Synthesis of Acrylate Microemulsion Modified by Alkoxy Silane

An acrylate emulsion was modified by adding vinyltriisopropoxy silane （trade name C-1706）. By adding the multiple emulsifier which consists of an anionic emulsifier, sodium dodecyl benzene sulfonate （SDBS） and nonionic emulsifier, octyl phenolic divinyl oxide （OP-10）, the acrylosilane microemulsion was synthesized by seeded emulsion polymerization. The influential factors including the kind and the adding amount of emulsifiers and the monomer variety of alkoxy silane and the added methods which influence on the properties of the microemulsion were investigated. It is found that SDBS and OP-10 as multiple emulsifiers with mass ratio of 1：1 and the adding amount of 2.5%-3.5% can act on co-effect for emulsion polymerization. The C-1706 possesses bulky isopropoxy substituent that can reduce hydrolysis reactivity during the polymerization process, so as to not only make the process smoothly but also advance the store stability of the emulsion. Moreover, the latter-addition mode of C-1706 can restrain its hydrolysis activity and polycondensation reaction during the polymerization process of the emulsion. The structure, the film cross section, the particle size and its distribution of the microemulsion were analyzed by the Fourier Transform Infrared Ray Spectrum （FTIR）, Scanning Electron Microscopy （SEM） and a particle size analyzer, respectively. The results show that the particle diameter of the modified microemulsion can be controlled between 50 and 70 nm and its film hardness is 7.3. Only adding 1.5% of C-1706 into the system of emulsion polymerization can apparently improve the weathering resistance of the microemulsion, which undergo degradation with chromatism（△E） is 1.6 after 3 600 hours of QUV-aging.

AN IMPROVED METHOD FOR PREPARING 2—ALKOXY—5—FLUORO—3H—4—PYRIMIDONE~△

In this paper, we report an improved method for preparing 2--alkoxy 5 fluoro--3H --4--pyrimidone from 2--chloro--5--fluoro--3H--4--pyrimidone and sodium alkoxide under normal pressure at reflux temperature. Some new compounds were synthesized in higher yield by this method.

MOLECULAR POLARIZATION INDUCTION IN CONCERTED MECHANISM OF ALKOXY MIGRATION

The rearrangement of α-substituted phenyl-α, α′-dimethoxypropanones (R1) was recently proved to he an [1, 3] siqmatropic migration of methoxy group by study of LFER, solvent effect, crossover experiment, and by other means. The rearrangement catalysed by trace of totuenesulfonic acid gave a negligible value of the Hammett reaction constant. Further experimental results show that the electronic effect of substituent on the aromatic ring for the rearrangement in neutral medium is much greater (Table 1). We propose sigmatropic migration

Introducing alkoxy groups as outer side chains and substituents ofπ-bridges obtains high-performance medium-bandgap polymerized small molecule acceptors

The medium-bandgap polymerized small molecule acceptors(PSMAs)have broad application scenarios.However,the effort in the molecular design of the high-performance medium-bandgap PSMAs is limited.In this article,we introduce alkoxy groups as outer side chains and as substituents of the thiopheneπ-bridges of the high-performance PSMA PY-IT to synthesize a mediumbandgap PSMA PO-TO.Due to the fact that the non-covalent interaction between the alkoxy groups and the terminal groups of the small molecule acceptor(SMA)unit can weaken the intramolecular charge transfer(ICT)effect,the bandgap of PO-TO is enlarged and its absorption is blue-shifted compared with PY-IT,while the absorbance of PO-TO solution and film is enhanced significantly compared with that of PY-IT.When blended PO-TO with the polymer donor PBQx-TF,the corresponding all-polymer solar cells(all-PSCs)exhibit an open-circuit voltage(V_(oc))exceeding 1.04 V with a power conversion efficiency(PCE)of 13.75%.Furthermore,PO-TO was used as the third component to fabricate ternary all-PSCs with PBQx-TF as the polymer donor and PY-IT as the main polymer acceptor,and the ternary all-PSCs based on PBQx-TF:PY-IT:PO-TO(1:1:0.2,w/w/w)demonstrated a high PCE of 17.71%with simultaneously improved V_(oc)of 0.940 V,short-circuit current density(J_(sc))of 24.60 m A cm^(-2)and fill factor(FF)of76.81%.In comparison,the binary all-PSCs based on PBQx-TF:PY-IT showed a PCE of 16.77%.This result indicates that introducing alkoxy groups is a promising strategy for synthesizing high-performance medium-bandgap PSMAs.

Synergetic Alkoxy Side-Chain and Chlorine-Contained End Group Strategy toward High Performance Ultra-Narrow Bandgap Small Molecule Acceptors

Ultra-narrow bandgap(ultra-NBG)small molecule acceptors(SMAs)show great potential in organic solar cells(OSCs)due to the extended near-infrared(NIR)absorption.In this work,a synergetic alkoxy side-chain and chlorine-contained end group strategy is employed to achieve A-DA'D-A type ultra-NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiopheneβposition as well as replacing the F atoms with Cl atoms in the end group.As a result,the heptacyclic BZO-4F shows a redshifted absorption onset(960 nm)compared with Y11(932 nm)without oxygen atoms in the side chains.Then,the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO-4Cl.The absorption onset of BZO-4Cl is further redshifted to 990 nm,corresponding to an optical ultra-NBG of 1.25 eV.When blending with the polymer donor PBDB-T,the binary devices based on PBDB-T:BZO-4F and PBDB-T:BZO-4Cl deliver power conversion efficiencies(PCEs)over 12%.Furthermore,ternary devices with the addition of BZ4F-O-1 into PBDB-T:BZO-4Cl system achieve the optimal PCE of 15.51%.This work proposes a synergetic alkoxy side-chain and chlorine-contained end group strategy to achieve A-DA'D-A type ultra-NBG SMAs,which is important for future molecular design.

Photoredox Ni-Catalyzed Selective Coupling of Organic Halides and Oxalates to Esters via Alkoxycarbonyl Radical Intermediates

A new approach for radical cross coupling of organic halides and oxalates toward esters has been developed via photoredox nickel dual catalysis.This method has been demonstrated for transformation of a wide range of aryl,heteroaryl,alkenyl,and alkyl bromides to various esters under mild conditions.Notably,fluoro-,chloro-,or iodo-substituents on the aryl bromides remain after the coupling reaction,which has been applied for the easy synthesis of drug molecules from simple aryl dihalides.Mechanistic studies indicate that an(alkoxycarbonyl)Ni(I)species might be generated via oxidation of Ni(0)species with an alkoxycarbonyl radical intermediate.Selective alkoxycarbonyl radical coupling over decarboxylative alkyl radical coupling is achieved here.

Alkoxy encapsulation of carbazole-based thermally activated delayed fluorescent dendrimers for highly efficient solution-processed organic light-emitting diodes

Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.

New conducting polythiophenes containing substituted polyfluorinated alkoxy chain

A series of poly(fluoroalkoxy thiophenes) have been prepared by electrochemical and chemical polymerization respectively. The substitution of thiophene by polyfluorinated alkoxy chains affords more favorable structures in electronic effect and higher stabilities of their polymers than conventional alkoxy chain substituted polymers.

SYNTHESIS AND POLYMERIZATION OF γ-ALKOXY β-HYDROXYPROPYL ACRYLATES

As a biomedical hydrogel, poly(β-hydroxyethyl methacrylate)has been widely studied and discussed, but studies on the synthesis and polymerization of those acrylates which contain both hydrophilic hydroxy group and alkoxy group in the same ester group have received comparatively less attention. However Mikhailov first reported the synthesis of some γ-alkoxy-β-hydroxypropyl methacrylates and γ-aryloxy β-hydroxypropyl methacrylates from methacrylic acid and γ-alkoxy propylene or γ-

Synthesis and mesomorphic evaluation of new calamitic liquid crystals containing benzothiazole core

The design and synthesis of new calamitic benzothiazole-based liquid crystals,2-[4-（4-alkyloxybenzoyloxy）-phenyl]ben-zothiazoles are presented.The target compound was characterized using spectroscopic techniques,such as FT-IR,NMR（~1H and ^（13）C）,microanalysis and EI-MS.The liquid crystalline behaviours of these compounds were thoroughly examined by differential scanning calorimetry and polarizing optical microscope techniques.These materials exhibited enantiotropic nematic phase with high thermal stability（168℃）.Smectic A phase starts to emerge as monotropic（metastable） phase from C10 member and changes into enantiotropic（stable） phase from C12 and persists up to C16 members.

Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides

Main observation and conclusion Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations.However,carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen,is scarce and underdeveloped.Herein,we report alkoxy radical,which was generated from alkyl radical and dioxygen,mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes,providing facile access to a variety of valuableβ-keto sulfones.Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselectiveβ-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C-C bond cleavage.Notably,the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.

Enhancement the photovoltaic performance of conjugated polymer based on simple head-to-head alkylthio side chains engineered bithiophene

In this article,three novel and simple molecular structure with donor-acceptor(D-A) type copolymers via only head-to-head alkoxy(OR) and/or alkylthio(SR) side chains onto the bithiophene(BT) as donor units and fluorinated benzotriazole(FBTA) as acceptor unit,namely,PBTOR-FBTA,PBTOSR-FBTA and PBTSRFBTA,were successfully designed and synthesized.The impacts of sulfur-oxygen(S…O) or sulfur-sulfur(S-S) noncovalent interactions on their physicochemical properties,molecular stacking,carrier mobility,morphologies of blend films,as well as their photovoltaic performance were deeply and systematically studied.The introduction of SR side-chains suddenly lowered the highest occupied molecular orbital(HOMO) energy levels,blue-shifted absorption,enhanced π-π stacking,as well as improved morphology of the photoactive layer blends in comparison with the re ference polymer without SR side-chain.Polymer solar cells(PSCs) were fabricated to estimate their photovoltaic performance of the polymers.Under an optimized blend ratio of PBTSR-FBTA:PC71BM(1:0.8,w/w),the PBTSR-FBTAbased device exhibits a higher power conversion efficiency(PCE) of 6.25%,which is about 3.34 and 1.87 folds than that of the PBTOR-FBTA and PBTOSR-FBTA-based devices,respectively.Our research results demonstrate that the modification of the simple and low-cost SR side chains is an effective strategy to improve the photovoltaic performance of the polymers.