Final Copolymer Research Articles

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization.

Reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to prepare well-defined ABCB tetrablock copolymer nanoparticles via sequential monomer addition at 30 °C. The A block comprises water-soluble poly(2-(N-acryloyloxy)ethyl pyrrolidone) (PNAEP), while the B and C blocks comprise poly(t-butyl acrylate) (PtBA) and poly(n-butyl acrylate) (PnBA), respectively. High conversions are achieved at each stage, and the final sterically stabilized spherical nanoparticles can be obtained at 20% w/w solids at pH 3 and at up to 40% w/w solids at pH 7. A relatively long PnBA block is targeted to ensure that the final tetrablock copolymer nanoparticles form highly transparent films on drying such aqueous dispersions at ambient temperature. The kinetics of polymerization and particle growth are studied using 1H nuclear magnetic resonance spectroscopy, dynamic light scattering, and transmission electron microscopy, while gel permeation chromatography analysis confirmed a high blocking efficiency for each stage of the polymerization. Differential scanning calorimetry and small-angle X-ray scattering studies confirm microphase separation between the hard PtBA and soft PnBA blocks, and preliminary mechanical property measurements indicate that such tetrablock copolymer films exhibit promising thermoplastic elastomeric behavior. Finally, it is emphasized that targeting an overall degree of polymerization of more than 1000 for such tetrablock copolymers mitigates the cost, color, and malodor conferred by the RAFT agent.

Multifunctional Poly(2-ethyl-2-oxazoline) Copolymers Containing Dithiolane and Pentafluorophenyl Esters as Effective Reactive Linkers for Gold Surface Coatings.

Surface functionalization with biological macromolecules is an important task for the development of sensor materials, whereby the interaction with other biological materials should be suppressed. In this work, we developed a novel multifunctional poly(2-ethyl-2-oxazoline)-dithiolane conjugate as a versatile linker for gold surface immobilization of amine-containing biomolecules, containing poly(2-ethyl-2-oxazoline) as antifouling polymer, dithiolane for surface immobilization, and activated esters for protein conjugation. First, a well-defined carboxylic acid containing copoly(2-ethyl-2-oxazoline) was synthesized by cationic ring-opening copolymerization of 2-ethyl-2-oxazoline with a methyl ester-containing 2-oxazoline monomer, followed by postpolymerization modifications. The side-chain carboxylic groups were then converted to amine-reactive pentafluorophenyl (PFP) ester groups. Part of the PFP groups was used for the attachment of the dithiolane moiety, which can efficiently bind to gold surfaces. The final copolymer contained 1.4 mol% of dithiolane groups and 4.5 mol% of PFP groups. The copolymer structure was confirmed by several analytical techniques, including NMR spectroscopy and size-exclusion chromatography. The kinetics of the PFP ester aminolysis and hydrolysis demonstrated significantly faster amidation compared to hydrolysis, which is essential for subsequent protein conjugation. Successful coating of gold surfaces with the polymer was confirmed by spectroscopic ellipsometry, showing a polymer brush thickness of 4.77 nm. Subsequent modification of the coated surfaces was achieved using bovine serum albumin as a model protein. This study introduces a novel reactive polymer linker for gold surface functionalization and offers a versatile polymer platform for various applications including biosensing and surface functionalization.

Mucin-mediated mucosal retention via end-terminal modified Pluronic F127-based hydrogel to increase drug accumulation in the lungs

Noninvasive lung drug delivery is critical for treating respiratory diseases. Pluronic-based copolymers have been used as multifunctional materials for medical and biological applications. However, the Pluronic F127-based hydrogel is rapidly degraded, adversely affecting the mechanical stability for prolonged drug release. Therefore, this study designed two thermosensitive copolymers by modifying the Pluronic F127 terminal groups with carboxyl (ADF127) or amine groups (EDF127) to improve the viscosity and storage modulus of drug formulations. β-alanine and ethylenediamine were conjugated at the terminal of Pluronic F127 using a two-step acetylation process, and the final copolymers were characterized using 1H nuclear magnetic resonance (1H NMR) and Fourier-transform infrared spectra. According to the 1H NMR spectra, Pluronic F127 was functionalized to form ADF127 and EDF127 with 85 % and 71 % functionalization degrees, respectively. Rheological studies revealed that the ADF127 (15 wt%) and EDF127 (15 wt%) viscosities increased from 1480 Pa.s (Pluronic F127) to 1700 Pa.s and 1800 Pa.s, respectively. Furthermore, the elastic modulus of ADF127 and EDF127 increased, compared with that of native Pluronic F127 with the addition of 5 % mucin, particularly for ADF127, thereby signifying the stronger adhesive nature of ADF127 and EDF127 with mucin. Additionally, ADF127 and EDF127 exhibited a decreased gelation temperature, decreasing from 33 °C (Pluronic F127 at 15 wt%) to 24 °C. Notably, the in vitro ADF127 and EDF127 drug release was prolonged (95 %; 48 h) by the hydrogel encapsulation of the liposome–Bdph combined with mucin, and the intermolecular hydrogen bonding between the mucin and the hydrogel increased the retention time and stiffness of the hydrogels. Furthermore, ADF127 and EDF127 incubated with NIH-3T3 cells exhibited biocompatibility within 2 mg/mL, compared with Pluronic F127. The nasal administration method was used to examine the biodistribution of the modified hydrogel carrying liposomes or exosomes with fluorescence using the IVIS system. Drug accumulation in the lungs decreased in the following order: ADF127 > EDF127 > liposomes or exosomes alone. These results indicated that the carboxyl group-modified Pluronic F127 enabled well-distributed drug accumulation in the lungs, which is beneficial for intranasal administration routes in treating diseases such as lung fibrosis.

An environmentally benign approach for the synthesis of low molar mass polybutenes from mixed C4 monomers using AlCl3/ionic-liquid initiating systems

In this research, four novel ionic liquid compounds supported on boehmite were synthesized and employed along with AlCl3 to catalyze polymerization of Raffinate 1 (composed of C4 based mixed monomers) to polybutene, for oils viscosity improver applications. To characterize the supported ionic liquids, FTIR, XRD, TGA, EDS, SEM and Elemental Mapping analyses were employed. Furthermore, 1HNMR,13C NMR and DEPT-135, GC-MS and GPC analyses were performed to assess the effect of designed ionic liquids on the characteristics of obtained polybutenes. Notably, the introduction of the supported ionic liquids led to polybutenes with comparable Mn and Ð to blank AlCl3 system, but with lower exo-olefins content, which makes the final copolymer more suitable for target application. 13C NMR and GC-MS analyses confirmed the high participation of isobutylene units in the resulted polybutenes, 75–85%. As an outstanding remark, the suggested AlCl3/ionic liquid initiating system benefits greener polymerization strategy by halving the dosage of hazardous AlCl3 compared to blank system using neat co-initiator.

Biobased and Compostable Multiblock Copolymer of Poly(l-lactic acid) Containing 2,5-Furandicarboxylic Acid for Sustainable Food Packaging: The Role of Parent Homopolymers in the Composting Kinetics and Mechanism.

In the last years, the exponential growth in the demand of petroleum-based plastic materials, besides the extreme exploitation of nonrenewable resources, lead to the mismanagement of their disposal and to serious ecological issues related to their dispersion in the environment. Among the possible practical solutions, the design of biobased and biodegradable polymers represents one of the most innovative challenges. In such a context, the eco-design of an aromatic-aliphatic multiblock copolymer based on poly(lactic acid) and containing 2,5-furandicarboxylic acid was carried out with the aim of improving the properties of poly(l-lactic acid) for sustainable packaging applications. The synthetic method followed a novel top-down approach, starting from industrial high-molecular-weight poly(l-lactic acid) (PLLA), which was reacted with 1,5-pentanediol to get hydroxyl-terminated PLLA and then chain-extended with hydroxyl-terminated poly(pentamethylene furanoate) (PPeF-OH). The final copolymer, called P(LLA50PeF50)-CE, was subjected to molecular, structural, and thermal characterization. Tensile and gas permeability tests were also carried out. According to the results obtained, PLLA thermal stability was improved, being the range of processing temperatures widened, and its stiffness and brittleness were decreased, making the new material suitable for the realization of films for flexible packaging. The oxygen permeability of PLLA was decreased by 40% and a similar improvement was measured also for carbon dioxide. P(LLA50PeF50)-CE was found to be completely biodegraded within 60 days of composting treatment. In terms of mechanism, the blocks of PPeF and PLLA were demonstrated to undergo surface erosion and bulk hydrolysis, respectively. In terms of kinetics, PPeF blocks degraded slower than PLLA ones.

Machine learning approach to polymer reaction engineering: Determining monomers reactivity ratios

In copolymerization, the monomers' reactivity ratios play an important role in shaping the final copolymer properties. Thus, the knowledge of reactivity ratio is essential to the polymer reaction engineering. However, the experimental methods of determining reactivity ratios are laborious and require many repetitions and testing at different compositions. Therefore, computational methods for determining the reactivity ratios based on the chemical structures of the reactants have attracted significant attention. Here, we demonstrate how machine learning enables the prediction of comonomers reactivity ratios based on the molecular structure of monomers. We combined multi-task learning, multi-inputs, and one of the state-of-the-art machine learning model – Graph Attention Network – to build a model capable of predicting reactivity ratios based on the monomers’ chemical structures. We found that the interpretable characteristics of Multi-Input-Multi-Output Graph Attention Network, along with its capability to learn chemical features facilitates the accurate prediction of the reactivity ratios. Such a predictive tool can be used in combination with macroscopic kinetic models to design new copolymers.

Synthesis of an original oxazoline based monomer containing a photosensitive azobenzene moiety and investigation of the behavior in solid state, in aqueous and vapor media of a photo and thermo-responsive polyoxazoline copolymer

In this paper, the synthesis of original thermo-sensitive polyoxazoline copolymers, also containing photo-sensitive azobenzene moieties is reported. An original oxazoline monomer containing an azobenzene moiety is first synthesized and then engaged in CROP copolymerization with 2-isopropyl-2-oxazoline. Copolymers with different ratio of azobenzene moieties are then fully characterized. The presence of azobenzene moieties clearly increases the glass transition temperature and decreases the cloud point temperature of the resulting copolymers due to their hydrophobicity. The presence of azobenzene moieties also influences the water uptake capacity of the copolymers. It is also demonstrated that the presence of a few azobenzene moieties increases the water sorption of the copolymer compared to a comparable polyoxazoline homopolymer. Finally, the trans-cis isomerization of the azobenzene moieties under UV radiation is used to tune different properties of the final copolymers such as the glass transition temperature in solid state, the cloud point temperature in aqueous media and the water uptake capacity in vapor state. Thus, thanks to this new photo-sensitive copolymer, it is possible to easily tune various properties with a simple light radiation which can be useful for various applications.

Synthesis and Characterization of Copolymers from Diallyldimethylammonium Hexafluorophosphate and Methyl Methacrylate

This work presents the radical copolymerization of diallyldimethylammonium hexafluorophosphate (DADMA(PF6)) and methyl methacrylate (MMA) with minimal added solvent. The ion exchange of DADMAC from chloride to hexafluorophosphate yielded a water-insoluble form of the ammonium monomer that is soluble in MMA. Copolymerizations were successfully carried out over a wide range of monomer feed ratios, which correlated strongly to the composition of the final copolymer and made it possible to incorporate large percentages of either monomer. Studies of copolymer composition at a range of reaction times indicated that the incorporation of MMA was slightly favored over that of DADMA(PF6). While all copolymers formed water-insoluble stand-alone films, qualitative examination of the films demonstrated that those with high incorporations of MMA had greater flexibility and optical clarity. A facile, reproducible polymerization method developed herein produced copolymers containing diallyldimethylammonium moieties that can be processed into water-insoluble polymer films for potential membrane applications.

Mass spectrometry insight into the electro-copolymerization mechanism of aniline with o-phenylenediamine

It has been a challenge to accurately characterize the chain growth mechanism during copolymerization. Herein, an electrochemistry-microtube-mass spectrometry (EC-mTube-MS) was developed for on-line monitoring of aniline (ANI) electro-copolymerized with o-phenylenediamine (oPD). Short-lived intermediates and co-oligomers belonging to polyANI-oPD were structural identified with tandem MS method for the first time. The free binding between ANI and oPD monomers determined the presence of more species for a given co-n-mer. Chain growth was found to compete with 2H+, 2e− intramolecular oxidation of co-oligomers, resulting in the units with quinone or phenazine structures. MS signals for polyANI and polyoPD were observed as well, indicating that the homopolymerization occurred simultaneously with the copolymerization, which may affect the formation efficiency even performance of the final copolymer. Investigations on the monomer feed ratio and solution pH provided data support for improving the copolymerization efficiency, and the recommended parameters are cANI: coPD ≥ 10:1 and pH = 7.

Anionic amphiphilic copolymers as potential agents for enhanced oil recovery

To develop “smart fluids” for enhanced oil recovery from reservoir rocks, comb-type amphiphilic copolymers were synthesized through free radical polymerization (FRP) of: (i) the hydrophilic, anionic monomer 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) that offer a hydrophilic character to the final copolymers; (ii) the weakly acidic hydrophilic monomer acrylic acid (AA); (iii) the hydrophobic monomer dodecyl methacrylate (DMA). The polymers were characterized by Proton Nuclear Magnetic Resonance (1H NMR), Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), fluorescence probing, Dynamic Light Scattering (DLS) and electrophoresis. Stable polymer solutions were prepared without and with the presence of salts (NaCl, CaCl2, MgSO4). The dynamic air/water surface and oil/water interfacial tensions were measured by the pendant drop method, and their steady-state values were estimated with fitting to asymptotic relations predicting the long-time behavior. Moreover, the wettability of water/air and water/oil to glass or poly(methyl methacrylate) (PMMA) surface was quantified by measuring the contact angles. Oil-in-water Pickering emulsions were prepared by mixing n-dodecane with polymer solutions and their stability was evaluated macroscopically with optical inspection, and microscopically by measuring the oil drop size distribution and shear viscosity. Polymer solutions and Pickering emulsions were tested as agents for the displacement of the residual n-dodecane from a glass-etched pore network. The long-lasting retention of polymer solution in the pore network makes the solid surface more hydrophilic, facilitating the fission of oil ganglia into smaller ones which are mobilized easier, resulting in a final EOR efficiency between 10% and 18%. When using an emulsion as displacing fluid, the viscosity ratio and capillary number increase by orders of magnitude, the viscous forces prevail against the capillary ones, and the growth pattern becomes a frontal drive leading to a high EOR efficiency of ∼94%.

Fully tuneable ethylene-propylene elastomers using a supported permethylindenyl-phenoxy (PHENI*) catalyst.

Using a highly active supported permethylindenyl-phenoxy (PHENI*) titanium catalyst, high molecular weight ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) elastomers are prepared using slurry-phase catalysis. Final copolymer composition was found to reflect the monomer feed ratio in a linear fashion, to access a continuum of material properties with a single catalyst. Post-polymerisation crosslinking of EPDM was also demonstrated in a model sulfur vulcanisation system.

Unexpected luminescence of non-conjugated biomass-based polymers: new approach in photothermal imaging.

Population growth, depletion of world resources and persistent toxic chemical production underline the need to seek new smart materials from inexpensive, biodegradable, and renewable feedstocks. Hence, "metal-free" ring-opening copolymerization to convert biomass carvone-based monomers into non-conventional luminescent biopolymers is considered a sustainable approach to achieve these goals. The non-conventional emission was studied in terms of steady-state and time-resolved spectroscopy in order to unravel the structure-properties for different carvone-based copolymers. The results highlighted the importance of the final copolymer folding structure as well as its environment in luminescent behavior (cluster-triggered emission). In all cases, their luminescent behavior is sensitive to small temperature fluctuations (where the minimum detected temperature is Tm ∼ 2 °C and relative sensitivity is Sr ∼ 6% °C) even at the microscopic scale, which endows these materials a great potential as thermosensitive smart polymers for photothermal imaging.

On the Precipitation Copolymerization of 1‐Octene and Glycidyl Methacrylate in Supercritical Carbon Dioxide

The free radical precipitation copolymerization of the polar monomer glycidyl methacrylate (GMA) and the non-polar monomer 1-octene (Oct) in supercritical carbon dioxide (sc-CO2) is reported under different conditions of pressure and temperature. According to 1H NMR studies, in the obtained statistical copolymers (GMA-stat-Oct) the molar fraction of the olefin (FOct) increases when the pressure and temperature of the reaction increased from the reference values T = 125 °C and P = 34 bar. In particular, when the initial molar fraction of Oct (fOct) is 0.83, the molar fraction of this monomer in the final copolymer reaches a maximum value of 0.22 at 124 bar and T = 155 °C. On the other hand, for fOct = 0.89, it was obtained that FOct = 0.25 at 124 bar and T = 155 °C. Copolymers obtained were characterized by NMR, SEM and SEC techniques. Finally, two copolymers were selected to demonstrate the feasibility of modifying the GMA moiety in order to introduce OH polar groups giving rise to Oct-stat-glycerol methacrylate copolymers. This article is protected by copyright. All rights reserved

Statistical analysis of parameters involved in the synthesis of polar copolymers using a nickel (II) α-diimine complex

In this article, the copolymerization of 1-hexene and butyl acrylate in the presence of a nickel(II) complex (α-diimine nickel (II) catalyst consisting of bulky 2,6-di (isopropyl) phenyl groups as imine substituents and a planar acenaphthyl backbone) as catalyst and methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC) as activators has been investigated. The main aim of this article is to provide a deep investigation of the effect of the type of activator, polymerization time, temperature, and comonomer content in the reactor feed on activity, comonomer incorporation, and molecular weight of resulting copolymers. Then, a nonlinear regression method was used to fit analytical results to a numeric model, which is very useful for predicting the properties of the final copolymers only by having the polymerization parameters.

Controllable Polymerization of N -Substituted β-Alanine N -Thiocarboxyanhydrides for Convenient Synthesis of Functional Poly(β-peptoid)s

Controllable Polymerization of <i>N</i> -Substituted β-Alanine <i>N</i> -Thiocarboxyanhydrides for Convenient Synthesis of Functional Poly(β-peptoid)s

Controlled Process of Radiation-Induced Grafting by Chemical Vapour Deposition for the Synthesis of Metal Adsorbent

Combination of high energy radiation and chemical vapour deposition in the grafting process for the synthesis of metal adsorbent was investigated. Radiation-induced grafting of glycidyl methacrylate onto kenaf fiber was performed in vapour phase to develop adsorbent for removal of aluminum from aqueous solution. Morphological changes of cross-section kenaf fiber was observed via scanning electron microscope and the thickness of co-monomer in the final graft co-polymer was determined. The comparison in cross-section morphology between ungrafted kenaf fibers and grafted kenaf fiber shows approximately 3.88 [μm] thick of additional grafted layer. The functionalization of the grafted fiber using imidazole was calculated grametrically and verified by elemental analysis. Imidazole has proven to be effective on the adsorption of aluminum ion. It was found that the adsorbent could remove more than 99% aluminum with the highest adsorption capacity of 4.93 [mg/g] at pH 4 and 60 minutes reaction time.

High‐performance blended membranes based on poly(arylene ether sulfone) and sulfonated poly(styrene‐isobutylene‐styrene) for direct methanol fuel cell applications

AbstractIn this study, two series of poly(arylene ether sulfone)s (PAES) with hydrophobic blocks made of 4,4′‐dihydroxyphenyl (BP) and 2,2‐bis(4‐hydroxyphenyl) propane (BPA) were synthesized. The copolymers were prepared by a coupling reaction between decafluorobiphenyl (DFBP) end‐capped nonsulfonated block (PAES A or B) and sulfonated block (SPAES B). The reactive behavior of DFBP facilitates the low‐temperature coupling reaction (below 105°C). The final copolymers were blended at distinct weight percent ratios (0, 20, 30, and 40) with poly(styrene‐b‐isobutylene‐b‐styrene) (SIBS) at a sulfonation level of 88% to obtain strong and flexible membranes. Morphological, thermal stability, and conduction properties of the resulting membranes were measured and reported here. Results suggest that phase segregation between hydrophobic and hydrophilic domains occurs below 1 meq. g−1 ion exchange capacity. These membranes have low water absorption and high thermal stability. Incorporating SIBS 88 into the blend added elastomeric behavior enhancing transport properties and additional ionic domains, achieving proton conductivities of 0.21 S cm−1 for BPA‐based membranes at 50°C (40% SIBS 88). The selectivity of the studied membranes surpasses Nafion® 117, making them strong candidates for proton exchange membranes in direct methanol fuel cell applications.

Controlled block-polymerization of styrene, divinylbenzene and ethylene oxide. Intermolecular cross-linking towards well-defined miktoarm copolymer stars

• Synthesis of well-defined miktoarm copolymer stars. • Control over the molecular weight and composition for both arm species. • Controlled polymerization of poly(divinylbenzene). • Intermolecular cross-linking of linear triblock terpolymers. A novel approach for the synthesis of miktoarm copolymer stars with divinylbenzene cross-linked core, via anionic polymerization is reported. This synthetic route gives access to polymers, characterized by low dispersity values and improved structural homogeneity for both arm species. Specifically, miktoarm copolymer stars of A n B n type, with cross-linked divinylbenzene (DVB) core and arms of polystyrene (PS) and poly(ethylene oxide) (PEO), are synthesized via anionic polymerization and sequential monomer addition, employing high vacuum techniques. Analytically, the first step involves the synthesis of a triblock terpolymer PS- b -PDVB- b -PEO. Then, in the presence of a free radical initiator the pending vinyl groups of the middle DVB block cross-link intermolecularly, leading to the final miktoarm copolymer star. The novelty of the proposed synthetic route, lies in the potassium alkoxide co -initiator, which is responsible for the controlled polymerization of both DVB and EO in one pot, without the need for end group modification between the two steps. Concerning the final polymer, there are numerous benefits advancing from this synthetic protocol, such as the control of the molecular characteristics of both arms, as well as the easily confirmed structural integrity of the precursor triblock which is inherited to the resulting miktoarm star. For comparison reasons, another batch of (PS)(PEO) miktoarm copolymers was synthesized, following the “in-out” synthetic route. For this reason, styrene was polymerized using s -BuLi, which is used as macroinitiator for the polymerization/cross-linking of DVB, resulting PS star with DVB cross-linked core. With the addition of EO, in the presence of p4 t -Bu phosphazene base, PEO arms are polymerized, initiating from the core’s active cites outwards.

TEOS-PDMS-Calcium Oxalate Hydrophobic Nanocomposite for Protection and Stone Consolidation

A treatment for both protection and consolidation, was synthesized in a simplified procedure through the sol gel process. Synthesized nano-calcium oxalate (CaOx) was incorporated into tetraethoxysilane (TEOS) and polydimethylsiloxane (PDMS), providing a hybrid hydrophobic consolidant nanocomposite. Oxalic acid was selected due to its ability to catalyse the hydrolysis of TEOS, as a drying control agent, but also because of its contribution at the formation of the calcium oxalate in reaction with calcium hydroxide. CaOx, incorporated into the silica matrix of the final copolymer, exhibits interfacial compatibility with the stone substrate and simultaneously strengthens the treated surface, since CaOx appears to be more stable than calcium carbonate. The hydrolysis of TEOS, as well as the formation of CaOx was evaluated through thermogravimetric analysis (TG/DTA). The nanocomposite consists of particles with approximately 7–700 nm in size range, as shown in TEM images. The consolidation, in combination with the hydrophobicity of surface resulted in an increase of the resistance to decay. Mechanical properties were enhanced as evaluated by ultrasonic pulse velocity on treated and untreated surfaces. Furthermore, water contact angle, as well as water absorption by capillarity test, showed improved water repellency of treated stones. Finally, this treatment doesn’t alter the aesthetic surface parameters, a fact that is essential in cultural heritage conservation, while the consolidant remains intact under UV and moisture exposure.

Tricyclic or Pentacyclic D Units: Design of D-π-A-Type Copolymers for High VOC Organic Photovoltaic Cells.

Although there are several electron-donating (D) units, only the classic benzo[1,2-b:4,5-b']dithiophenes (BDT) unit was utilized to develop D-π-A-type copolymers for high-voltage organic photovoltaic (OPV) cells. Hence, in this work, we chose two tricyclic D units, BDT and benzo[1,2-b:4,5-b']difurans (BDF), together with one pentacyclic ring, dithieno[2,3-d;2',3'-d']benzo[1,2-b;4,5-b']dithiophenes (DTBDT), to comprehensively study the effect of different D units on the optoelectronic properties and photovoltaic performance. By copolymerized with the benzo[1,2,3]triazole (BTA) electron-accepting unit, the final copolymers J52-Cl, F11, and PE52 were combined with a nonfullerene acceptor (NFA) F-BTA3 according to the "Same-A-Strategy." As we preconceived, all the three single-junction OPV cells can obtain high open-circuit voltage (VOC) over 1.10 V. Although the tricyclic D unit of BDF exhibits a slightly lower VOC of 1.12 V because of its mildly larger energy loss of 0.698 eV, its higher carrier mobilities and exciton dissociation efficiency strikingly boost the short-circuit current (JSC) and fill factor, which contribute to a comparable PCE of 10.04% with J52-Cl (10.10%). However, the DTBDT-based polymer PE52 shows the worst performance with a PCE of 6.78% and a VOC of 1.14 V, owing to the higher bimolecular recombination and disordered molecular stacking. Our results indicate that tricyclic D units should be a better choice for constructing D-π-A-type polymers for high-voltage photovoltaic materials than the pentacyclic analogues.