STUDY ON THE SYNTHESIS AND PROPERTIES OF POLY(ESTER-IMIDEETHER)MULTIBLOCK COPOLYMERS

A new class of poly(ester-imide-ether) multiblock copolymers was synthesized by transes-terification and melt copolymerization of dimethyl terephthalate (DMT) and N-(4-carbomethoxyphenyl)-4-(carbomethoxy)-phthalimide with ethylene glycol (EG) and polytetramethylene glycol (PTMG). The structure of the above copolymers was characterized by H-1-NMR and IR spectroscopy. Some properties of the coplymers were also examined. It was found that their mechanical properties and heat stability, compared with poly(ether-ester) copolymers, were obviously improved.

Synthesis of Methyl-substituted Phthalazinone-based Aromatic Poly(amide imide)s

A series of novel aromatic poly ( amide imide)s containing phthalazinone moieties were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with four diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36~0.65 dL/g. These polymers had high glass transition temperatures above 300C and they lost 10% weight between 426~475C in N2. The structure of diamine 1 and the polymers was confirmed by IR, 1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP, m-cresol etc. and easily cast into tough, flexible films. The X-ray indicated that they are all amorphous.

Synthesis and Characterization of Poly(ether imide)s Containing m-Methyl and Phthalazinone Moieties

Three novel poly(ether imide)s were synthesized by one-step solution polymerization from 2-(3, 4-dicarboxyl-N-phenyl)-4-(3, 4-dicarboxyl-phenoxyl-4-(2-methyl)-phenyl)-2, 3- phthal-azin-1-one dianhydride and three amines, and characterized. The polymers show good solubility and thermal properties.

SYNTHESIS OF NEW AROMATIC POLY(AMIDE IMIDE)S FROM UNSYMMETRICAL EXTENDED DIAMINE CONTAINING A PHTHALAZINONE MOIETY

The direct polymerization of an unsymmetrical kink non-coplanar heterocyclic diamine (1) with various aromatic bis(trimellitimide)s (2a-e) using triphenyl phosphite and pyridine as condensing agents could generate a series of new aromatic poly(amide imide)s (3a-e) containing the kink non-coplanar phthalazinone heterocyclic units in the polymer main chains with inherent viscosities of 0.58-0.66 dL/g. The polymers are readily soluble in a variety of solvents such as N,N- dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, pyridine and m-cresol and can be cast to form flexible and tough films. The glass transition temperatures of polymers (Tg) are in the range of 301-327°C, and the temperatures for 5% weight loss in nitrogen are in the range of 498-521 'C.

Synthesis and Characterization of Poly (ether imide)s Containing Phthalazinone and Isopropyl Moieties

A novel poly(ether imide)s containing phthalazinone and isopropyl moieties derived from 2-(4-aminophenyl)-4-[4-(4-aminophenoxy)phenyl]-phthalazin-1-one and bisphenol-A diphthalic anhydride was synthesized by one-step solution condensation polymerization in nr-cresol. The polymer was characterized by FTIR, NMR, molecular weights, glass transition temperature, thermal degradation temperature and WAXD.

Influence of Curing Accelerators on the Imidization of Polyamic Acids and Properties of Polyimide Films

In order to lower the imidization temperature of polyamic acids（PAA）, the catalytic activities of the curing agents p-hydroxybenzoic acid（PHA）, quinoline（QL）, benzimidazole（BI）, benzotriazole（BTA）, triethylamine（Et_3N） and 1, 8-diazabicyclo [5.4.0]undec-7-ene（DBU） were investigated in the process of thermal imidization of PAA. In addition, the effect of these various curing agents on the thermal stabilities and mechanical properties of the resultant polyimide（PI） films was determined. Quinoline was found to be an effective curing accelerator in the use of two-step method for synthesizing PI. Due to its moderate base strength, low steric crowding effect and moderate boiling point, quinoline could not only accelerate PAA to achieve imidization completely at 180 ℃, but also maintain the mechanical properties and thermal stability of the ordinary PI film. Any residual quinoline could be removed from PI films by heating at 250 ℃ for 4 h.

Acidic Polyester Imides as Thermally Stable Binder Polymers for Negative-Tone Black Photoresist

Polyimides are well-known for their high chemical inertness and thermal stability. However, it is usually challenging to synthesize UV-curable polyimides since the imidization reaction requires such harsh conditions that acrylate type double bonds cannot withstand. In this work, synthetic methods are developed to obtain polyester-imide type binder polymers with high thermal stability, high compatibility with the other components of the black photoresist, and fine photolithographic patterning property for the negative-tone black photoresist. The syntheses of diimide-diacid or diimide-diol intermediates for the polyesterification with dianhydride gave polyester imides which meets this requirement. The photolithographic tests have shown that the patterning of the micron-sized PDL of the organic light emitting diode (OLED) panel could be obtained. This work will interest the researchers working on the design and optimization of thermally stable binder polymers.

Implementation of a choline bis(trifluoromethylsulfonyl)imide aqueous electrolyte for low temperature EDLCs enabled by a cosolvent

We report a carbon/carbon capacitor based on micro/mesoporous carbon electrodes with cost-effective and eco-friendly aqueous choline bis(trifluoromethylsulfonyl)imide(Ch TFSI)electrolyte with a cosolvent enabling low-temperature operation down to-30℃.For this purpose,a Mg O-templated hierarchical carbon(MP98B)with an average mesopore diameter of 3.5 nm was prepared by pyrolysis of magnesium citrate hydrate at 900℃.To reach lower temperatures,the melting point and viscosity of the aqueous electrolyte were reduced by mixing water(W)with an organic solvent(methanol,M,or isopropanol,I)of high dielectric constant and low viscosity.5 mol kg^(-1)(5 m)Ch TFSI in an optimized volume fraction of cosolvent,M_(0.75)W_(0.25),and I_(0.75)W_(0.25),showed the highest conductivity;the higher conductivity in M_(0.75)W_(0.25)(22.8 and 3.1 m S cm^(-1) at 20 and-30℃,respectively)than in I_(0.75)W_(0.25)(8.5 and0.5 m S cm^(-1)at 20 and-30℃,respectively)is attributed to the lower viscosity of the M_(0.75)W_(0.25)solution.The electrochemical stability window(ESW)of 5 m Ch TFSI in M_(0.75)W_(0.25)and I_(0.75)W_(0.25)(1.6 V)on an MP98B electrode was determined by applying the S-method.Meanwhile,by adjusting the mass ratio of the two electrodes,a MP98B/MP98B capacitor using the 5 m electrolyte in M_(0.75)W_(0.25)could operate with a good life span up to 1.6 V while exhibiting a better charge propagation,greater specific capacitance,and higher specific energy than in I_(0.75)W_(0.25).

Synthesis of Poly(aryl amide imide)s Derived from o-diphenyltrimellitic Anhydride

The synthesis and characterization of a series of novel poly(aryl amide imide)s based on o diphenyltrimellitic anhydride are described.The poly(aryl amide imide)s having inherent viscosities of 0.39-1.43dL/g in N methyl 2 pyrrolidinone at 30℃,were prepared by polymerization with aromatic diamines in N,N-dimethylacetamide and subsequent chemical imidization.All the polymers were amorphous,readily soluble in aprotic polar solvents such as DMAC,NMP,DMF,DMSO,and m cresol,and could be cast to form flexible and tough films.The glass trsanition temperatures were in the range of 284-336℃,and the temperatures for 5% weight loss in nitrogen were above 468℃.

Synthesis and Crystal Structure of N-Phenylbis(ferrocenecarboxyl)imide

The ferrocenyl compound, N-phenylbis（ferrocenecarboxyl）imide （C28H23NO2Fe2, Mr = 517.17）, was synthesized and structurally characterized by means of X-ray single-crystal diffraction. It crystallizes in monoclinic, space group C2/c with a = 21.374（14）, b = 10.430（7）, c = 10.741（7） A, β= 114.184（8）°, V= 2184（2） A^3, Z= 4, Dc = 1.573 g/cm^3, F（000） = 1064, μ（MoKα） = 1.355 mm ^-1, T= 291（2） K, the final R = 0.0548 and wR = 0.1437 for 1524 observed reflections with 1 〉 2σ（I）. In this compound, the nitrogen atom links two ferrocenyl groups and one phenyl group forming a novel imido derivative.

Solvothermal Synthesis,Crystal Structure and Antimicrobial Activity of a Novel Imide Nickel Complex [Ni(CH_3CONCOCH_3)_2·2(H_2O)]

A novel imide nickel complex [Ni（CH3CONCOCH3）2·2（H2O）] was synthesized by the solvothermal reaction of nickel acetate tetrahydrate and acetonitrile.What amazed us is that acetonitrile had changed into acetyl imide in enol form during the formation process of the title complex.The complex was characterized by elemental analysis,IR spectrum and X-ray single-crystal diffraction analysis.It crystallizes in the orthorhombic system,space group Pbca with a = 7.4503（7）,b = 13.1089（12）,c = 14.1303（14）,V = 1380.0（2）3,Dc = 1.420 g/cm3,Mr = 294.94,Z = 4,F（000） = 616,μ = 1.422 mm-1,the final R = 0.0487 and wR = 0.1482.The four-coordinated nickel（II） center is surrounded by 4O atoms from two imide ligands and has a distorted square planar geometry.The complex is connected to form a supramolecule with an infinite three-dimensional network through intramolecular and intermolecular hydrogen bonds.Antimicrobial activity was investigated by agar diffusion method,and the result showed that the complex was active against coli bacillus,staphylococcus aureus and bacillus subtilis.The thermal stability of the title complex was also studied by TG-DTA method.

Design,Synthesis and Electrochromic Properties of Anthraquinone Imide-based Donor-acceptor Type of Near Infrared Chromophores

A new series of near infrared（NIR） electrochromic anthraquinone imides containing a triphenylamine moiety as an electron donor was synthesized and their electrochemical and spectroelectrochemical behavior were investigated.The results show that the new anthraquinone imides are redox active which can be reduced electrochemically from the neutral state to the radical anion form that absorbs in a range of 700―1200 nm.

Hydroxyalkylation of Cyclic Imides with Oxiranes Part I. Kinetics of Reaction in Presence of Triethylamine as Catalyst

Literature describes kinetics of reactions of alcohols, phenols, carboxylic acids, amines and amides with oxiranes such as ethylene oxide and propylene oxide. However, there is no information regarding kinetic of reaction of imides with oxiranes. In this article the kinetics of the reaction of cyclic monoimides: succinimide, phtalimide, and glutarimide, with ethylene and propylene oxides in presence of triethylamine in aprotic solvent was studied. The rate laws for those processes were established based upon on dilatometric measurements. I was said that cyclic monoimides react with oxiranes in presence of triethylamine to give N-(2-hydroxyalkyl)imides as major product. This product react further with oxiranes in consecutive reaction. The kinetics of the reaction of cyclic mono-imides with oxiranes obey the following rate law: V = k1/2 c1/2cat c3/2imide c1/2oxirane. Based upon kinetic data the following orders of reactivity of imides and oxiranes were obtained: phtalimide ≥ succinimide > glutarimide and ethylene oxide > propylene oxide. The solvent (DMF, DMSO and dioxane) effect was also studied. From temperature dependences the thermodynamic parameters: activation energy, enthalpy and entropy from linear Eyring plots were obtained.

Hydroxyalkylation of Cyclic Imides with Oxiranes Part III. Mechanism of the Reaction in Presence of Sodium Hydroxide Catalyst

The kinetics of reaction between cyclic monoimides (succinimide, phtalimide, and glutarimide) with ethylene and propylene oxides in presence of sodium hydroxide was studied. The effect of substrate and catalyst concentrations on the course of the reaction was investigated. Kinetics of reaction was studied by dilatometry, i.e. by measuring volume contraction of reaction mixture. The kinetic law describing the reaction of imides with oxiranes is: . where ccat, cAH and cB are concentrations of catalyst, imide, and oxirane, respectively. The relative reactivity of imides and oxiranes was: GI > PI ≥ SI and EO > PO. The reaction mechanism was proposed based upon experimentally determined rate law for the reaction of cyclic monoimides and oxiranes as well as analytical and instrumental analysis of products. The elementary reaction between oxirane and imide anion is rate determining step. The imide anion is formed by hydrogen cation transfer into catalytic hydroxide anion from dissociated NaOH. In the consecutive elemental reaction an imidate anion attack on the oxirane molecule occurs. It is the slowest stage of the reaction, limiting the entire process. All the studied reactions obey the same mechanism as can be concluded from isokinetic relationship of studied systems)

Hydroxyalkylation of Cyclic Imides with Oxiranes. Part II. The Mechanism of Reaction in Presence of Triethylamine

The mechanism of reaction of cyclic monoimides with oxiranes was established based upon kinetic studies and product analysis. It has been established that the reaction proceeds through initial formation of an adduct of imide and triethylamine. The crucial bond in adduct has ionic character;in non-aqueous solvents it is present as ion pair, while in water the adduct dissociate and free ions are present. The adduct enables the proton transfer from imide to oxirane. The rate determining step is reaction of imide and this adduct. Different values of entropy of transition states obtained from thermodynamic calculations suggest slightly different structure of transition state of rate determining step.

Instability of lithium bis(fluorosulfonyl)imide(LiFSI)–potassium bis(fluorosulfonyl)imide(KFSI) system with LiCoO_2 at high voltage

The cycling performance, impedance variation, and cathode surface evolution of the Li/LiCoO2 cell using Li FSI–KFSI molten salt electrolyte are reported. It is found that this battery shows poor cycling performance, with capacity retention of only about 67% after 20 cycles. It is essential to understand the origin of the instability. It is noticed that the polarization voltage and the impedance of the cell both increase slowly upon cycling. The structure and the properties of the pristine and the cycled LiCoO2 cathodes are investigated by x-ray diffraction（XRD）, scanning electron microscopy（SEM）, Raman spectroscopy, x-ray photoelectron spectroscopy（XPS）, and transmission electron microscopy（TEM）. It is found that the LiCoO2 particles are corroded by this molten salt electrolyte, and the decomposition by-product covers the surface of the LiCoO2 cathode after 20 cycles. Therefore, the surface side reaction explains the instability of the molten salt electrolyte with LiCoO2.

Extension of Highly Efficient Alcohol-promoted Rearrangement into One-pot Domino Palladium-catalyzed Carbonylation for Sterically Crowded Aromatic Six-membered Imides

Aromatic six-membered imides suffer the introduction of bulky substituents at the imide positions due to the formation of isoimides and low reactivity,preventing from the investigation of the intrinsic molecular properties.Here,we found a highly efficient alcohol-promoted rearrangement from isonaphthalimide to naphthalimide under acid or basic nonaqueous conditions,which can be regarded as model compounds for aromatic six-membered imides.We proposed two-step nucleophilic substitutions in the isomerization mechanistic pathways that were verified by the separation of a key intermediate.Furthermore,in-situ ^(1)H NMR exhibited the first-order kinetics for the isoimide loss process.Finally,the alcohol-promoted isoimide-imide rearrangement was extended to a palladium-catalyzed one-pot domino carbonylation reaction toward sterically crowded aromatic six-membered imides.

Lithium(fluorosulfonyl)(n-nonafluorobutanesulfonyl)imide for stabilizing cathode-electrolyte interface in sulfonamide electrolytes

Rechargeable lithium metal batteries(RLMBs)have been regarded as promising successors for contemporary lithium-ion batteries,in view of their high gravimetric and volumetric energy densities.Conventional non-aqueous liquid electrolytes containing organic carbonate solvents possess high chemical reactivities with metallic lithium anode and high flammability,which induces considerable safety threats under extreme conditions(e.g.,overcharging and thermal runaway).Herein,we propose the utilization of fluorinated sulfonamide(i.e.,N,N-dimethyl fluorosulfonamide(DMFSA))as solvent,together with lithium(fluorosulfonyl)(n-nonafluorobutanesulfonyl)imide(LiFNFSI)as co-salt and/or electrolyte additive for accessing safer and highperforming RLMBs.Comprehensive physical(e.g.,thermal transition,viscosity,and ionic conductivity)and electrochemical(e.g.,anodic stability on different electrodes)characterizations have been performed,aiming to reveal the inherent characteristics of the sulfonamide-based electrolytes and the particular role of LiFNFSI on the stabilization of LiCoO_(2) cathode.It has been demonstrated that the sulfonamide-based electrolytes exhibit superior flame-retardant abilities and decent ionic conductivities(>1 mS·cm^(-1)at room temperature).The incorporation of LiFNFSI as co-salt and/or electrolyte additive could significantly suppress the side reactions occurring at the cathode compartment,through the preferential decompositions of the FNFSI-anion.This work is anticipated to give an in-depth understanding on the working mechanism of LiFNFSI in the sulfonamide-based electrolytes,and also spurs the development of high-energy and safer RLMBs.

N,N-Dimethyl fluorosulfonamide for suppressed aluminum corrosion in lithium bis(trifluoromethanesulfonyl)imide-based electrolytes

Effective passivation of aluminum(Al)current collector at high potentials(>4.0 V vs.Li/Li^(+))is of essence for the long-term operation of lithium-based batteries.Unfortunately,the non-aqueous liquid electrolytes comprising lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)and organic carbonates are corrosive toward Al current collector at high potentials(>4.0 V vs.Li/Li^(+)),despite their intriguing features(e.g.,good chemical stability and high ionic conductivity).Herein,we propose the utilization of N,N-dimethyl fluorosulfonamide(DMFSA)as electrolyte solvent for suppressing Al corrosion in the LiTFSI-based electrolytes.It has been demonstrated that the electrolyte of 1.0 M LiTFSI-DMFSA shows decent ionic conductivities(1.76 mS·cm^(−1)at 25℃)with good fluidities(2.44 cP at 25℃).In particular,the replacement of organic carbonates(e.g.,ethylene carbonate and ethyl methyl carbonate)with DMFSA leads to significant suppressed Al corrosion.Morphological and compositional characterizations utilizing scanning electron microscopy(SEM)and X-ray photoelectron spectroscopy(XPS)reveal that DMFSA favors the formation of insoluble species(i.e.,aluminum fluoride(AlF_(3)))on the surface of Al electrode,which effectively inhibits continuous exposure of fresh Al surface to electrolyte during cycling.This work provides not only a deeper understanding on the Al corrosion in LiTFSI-based electrolyte but also an elegant path to stabilize the Al current collector at high potentials(>4.0 V vs.Li/Li^(+)),which may give an impetus into the development of lithium-based batteries.

Efficient synthesis of cyclic imides by the tandem N-arylation-acylation and rearrangement reaction of cyanoesters with diaryliodonium salts

Available online An efficient method for the synthesis of multi-substituted cyclic imides was developed with cyanoesters and diaryliodonium salts.This method proceeds through a cascade of N-arylationacylation and rearrangement to give target heterocycles in good yields(up to 99%).This method has the major advantages of a broad substrate scope,excellent functional group compatibility.The strategy was also extended to the fused cyclic imides,such as malonimides,succinimides and glutarimides.