed for the εCL and δCL homopolymers to screen and establish important formulation parameters (organic solvent, polymer and surfactant concentration). Next, BRP-187-loaded PCL nanoparticles were prepared by batch nanoprecipitation and characterized using dynamic light scattering, scanning electron microscopy and UV-Vis spectroscopy to determine and to compare particle size, polydispersity, zeta potential, drug loading as well as the apparent enzymatic degradation as a function of the copolymer composition. Ultimately, NPs were examined for their potency in vitro in human polymorphonuclear leukocytes to inhibit the BRP-187 target 5-lipoxygenase-activating protein (FLAP). It was evident by Tukey’s multi-comparison test that the degree of crystallinity of copolymers directly influenced their apparent enzymatic degradation and consequently their efficiency to inhibit the drug target.

Synthesis of sulfonated poly(styrene‐co‐methyl methacrylate) by semicontinuous heterophase polymerization for filtration membranes

AbstractIn this study, styrene (St) and methyl methacrylate (MMA) were copolymerized in semicontinuous heterophase using Hitenol‐BC10 (HBC10) as polymerizable surfactant and ammonium persulfate as initiator to obtain copolymers of poly(St‐co‐MMA). The effects of St/MMA weight ratio and surfactant concentration on kinetics, and colloidal properties of latexes were studied. Copolymers and latexes were characterized by scanning electron microscopy, thermogravimetric analysis (TGA), gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and X‐ray diffraction analysis. Fast reaction rates under monomer starved conditions and high conversions (>85%) were observed in all cases, with a weight‐average molecular weight in the range of 2.10 × 106 to 0.96 × 106 g mol−1, decreasing with the HBC10 concentration due to an effect of chain transference to surfactant. Stable latexes with spherical particles with average diameter in the interval of 65–41 nm and Z‐potential in the interval of −68.24 to −38.44 mV were obtained. Copolymers were sulfonated using acetyl sulfate as sulfonating agents and subsequently used for filtration membrane fabrication through the phase inversion method. Membranes were tested in simulated seawater filtration (3.5% NaCl) under constant pressure. At a pressure of 20 psia, permeated flux (J) of pure water and salt rejection (R) varied from 13.8 to 20.5 L m−2 h−1 and 37.8%–50.7%, respectively. It was concluded that membrane's performance is dependent on copolymer composition, the crystallinity of copolymers, and the ionic exchange capacity of membranes, being the best membrane composed of 90/10 of St‐to‐MMA weight ratio and using a monomer‐to‐surfactant weight ratio of 29.9.

Block Junction-Functionalized All-Conjugated Donor-Acceptor Block Copolymers.

Junction-functionalized donor-acceptor (D-A) block copolymers (BCPs) enable spatial and electronic control over interfacial charge dynamics in excitonic devices such as solar cells. Here, we present the design, synthesis, morphology, and electronic characterization of block junction-functionalized, all-conjugated, all-crystalline D-A BCPs. Poly(3-hexylthiophene) (P3HT), a single thienylated diketopyrrolopyrrole (Th xDPPTh x, x = 1 or 2) unit, and poly{[ N, N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]- alt-5,5'-(2,2'-bithiophene)} (PNDIT2) are used as donor, interfacial unit, and acceptor, respectively. Almost all C-C coupling steps are accomplished by virtue of C-H activation. Synthesis of the macroreagent H-P3HT-Th xDPPTh x, with x determining its C-H reactivity, is key to the synthesis of various BCPs of type H-P3HT-Th xDPPTh x- block-PNDIT2. Morphology is determined from a combination of calorimetry, transmission electron microscopy (TEM), and thin-film scattering. Block copolymer crystallinity of P3HT and PNDIT2 is reduced, indicating frustrated crystallization. A long period lp is invisible from TEM, but shows up in resonant soft X-ray scattering experiments at a length scale of lp ∼ 60 nm. Photoluminescence of H-P3HT-Th xDPPTh x indicates efficient transfer of the excitation energy to the DPP chain end, but is quenched in BCP films. Transient absorption and pump-push photocurrent spectroscopies reveal geminate recombination (GR) as the main loss channel in as-prepared BCP films independent of junction functionalization. Melt annealing increases GR as a result of the low degree of crystallinity and poorly defined interfaces and additionally changes backbone orientation of PNDIT2 from face-on to edge-on. These morphological effects dominate solar cell performance and cause an insensitivity to the presence of the block junction.

Effect of Electron Beam Irradiation on Thermal and Mechanical Properties of Polyamide Copolymer/Multiwall Carbon Nanotube Composites

Ternary polyamide (tPA) copolymer is susceptible to degradation when it is irradiated by electron beam (e-beam), and effective methods to avoid degradation and increase gel content are highly desirable for crosslinking. Carboxylated multiwall carbon nanotube (MWCNT) is modified by hydroxyethyl acrylate (HEA) in this paper and used as a co-agent for the e-beam irradiation crosslinking of tPA copolymer. HEA modified MWCNT can function as an effective co-agent for the e-beam irradiation crosslinking of tPA copolymer to increase the gel content and improve the mechanical properties of tPA copolymer. Under an irradiation of 160 kGy, addition of 2 parts per hundred (phr) HEA modified MWCNT into tPA copolymer can increase the gel content of tPA copolymer from about 20% to 40% (mass ratio) and increase the tensile strength from 45 to 59MPa. The irradiation also affects the glass transition temperature of tPA copolymer by increasing the gel content. The results show that HEA modified MWCNT can act as a nucleating agent to increase the crystallization temperature, melting temperature and crystallinity of tPA copolymer.

Spinnability of Polyacrylonitrile Gel Dope in the Mixed Solvent of Dimethyl Sulfoxide/Dimethylacetamide and Characterization of the Nascent Fibers

In this work, acrylonitrile copolymers were prepared via precipitation polymerization. The copolymer solutions prepared at various ratio of dimethyl sulfoxide and dimethylacetamide were tested to prepare the nascent fibers by one-step wet-spun method. The effect of temperature, solvent ratio, molecular weight and the solid content on the rheological properties of polyacrylonitrile gel solution in different mixed solvent were studied. It was shown that the viscosity decreased with the increase of the temperature and fluctuated with the different solvent ratio reaching the minimal value at the ratio of dimethyl sulfoxide to dimethylacetamide equal to 1.25. The crystallinity of copolymers and the structure of the nascent fiber surface also depended from the solvent ratio in polymerization. The optimum conditions for spinnability of copolymers were determined. The high-quality polyacrylonitrile precursor was achieved with the controllable range of 0.5–0.8 dtex and the toughness of polyacrylonitrile precursor was greater than 6.0 cN/dtex after the wet spinning process, while the tensile strength of carbon fiber is up to 6.25 GPa after their pre-oxidation and carbonization process.

Crystallinity of block copolymer controlled by cyclodextrin

We report a differential scanning calorimetry study to investigate the effect of cyclodextrins (CD) on the crystallinity of a copolymer. Tetronics was selected as copolymer with star-like shape formed by four polyethylene oxide flanked by four polypropylene oxide blocks linked to ethylenediamine central group. The use of CD with different cavity size was exploited for a block selective inclusion. A model for supramolecular association was considered for a quantitative description of the enthalpy data. The polymer chain incorporation into the CD cavity generates a loss of crystallinity. The stoichiometry of the CD/copolymer aggregates can be tuned by changing the CD cavity size. The investigated systems represent interesting necklace-like supramolecular structures with tunable crystallinity.

Synthesis and characterization of poly(trifluoroethylene-co-hexafluoropropylene) and the optical properties of its thin films

Copolymers of trifluoroethylene (TrFE) and hexafluoropropylene (HFP) were synthesized and characterized by various instrumental techniques. The maximum incorporation of HFP was 19.6 mol%. It was found that the reactivity ratios of TrFE and HFP were r TrFE =4.12 and r HFP ≈0, respectively, by applying Mayo-Lewis method. It was also found that the incorporation of HFP in copolymer chain influenced thermal properties. As increasing HFP content in copolymers, the melting temperature and crystallinity of copolymers were decreased and the glass transition temperature of copolymers gradually shifted to low temperature. Reduced crystallinity of copolymers was helpful to prepare coating layers having much even surface. Compared with coating layer prepared from TrFE homopolymer, the surface roughness was decreased and light transmittance through the coating layer increased when the copolymers of TrFE and HFP were used. This tendency was more appreciable as increasing HFP content in the copolymers.

Copolymerization with Polyether Segments Improves the Mechanical Properties of Biodegradable Polyesters.

To improve the properties of poly(butylene succinate) (PBS), a series of poly[(butylene succinate)-co-poly(tetramethylene glycol)]s (PBSTMGs) with different poly(tetramethylene glycol) (PTMG) contents were successfully prepared by the catalyzed melt polycondensation process. The effect of introducing flexible PTMG segments on the properties was investigated, and they were compared to those of PBS. The differential scanning calorimetry results indicated that the melting temperature, crystallization temperature, and crystallinity of PBSTMG copolymers were slightly lower than those of PBS. Furthermore, these thermal parameters decreased gradually with the increase of PTMG content. Dynamic mechanical analysis showed that there was a significant decline of storage modulus (E′) in the overall temperature range of copolymers compared to that of PBS. The incorporation of PTMG did not modify the crystal lattice of PBS according to the wide-angle X-ray diffraction analysis. Because of copolymerization, the size of the spherulites was reduced at high PTMG contents. The soft domain in the copolymers might contribute to the enhanced tear strength of PBSTMG. The elongation at break and impact strength of PBSTMG copolymers were greatly improved as a result of the phase separation structure and lower degree of crystallinity. Especially, when the PTMG content was 10 mol %, the impact strength of the copolymer reached up to 4.5 times that of PBS. In addition, with more soft segments introduced, the biodegradability of the copolymers became much better than that of PBS.

The effect of ethylene glycol on starch‐g‐PCL graft copolymer synthesis

The synthesis of the graft copolymer starch‐g‐PCL was carried out in a single phase, using molybdenum oxide as a catalyst, at a temperature of 150°C over a period of 24 h. Infrared spectroscopy and nuclear magnetic resonance analyses indicated that the graft copolymer was successfully synthesized, obtaining an 84% conversion yield. The introduction of ethylene glycol to the reaction influences the copolymer synthesis, affecting conversion yields and the physicochemical properties of the resultant copolymer. X‐ray diffraction analysis indicates that the copolymer crystallinity decreases as ethylene glycol concentration increases. An investigation of the thermal properties of the graft copolymer suggested that the decomposition temperature of the copolymer, compared to that of the homopolymer, decreases with exposure to ethylene glycol. Scanning electron microscopy revealed the formation of clusters between the starch granules and the grafted copolymer due to the interaction of the hydroxyl groups of the starch and PCL.

Influence of a low content of PEO segment on the thermal, surface and morphological properties of triblock and diblock PCL copolymers

Two series, one of triblock (PCL/PEO/PCL) and the other of diblock (PCL/PEO) copolymers were prepared by ring-opening polymerization of e-caprolactone catalized with tin(II) octoate and by using dihydroxy or monohydroxy poly(ethylene oxide) as the macroinitiator. The PEO block length was fixed (Mn 1,000 g/mol) and the PCL block lengths (Mn 10,000-40,000 g/mol) were tailored by changing weight ratio of e-CL/PEO. The copolymers’ structure was confirmed by 1H and quantitative 13C NMR spectroscopy while their molecular weights were determined by GPC analysis. The thermal properties and the degree of crystallinity of the copolymers were investigated and compared by using DSC and WAXS. Both types of copolymers were semicrystalline with the orthorhombic PCL crystal lattice. The surface morphology of the copolymer films was investigated by using optical microscopy and AFM analysis, which confirmed the spherulitic lamellar structure with spherulites of different diameters. Data indicated that a low content of PEO segment had an influence on thermal degradation behavior, crystallinity and morphology of copolymers. Roughness of copolymer films was affected by the content of PEO and correlated with the spherulites’ diameter. The small changes in water and moisture absorption properties of copolymers compared to homopolymer PCL were observed.

Composite Nanoformulation Therapeutics for Long-Term Ocular Delivery of Macromolecules.

The purpose of this investigation is to design and synthesize novel pentablock (PB) copolymer (PB-1: PCL-PLA-PEG-PLA-PCL) based nanoformulations suspended in a thermosensitive gelling copolymer (PB-2: mPEG-PCL-PLA-PCL-PEGm) termed as composite nanoformulation. The composite nanoformulation was prepared to provide a sustained delivery of macromolecules over a longer duration with negligible burst release effect. The delivery system was designed to be utilized for the treatment of posterior segment ocular diseases such as age-related (wet) macular degeneration, diabetic retinopathy, and diabetic macular edema. The novel PB copolymers were characterized for their functional groups by Fourier transform infrared spectroscopy, molecular weight and purity by (1)H NMR spectroscopy, and gel permeation chromatography. X-ray diffraction analysis was used to determine the crystallinity of copolymers. The size distribution of PB-1 nanoparticles (NPs) prepared using emulsification-solvent evaporation method was found to be ∼150 nm analyzed by nanoparticle tracking analysis. The % encapsulation efficiency and % drug loading were found to be 66.64% w/w ± 1.75 and 18.17% w/w ± 0.39, respectively, (n = 3). Different weight percentages (15 and 20 wt %) of the PB-2 copolymer have been utilized for in vitro release studies of IgG-Fab from composite nanoformulation. A negligible burst release with continuous near zero-order release has been observed from the composite nanoformulation analyzed up to 80 days. In vitro cell viability and biocompatibility studies performed on ocular (human corneal epithelial and retinal pigment epithelium) and mouse macrophage (RAW 264.7) cell lines showed that the synthesized PB copolymer based composite nanoformulations were safe for clinical applications. On the basis of the results observed, it is concluded that PB copolymer based composite nanoformulations can serve as a platform for ocular delivery of therapeutic proteins. In addition, the composite nanoformulation may provide minimal side effects associated with frequent intravitreal injections.