Effect of Mixed Dispersants on Suppression of the Gel Effect during Aqueous Adiabatic Terpolymerization of AM,NaAA,and DMC

Gelation adversely affects the aqueous adiabatic terpolymerization of acrylamide (AM), sodium acrylate (NaAA),and 2-methacryloyloxyethyl trimethylammonium chloride (DMC). Here, the mixed dispersants sorbitan monooleate (Span80) and polyoxyethylene sorbitan monooleate (Tween 80) were introduced to the terpolymerization system in an attemptto mitigate the gel effect. This enabled the preparation of high-performance amphoteric polyacrylamides, which werecharacterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. The influences of the dispersanttype and content as well as the hydrophilic-lipophilic balance (HLB) on the gel effect were examined, and the mechanismunderlying the suppression of the gel effect was considered. The obtained results indicated that the gel effect can beeffectively mitigated using an aqueous adiabatic terpolymerization system containing mixed Span 80/Tween 80 dispersantsat various contents. In particular, mixed dispersant contents of 0.6%–0.8% with HLB values of 5.0–6.0 afforded the optimalperformance (e.g., high viscosity, fast aqueous dissolution time, and the like).

Optimizing polymer aggregation and blend morphology for boosting the photovoltaic performance of polymer solar cells via a random terpolymerization strategy

Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.

^(13)C NMR Study of Ethylene/propylene/octene-1 Terpolymers Synthesized with TiCl_4/MgCl_2/ i -Bu_3Al as the Catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the 13 C NMR spectra of the ethylene/propylene and ethylene/octene 1 copolymers. Using the parameters derived above and the DEPT technique, we then entirely assigned the 13 C NMR spectra of the ethylene/propylene/octene 1 terpolymers synthesized in the presence of the same heterogeneous supported Ziegler Natta catalyst, TiCl 4/MgCl 2/ i Bu 3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene 1 terpolymers.

Synthesis and Characterization of Styrene-Maleic Anhydride-Butyl Acrylate Terpolymer

A novel surface modifying agent and internal compatilizer of inorganic and macromolecule composite materials,P(St/MAH/BA)terpolymer,was synthesized in butanone by solution polymerization method using styrene(St),maleic anhydride(MAH),and butyl acrylate(BA)as monomers and azobisisobutyronitrile(AIBN)as an initiator.Some affecting factors on terpolymers yields such as polymerization time,reaction temperature,solvent volume,initiator content,and reactants ratios were studied.Furthermore,the structure and thermal properties of terpolymers were primarily characterized and determined by Fourier Transform Infrared Spectroscopy(FTIR),nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),and gel permeation chromatography(GPC).The results indicate that the terpolymers are random polymers and the yields are low,but the thermal decomposed temperature of terpolymers P(St/MAH/BA)is around 220 ℃ and the average molecular weights(Mw)achieve 1.189×105 g·mol-1.

Synthesis, Kinetics and Mechanism of Terpolymerization of Styrene, Vinyl Acetate with Acrylonitrile Initiated by P-Nitrobenzyl Triphenyl Phosphonium Ylide

Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one electron-accepting monomer, i.e. acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in dioxane as diluent at 65°C for 150 min has been studied. The kinetic expression is Rpα[I]0.8[Sty] 1.2[VA] 1.4 [AN]1.2. The terpolymer composition was determined by the Kelen-Tüdos method. The values of reactivity ratios using r1 (Sty + VA) = 0.1 and r2 (AN) = 0.005. The overall activation energy is 46 kJ●mol●L–1. The formation of terpolymer is confirmed by the FTIR spectra showing bands at 3030 cm–1, 1598 cm–1, and 2362 cm–1, confirming the presence of phenyl, acetoxy and nitrile group respectively. The terpolymer has been characterized by 1H-Nuclear Magnetic Resonance, 13C-Nuclear Magnetic Resonance. The Differential Scanning Calorimetric curve shows the Tg of the polymer as 149.5°C. A scanning electron microscope confirms the polymer to be phosphorus free. Electron.Spin.Resonance spectra confirms phenyl radical responsible for initiation.

SYNTHESIS OF FUNCTIONAL UNSATURATED POLYESTER BY USING RARE EARTH CATALYSTS 2.TERPOLYMERIZATION OF EPICHLOROHYDRINMALEIC ANHYDRIDE-CARBON DIOXIDE WITH Y(P_(204))_3-Al(i-Bu)_3

Teroolymerization of enichlorohydrin（ECH）-maleic anhydride（MAn）-carbon dioxide（CO;） was carried out by using Y(P;);-Al（i-Bu）;as catalyst for the first time.The terpolymersobtained were characterized by IR and;H-NMR.It was foundthat the composition of the teroolymer was influenced by theaddition mode,initial monomer charge ratio,etc.

Scavenging Properties of the Polyamine Functionalized Gels Based on the Glycidyl Methacrylate Terpolymers

Scavenging abilities of the ethylenediamine, diethylenetriamine and tris(2-aminoethyl)amine functionalized resins derived from the low cross-linked glycidyl methacrylate-styrene gels in relation to the selected transition metal ions and organic (acid chlorides) electrophiles were explored. The synergetic effects of the solvents were found for the metal ion uptake. In this case a pair of solvents capable simultaneously to swell the hydrophobic core of the resins and interact with the polar amine groups turned out to be a more effective medium for activation of the nucleophilic functionalities of the resins. The resin with ethylenediamine moieties proved to be effective in scavenging acyl chlorides from methylene chloride as well. However, it did not provide complete removing sulphonyl chlorides from the solutions. These organic electrophiles were removed effectively by the resins bearing tris(2-aminoethyl)amine functionalities.

Random Terpolymer Based on Simple Siloxane-functionalized Thiophene Unit Enabling High-performance Non-fullerene Organic Solar Cells

Incorporation of siloxane-functionalized units into polymers backbone has proven to be an efficient strategy to improve photovoltaic performance. In this work, a low-cost siloxane-containing unit was developed to construct a series of terpolymers, and the effects of siloxane on the polymer performance were systematically studied. Different contents of thiophene containing siloxane-functionalized side chain were introduced into PM6 to obtain a series of polymers(PM6, PM6-SiO-10, PM6-SiO-20 and PM6-SiO-30). The siloxane-functionalized side chains in polymers have only a slight effect on the absorption behavior and frontier molecular orbitals. However, when the siloxane content increased, the terpolymers' aggregation property decreased and the temperature-dependency increased, leading to improved donor-acceptor compatibility. The power conversion efficiency(PCE) based on PM6:Y6, PM6-SiO-20:Y6 and PM6-SiO-30:Y6 devices was 15.64%, 16.03% and 15.82%, respectively. In comparison, the active layer based on PM6-SiO-10:Y6 exhibits the most appropriate phase separation morphology, resulting in effective exciton dissociation, more balanced hole-electron transport and less recombination. Consequently, the highest PCE of 16.69% with an outstanding shortcircuit current density of 26.96 mA·cm^(-2) was obtained, which are one of the highest values for siloxane-functionalized polymer-based devices.This work demonstrates that finely controlling the content of siloxane-functionalized thiophene is beneficial for obtaining high-performance terpolymer donors and provides a novel and low-cost method to improve photovoltaic performance.

Effect of poly(4-tert-butylstyrene)block length on the microphase structure of poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)triblock terpolymers

A series of linear poly(ethylene oxide)-b-poly(4-vinylbenzyl chloride)-b-poly(4-tert-butylstyrene)(PEO_(113)-b-PVBC_(130)-b-Pt BS_(x)or E_(113)V_(130)T_(x))triblock terpolymers with various lengths x(=20,33,66,104,215)of Pt BS block were synthesized via a two-step reversible addition-fragmentation chain transfer(RAFT)polymerization.The E_(113)V_(130)T_(x)triblock terpolymers were non-crystalline because the PVBC and Pt BS blocks strongly hindered the crystallization of PEO block.The effects of Pt BS block length x on the phase structures of E_(113)V_(130)T_(x)triblock terpolymers were investigated by combined techniques of small-angle X-ray scattering(SAXS)and transmission electron microscopy(TEM).It was found that with increasing x from20 to 215,the phase structure of E_(113)V_(130)T_(x)triblock terpolymers became more ordered and changed from disordered structure,hexagonally-packed cylinder(HEX),hexagonally perforated layer(HPL),to lamellar(LAM)phase structures.Temperature-variable SAXS measurements showed that the HEX,HPL and LAM phase structures obtained for E_(113)V_(130)T_(66),E_(113)V_(130)T_(104)and E_(113)V_(130)T_(215)by thermal annealing,respectively,were thermodynamically stable in the temperature range of 30-170℃.

Highly Efficient Random Terpolymers for Photovoltaic Applications with Enhanced Absorption and Molecular Aggregation

A series of copolymers, based on benzo[1,2-b：4,5-b＇]dithiophene （BDT） as the electron donor and 2,1,3- benzothiadiazole （BT）/diketopyrrolo[3,4-c]pyrrole （DPP） as the electron acceptors, were synthesized for highly efficient polymer solar cells. By changing the BT/DPP ratio in the conjugated backbone, the absorption, energy levels, molecular aggregation and carrier mobility could be finely tuned. With increased DPP content, the absorption range was extended to the longer wavelength region with narrower bandgaps. The highest occupied molecular orbital （HOMO） levels were also raised up and the molecular aggregation was enhanced. The balance of these factors would afford a remarkable device performance enhancement. Polymer P3 with BT：DPP = 0.7：0.3 （molar ratio） exhibited the highest power conversion efficiency （PCE） of 9.01%, with open circuit voltage （Voc） = 0.73 V, short current density （Jsc） = 18.45 mA.cm-2, and fill factor （FF） - 66.9%. The PCE value was improved by 48.7% compared to P1 and by 117.6% compared to P7, respectively, indicating a great potential in photovoltaic application.

Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells

A series of random terpolymers P2-P5 were designed and synthesized by randomly embedding 5 mol%, 10 mol%, 15 mol% and 25 mol% feed ratios of low cost 2,2-bithiophene as the third monomer to the famous donor-acceptor （D-A） type copolymer PTBT-Th （P1）. All polymers showed similar molecular weight with number-average molecular weight （Mn） and weight-average molecular weight （Mw） in the range of （59-74） and （93-114） kg·mol-1, respectively, to ensure a fair comparison on the structure-property relationships. Compared with the control copolymer PTBT-Th, the random terpolymers exhibited enhanced absorption intensity in a wide range from 400 nm to 650 nm in both solution and film as well as in polymer/PC71BM blends. From grazing incident wide-angle X-ray diffraction （GIWAXS）, compared with the regularly alternated copolymer PTB7-Th, the random terpolymers demonstrated mild structural disorder with reduced （100） lamellar stacking and slightly weakened （010） π-π stacking for the polymers as well as slightly reduced PC71BM aggregation in polymer/PC71BM blends. However, the measured hole mobility for terpolymers （（1.20-3.73） × 10 -4 cm2·V-1·s-1） was evaluated to be comparable or even higher than 1.35 × 10 -4 cm2·V-1 ·s-1 of the alternative copolymer. Enhanced average power conversion efficiency （PCE） from 7.35% to 8.11% and 7.79% to 8.37% was observed in both conventional and inverted device architectures from copolymer P1 to terpolymers P4, while further increasing the 2,2-bithiophene feed ratio decreased the PCE.

Synthesis of Polycarbonate Block Terpolymers Using Robust Cobalt Catalyst Systems

This contribution reports an efficient approach for preparing polycarbonate block terpolymers by immortal stepwise copolymerization of CO2 with different epoxides in the presence of enol chain transfer,mediated by robust cobalt catalyst systems consisting of the fluorine substituted salen Co(Ⅲ)NO3 or biphenol-linker bimetallic Co(Ⅲ)complex in conjunction with an ionic cocatalyst,PPNX(PPN=bis(triphenylphosphine)iminium,X=NO3–or 2,4-dinitrophenoxide).Various polycarbonate block terpolymers were obtained in perfectly unimodal distribution of their molecular weights with narrow polydispersity.They all possessed only one broad glass transition temperature,which could be adjusted by altering the length of different polycarbonate segments.

Alternating Terpolymers Based on Tunable Bi-donors with Manipulating Energy Levels and Molecular Geometry

Three novel regular acceptor-donorl-acceptor-donor2（A-D1-A-D2） terpolymers were prepared via em-bedding a second donor（D2） unit into the traditional D-A backbone to manipulate the energy levels and moleculargeometry with no complex synthesis or solubility loss. In these A-D1-A-D2 terpolymers, benzodithiophene（BDT, D1）and diketopyrrolopyrrole（DPP, A） were selected as the basic skeleton, and the dithienopyrrole（DTPy）, carbazole（CZ）and fluorine（FL） units with different electron donating ability were chosen as the second donor trait（D2）. The HOMOenergy levels can be effectively modulated by only varying D2 unit because of the push-pull interaction between do-nor and acceptor units. Versus the D-A bipolymer PDPP-BDT, incorporation of the D2 unit into the copolymers candistinctly lower the highest occupied molecular orbital（HOMO） levels to -5.47 eV for PDDPP-BDT-DTPy, -5.38 eVfor PDDPP-BDT-CZ and -5.23 eV for PDDPP-BDT-FL, which shows the strong dependence on electron-donatingability. Density functional theory（DFT） simulation and X-ray diffraction（XRD） measurements also reveal the effectof the D2 units on the molecular geometry of the terpolymers and their molecular packing. Notably, aPDDPP-BDT-DTPy combined with a thiophene ring and forked tail pendant away from the backbone had less back-bone torsion and more compact packing than the other two counterparts. These results demonstrate that embedding asecond donor（D2） unit into the backbone to construct an A-D1-A-D2 structure can be an effective and direct strategyto manipulate the energy levels and molecular geometry and develop organic semiconducting materials.

One-Pot Terpolymerization of CO2, Propylene Oxide and Lac- tide Using Rare-earth Ternary Catalyst

A convenient one-pot terpolymerization of CO2, propylene oxide （PO）, and L-lactide （L-LA） in short polymerization time （10 h or shorter） to afford poly（propylene carbonate-lactide） with excellent mechanical property and thermal stability using Y（CCl3COO）3-ZnEtz-glycerin rare-earth ternary catalyst is reported. The yield of the co- polymerization was between 69.7 and 111.7 g/（g Zn）, corresponding to L-LA/PO molar feed ratio varying from 0 to 0.1, and the number average molecular weight was between 5.5×10^4 and 11.9 × 10^4. The L-LA content in the ter- polymer increased from 1.1% to 34.7% when L-LA/PO molar feed ratio changed from 0.01 to 0.1. Introducing L-LA as the third comonomer could significantly improve the mechanical strength and thermal stability of PPC. For the terpolymer obtained from L-LA/PO molar feed ratio of 1：50, the elongation at break reached 40.5%, which is 3 times of that of pure PPC, and the thermal decomposition temperature increased by 32℃ compared with pure PPC.

Controlled Random Terpolymerization of β-Propiolactone,Epoxides,and CO_(2) via Regioselective Lactone Ring Opening

The random ring-opening terpolymerization of CO_(2),epoxides,and lactones remains challenging,mainly because CO_(2)/epoxide copolymerization and lactone ring-opening polymerization typically proceed at very different rates.Herein,we report the preparation of novel statistical terpolymers with random distributions of carbonate and ester units(up to 40%junction units)via the one-pot reaction ofβ-propiolactone(BPL),epoxides,and CO_(2) under mild conditions using a binary catalyst system consisting of SalcyCo(III)OTs(Salcy=N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane;OTs=p-toluenesulfonate)and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.Since this catalytic system could yield similar reaction rates for alternating epoxide/CO_(2) copolymerization and BPL polymerization,terpolymers with nearly identical compositions were produced at various time points.CO_(2) played an important role in preventing intra-and/or intermolecular transesterification side reactions.Thereby,the terpolymerization proceeded in a controlled manner,allowing for the fine-tuning of molecular weight and composition.Two-dimensional nuclear magnetic resonance(NMR)analysis and density functional theory(DFT)calculations suggested that the nucleophilic attack of the coordinated BPL by carbonate ions cleaved the alkyl C–O bond predominantly rather than the acyl C(=O)–O bond,typically observable during the nucleophilic ring-opening polymerization of BPL.These findings have opened up a new avenue for preparing a broad family of biodegradable polymers with adjustable properties.

New insight into surface properties of LB film of an amphiphilic terpolymer

Amphiphilic terpolymer（TPR） exhibits good film-forming behavior on pure water observed by means ofπ-A isotherms.To gain insight into physical properties of TPR,the films have been deposited on silicon substrates at different surface pressure by Langmuir-Blodgett（LB） technique.It was found that the increase in peak intensities of stretching mode was due to orderly packing of the films.The contact angles increased with increasing surface pressure,indicating an increase in hydrophobicity due to dense packing of chains of TPR.The cyclic voltammetric measurements indicated that TPR showed good current shielding effect for electron-transfer.In a word,LB films of TPR can produce a variety of structures with varied topography,enabling us to control not only the functionality of the surface,but also the interfacial transport characteristics.

Amphiphilic ABC Triblock Terpolymer Templating for Mesoporous Silica

Self-assembled triblock terpolymers have attracted intense attention in recent years because of their abundant variety of assembly mesostructure. We reported the synthesis of mesoporous silica materials with the am- phiphilic ABC triblock terpolymer polyethylene-poly（ethylene oxide）-polycaprolactone（PE-PEO-PCL） as a template and tetraethoxysilane（TEOS） as a silica source. Increasing the hydrophilic head group（PEO） led to the decrease of packing parameter g, which gave rise to the mesophase transformation from a cylindrical two-dimensional hexagonal P6mm structure to a cage-type face centered cubic closed-packing mesostructure. This new templating route provided a new insight into the template factor governed inorganic-organic self-assembly mesophases.

二氧化碳/环氧丙烷/γ-丁内酯的三元共聚合和表征

通过二氧化碳(CO2 )、环氧丙烷(PO)与γ- 丁内酯(GBL)的三元开环共聚反应,得到一种三元共聚物,脂肪族聚碳酸酯(PPCG) .对PPCG的结构进行了FTIR、1 H- NMR及1 3C -NMR表征,表明GBL被开环嵌入PO CO2分子链中,使得共聚物中引入了易水解的羧酸酯单元.对PPCG的热性能、降解性能进行了测试.结果表明,在一定范围内,随着γ丁内酯单元的增加,特性粘数降低,PPCG的玻璃化转变温度升高,材料降解性增强;不同的聚合反应时间对PPCG的特性粘数和和玻璃化转变温度也有着明显的影响.

二氧化碳/环氧丙烷/邻苯二甲酸酐三元共聚物的合成及性能

利用负载戊二酸锌(s-ZnGA)催化二氧化碳(CO2)、环氧丙烷(PO)和邻苯二甲酸酐(PA)三元共聚反应,得到一种新型的三元聚合物聚碳酸亚丙酯苯酐(PPCPA)。用核磁共振谱(1H-NMR和13C-NMR)表征了聚合物结构。研究了PPCPA的热性能和力学性能,结果表明,PA的引入可以提高聚碳酸亚丙酯(PPC)的热稳定性能和力学性能,随着PA含量的增加,PPCPA的热分解温度显著升高,其玻璃化温度(Tg)和拉伸强度先增高后降低,主要是由于聚合物中聚醚含量增加所致。

离子液体中AM／AMPS／N8AM三元共聚物的合成及溶液性能

The tercopolymer AM-AMPS-N8AM was prepared through radical polymerization with 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquids as the reaction medium of polymerization,benzoperoxide/N,N-dimethylaniline(BPO/DMA)redox system as the initiator,acrylamide(AM)and 2-acrylamido-2-methylpropane sulfonic acid(AMPS)as the hydrophilic monomer,N-octylacrylamide(N8AM)as the hydraphobic monomer.The structure of polymer was identified by 1H NMR,13C NMR and element analysis.The apparent viscosity of the terpolymer aqueous solution is measured,and the result shows that the terpolymer synthesized in ionic liquids has an excellent tackifying ability.When the mass concentration of solution is 1.2 g/L,the apparent viscosity can reach 220.1 mPa·s,when the temperature changes from 45 ℃ to 90 ℃,the viscosity remaining rate is 65% and when the shear rate increases to 24.48 s-1,the viscosity remaining rate is 43.5%.It is shown that the tercopolymer solution has better temperature tolerance and shearing resistance.