Polyimides as Promising Materials for Lithium-Ion Batteries:A Review

Lithium-ion batteries(LIBs)have helped revolutionize the modern world and are now advancing the alternative energy field.Several technical challenges are associated with LIBs,such as increasing their energy density,improving their safety,and prolonging their lifespan.Pressed by these issues,researchers are striving to find effective solutions and new materials for next-generation LIBs.Polymers play a more and more important role in satisfying the ever-increasing requirements for LIBs.Polyimides(PIs),a special functional polymer,possess unparalleled advantages,such as excellent mechanical strength,extremely high thermal stability,and excellent chemical inertness;they are a promising material for LIBs.Herein,we discuss the current applications of PIs in LIBs,including coatings,separators,binders,solid-state polymer electrolytes,and active storage materials,to improve high-voltage performance,safety,cyclability,flexibility,and sustainability.Existing technical challenges are described,and strategies for solving current issues are proposed.Finally,potential directions for implementing PIs in LIBs are outlined.

SYNTHESIS AND CHARACTERIZATION OF HIGHLY ORGANO-SOLUBLE POLYIMIDES BASED ON ALICYCLIC 1,8-DIMETHYL-BICYCLO[2.2.2]OCT-7- ENE-2,3,5,6-TETRACARBOXYLIC DIANHYDRIDE AND AROMATIC DIAMINES

Organo-soluble alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, 1,8-dimethyl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (DMEA) and several multialkyl-substituted 4,4'-diaminodiphenylmethane compounds, including 3,3'-dimethyl-4,4'-diaminodiphenyt methane (DMDA), 3,31,5,5'-tetramethyl-4,4'-diaminodiphenyl methane (TMDA) and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (TEDA). For comparison, the aromatic polyimides (ARPIs) were synthesized from the aromatic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and the same diamines. The ALPIs exhibited better solubility and transparency, but worse thermal stabilities and mechanical properties than those of the ARPIs. And the ALPIs could be dissolved in common organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), chloroform, tetrahydrofuran, m-cresol and so on. The ALPI films had an UV-Vis cut-off at 320 nm and a transmittance of higher than 80% in the visible region. In addition, the ALPIs showed thermal decomposition temperatures (T-d) of about 450degreesC, which was nearly 100degreesC lower than that of the ARPIs.

Novel hyperbranched polyimides from 2,6,12-triaminotriptycene

The monomer 2,6,12-triaminotriptycene was synthesized and the structure was confirmed by IR and 1H NMR spectra. Hyperbranched polyimides modified with different terminal groups were obtained from precursors, anhydride- and aminoterminated hyperbranched poly（amic acid）s from polymerization of A2 ＋ B3 system. From gel permeation chromatograrn （GPC） characterization, representative products had high molecular weight. All polymers had good solubility in CHCl3, DMF and tetrahydrofuran （THF）, and performed no detective Tgs in the range of 50-300 ℃ and high Tds above 455 ℃ when 5% weight loss.

SYNTHESIS AND CHARACTERIZATION OF ORGANSOLUBLE POLYIMIDE AND COPOLYIMIDES FROM ALICYCLIC DIANHYDRIDE

A kind of highly organsoluble polyimide and copolyimides were successfully synthesized from bicyclo（2.2.2）-oct- 7-ene-2,3,5,6-tetracarboxylic dianhydride （BCDA）, the commercial diamine 4,4＇-methylenedianiline （MDA） and the designed diamine 4,4＇-methylenebis-（2-tert-butylaniline） （MBTBA）. The polyimide from BCDA and MBTBA is highly soluble in conventional low boiling point solvents （such as chloroform, tetrahydrofuran） at room temperature. But the solubility of the copolyimides in conventional solvents decreased with the molar ratio of MBTBA and MDA decreased. When the molar ratio of MBTBA and MDA was larger than 7/3, the copolyimides can be soluble in low boiling point solvents at room temperature to form a transparent, flexible, tough film by solution casting. When the molar ratio of MBTBA and MDA was between 7/3 and 1/9, they can only be soluble in hot dipolar aprotic solvents （such as DMF, NMP etc.） and form films too. The copolyimide was only soluble in m-cresol when the molar ratio of MBTBA and MDA was lower than 1/9. The number-average molecular weights of the soluble copolyimides were larger than 5.8 × 1064 g/mol by GPC and their polydispersity indices were higher than 1.4. Only one glass transition temperature of these copolyimides was detected around 400℃ by DMA. The copolyimides did not show appreciable decomposition up to 430℃ in N2.

STUDY ON SYNTHESES AND PROPERTIES OF SOME NOVEL POLYIMIDES CONTAINING BISTHIAZOLE RINGS

Some novel polyimides containing bisthiazole rings were prepared by reacting 2,2'-diamino-4, 4'-bisthiazole (DART) with different aromatic dianhydride. The polyimides obtained had inherent viscosities of 0.37-0.82 dl/g. Thermogravimetric analysis of the polyimides showed good thermal stability, the temperature at 5% weight loss being from 450 degrees to 560 degrees C. The permeability of two polymer membranes to H-2, O-2 and N-2 was determined, respectively. Three kinds of polyimide films were converted into electrical conductor by pyrolysis at high temperature in nitrogen atmosphere. The maximum room temperature conductivity as high as 3.9x10(2) S/cm for PI him pyrolyzed at 1200 degrees C for 10 min was obtained, and it was very stable in air.

ORGANO-SOLUBLE FLUORINATED POLYIMIDES DERIVED FROM α,α-BIS(4-AMINO-3,5-DIMETHYLPHENYL)-4'-FLUOROPHENYL METHANE AND VARIOUS AROMATIC DIANHYDRIDES

Organo-soluble fluorinated polyimides were synthesized by the polycondensation of a new aromatic diamine α,α-bis(4-amino-3,5-dimethylphenyl)-4'-fluorophenyl methane with several aromatic dianhydrides.The one-step polymerizationprocedure was conducted at 180℃ in m-cresol,producing the polyimides with inherent viscosities of 0.68-0.76 dL.g^(-1).Thepolyimides could be soluble not only in polar aprotic solvents,such as N-methyl-2-pyrrolidinone,and N,N-dimethylacetamide,but also in common organic solvents,such as chloroform,cyclopentanone,m-cresol and so on.Thepolyimide films show excellent transparency with the UV-Vis cut-off lengths of 310-360 nm and light transmittances ofhigher than 80% in the visible region.In addition,the polyimides exhibit good thermal stability with an initial decompositiontemperature(T_d)higher than 530℃ and have more than 60% of residual weight retentions at 700℃.

Synthesis and Characterization of Novel Polyimides Based on Pyridine-containing Diamine

A new aromatic diamine monomer containing pyridine unit, 2,6-bis （4-aminophenoxy- 4＇-benzoyl）pyridine（BABP）, was synthesized in three steps, starting from 2,6-pyridinedicarboxyl chloride. A series of novel pyridine-containing polyimides were prepared v/a the polycondensation of BABP with various aromatic dianhydrides through poly（amic acid） precursors, and thermal or chemical imidization of the precursors. The polyimides exhibit desirable properties, e.g., good solubility in N-methyl-2-pyrrolidone and m-cresol, excellent thermal stability and film-forming capability, as well as high inherent viscosity, indicating high molecular weight.

A MOLECULAR APPROACH TO THE SYNTHESIS OF NOVEL POLYIMIDES

In the past ten years there has been a flurry of activity in the synthesis of new specialty polymers,largely as a result of the increased need for high technology materials. Interest is mainly shown in two distinctcategories of polymers: a) polymers which are used in very small quantities to fulfill critical needs as a part ofdevice systems, and b) high-performance engineering polymers which significantly extend their mechanicaland thermal properties for structural applications. Polyimides and their unparalleled versatility have capturedthe attention and imagination of scientists and engineers. This article describes some of the recent work doneby the author's group on the rational design at the molecular level and the synthesis of polyimides that haveunusual structures and novel properties.

Synthesis of a Novel Diamine 4-[(4'-Butoxyphenoxy)carbonyl]phenyl-3",5"-diaminobenzoate and Corresponding Polyimides

A novel diamine 4-[（4＇-butoxyphenoxy）carbonyl]phenyl-3＂,5＂-diaminobenzoate （BCDA） was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4＇-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature, solubility and the pretilt angles, were carded out.

ORDERED STRUCTURAL EVOLUTION AND RELAXATION BEHAVIORS OF A SERIES MICROPHASE SEPARATED“HAIRY-ROD”POLYIMIDES WITH MULTIPLE ALKYL SIDE CHAINS

A series of“hairy-rod”polyimides,BBPA(n),with multiple alkyl side chains was prepared from 3,3',4,4'-biphenyltetracarboxylic dianhydride(BPDA)and 4,4'-biphenyldiamine substituted in the 2,2'-positions with benzoate,whichwas substituted in the 3,4,5-positions with ether side chains of varying lengths.The number of the methylene units,n,inthese alkyl side chains were in even numbers ranging from 8 to 18.Combining techniques of one-dimensional(1D)and 2Dwide angle x-ray diffraction,1D small angle X-ray scattering,differential scanning calorimetry experiments,it was found thatthis series of“hairy-rod”polyimides possess a micro-phase separation between the backbones and side chains.This led to theformation of ordered structures in two different length scales,of which both are hexagonal packing:one is attributed to thealkyl side chains on the sub-nanometer scale,and another is for the whole polymer chains on the nanometer scale.Thedevelopment of the hexagonal structure on the sub-nanometer scale was critically dependent upon the lengths of the alkylside chains.Three relaxation processes were captured by dynamic mechanical analysis,i.e.,segmental motion of thebackbones,α,the melting of the side chain crystals,β_1,which exits only for the materials with longer side chains(n=18,16);and the subglass relaxation of side chains,β_2.The peak relaxation temperature of the α process decreased withincreasing the length of side chains,while the one of the β_2 process increased.The activation energy of the α relaxation wasrelatively independent on the length of side chain,whereas,β_2 process showed the increasing of activation energy withincreasing the length of side chains.

FLUORINATED PHTHALAZINONE-CONTAINING COPOLYIMIDES FOR PASSIVE OPTICAL WAVEGUIDES

A series of fluorinated copolyimides containing phthalazinone moieties were prepared from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride(6FDA),3,3'4,4'-benzophenone-tetracarboxylic dianhydride(BPDA)and2-(4-aminophenyl)-4-[4-(4-aminophenoxyl)phenyl]-2,3-phthalazin-1-one(DHPZ-2NH_2)for making polymeric opticalwaveguides.The resulting copolymers containing 0-50 mo1% BPDA/DHPZ-2NH_2 show good solubility and are soluble insome organic polar aprotic solvents.The copolyimides also present excellent thermal stability.These polymers possess highglass transition temperature higher than 603 K and high decomposition temperature above 742 K determined by differentialscanning calorimetry and thennogravimetric analysis,respectively,under a nitrogen atmosphere.Their refractive indicescould be controlled by varying the ratio of 6FDA and BPDA in the copolymer from 0.5 to 1.0,and the in-plane refractiveindices(n_(TE))range from 1.6366 to 1.6668 and the out-of-plane refractive indices(n_(TM))from 1.6024 to 1.6280 at 632.8 nm.The polymers birefringence(0.0342-0.0388)is almost independent of the 6FDA content of copolymer,which indicated thatthe phthalazinone-containing copolyimides could be suitable to fabricate optical waveguides possessing a low polarizationdependent loss(PDL).

A FACILE SYNTHESIS OF HYPERBRANCHED POLYIMIDES FROM 2,6,12-TRIAMINOTRIPTYCENE

Based on monomer 2,6,12-triaminotriptycene, hyperbranched polyimides with high molecular weight modified with different terminal functional groups were obtained by polymerization of A2 ＋ B3 system. The prepared hyperbranched polyimides had good solubility in CHCl3, DMF and THF, and performed no detective Tgs in the range of 50-330℃ and high TdS （5%） above 455℃.

TRANSIMIDIZATION IN THERMOPLASTIC POLYIMIDES

In order to improve the processibility in thermoplastic polyimides, a new method, termed the'reactive plasticizer' approach, has been proposed. This method uses a small amount (5～15 mol%) of a lessactivated, weak nucleophilic diamine co-monomer as a 'reactive plasticizer' to obtain copolyimide resinswhich possess relatively low viscosity at low temperatures and can be readily processed through the autoclavecycle at low pressures. During a high temperature treatment, the reactive plasticizers join the reaction to formhigh molecular weight copolyimides, and the preferred material properties are thus achieved. The mosteffective reactive plasticizer is aromatic heterocyclic diamines, such as 2, 6-diaminopyridine diamine (DAP),and the transimidization involved with a reactive plasticizer has been proposed to play a major role for thesuccess of this approach. In order to understand the transimidization mechanism, three steps have been takenin this research: first, a copolyimide system of 50% of DAP and 50% 1, 4 -bis [4-aminophenoxy] benzenediamine (DODA) with 100% of 2, 2'-bis[4-(3, 4-dicarboxyphenoxy)phenyl] propane dianhydride (Ultem^(R)DA) is prepared. Second, several specifically designed polyimide mixture systems were used, and they consistof two homopolyimides: one is Ultem^(R) DA-DODA, and the other is Ultem^(R) DA-DAP. The third step is toinvestigate two mixture systems in which Ultem^(R) DA-DODA is mixed with DAP monomer solution andUltem^(R) DA-DAP is mixed with DODA monomer solution. For all systems, with increasing degree oftransimidization upon heat-treatment, the chain structures of the mixtures and their thermal and dynamicmechanical transition behaviors are investigated via one-dimensional and two-dimensional nuclear magneticresonance, differential scanning calorimetry, and dynamic mechanical analysis experiments. Experimentalresults indicate that in the mixture of two homopolyimides, transimidization takes place much moreefficiently in solution than in the melt. For the two mixtures with monomer solutions, the transimidizationcan only be found in the mixture of Ultem^(R) DAP/DODA system in p-chlorophenol, and this process does noteffectively occur in the Ultem^(R) DODA/DAP system in p-chlorophenol, indicating that free DODA canefficiently attack the imide linkage of Ultem^(R) DA-DAP. The final product resulting from the transimidizationin the mixtures is a random copolyimide with a major population of DAP as end groups for the copolymersystem.

Electrical Properties of Fluoro-Containing Alicyclic Polyimides

The electrical, physical, mechanical and thermal properties of fluorine-containing alicyclic polyimides have been investigated. It was shown that the minimum value of the dielectric constant 1.91 at room temperature and 1 kHz frequency was achieved for polymers containing only one fluorine atom in the structure. The dielectric loss tangent of new polymers was （I -4）~ 103. Electro-physical parameters were stable during polymer heating up to 300 ~C, and at the frequency from 1 to 20 kHz. Resistivity by heating in the air up to 320-380 ~C has been investigated depending on the polyimides structure. The coefficient of moisture absorption for the fluorine-containing polyimide based on dianhydride with 4,4＇-oxydianiline was determined at 50% humidity and 25 ℃. It was around 0.6, but after immersion in the water for 24 and 48 h was 0.8% and 1.2%, respectively. Manufactured films had tensile strength to 160-170 MPa, and elongation up to 55%.

New Soluble Fluorinated Polyimides

The synthesis and properties of a class of soluble fluorine-containing aromatic polyimides are described. The polyimides show desirable features of materials for microelectronics applications.

Chain Conformation and Local Rigidity of Soluble Polyimides(II):Isomerized Polyimides in THF

Two soluble isomerized polyimides（PIs） synthesized from 2,2＇-bis（3,4-dicarboxyphenyl）hexafluoropropane dianhydride（6FDA） with either 2,2＇-dimethylbenzidine（2,2＇-DMB） or 3,3＇-DMB were investigated by means of size-exclusion chromatography coupled with multi-angle laser light scattering,a viscometer and a refractive index detector in tetrahydrofuran（THF） with tetrabutylammonium bromide（TBAB） at 35 ℃.The corresponding parameters related to conformations α and ν,evaluated from the scaling relationships [η]=K η M α and R g =K g M ν,respectively,were 0.66±0.01 and 0.55±0.02 for poly（6FDA/3,3＇-DMB）,and 0.67±0.01 and 0.56±0.01 for poly（6FDA/2,2＇-DMB）,indicating a random coil conformation for both the samples in this mobile system.The persistence length l p and shift factor M L（relative molecular weight per unit contour length） were estimated from the relationship between intrinsic viscosity and molecular weight for the wormlike cylinder model proposed by Bohdanecky.Both l p and M L showed that the two PIs in THF are flexible chains and exhibit some local rigidity to some extent.

SYNTHESIS AND CHARACTERIZATION OF ORGANO-SOLUBLE FLUORINATED POLYIMIDES FROM 4,4'-BIS(3-AMINO-5-TRIFLUOROMETHYLPHENOXY)-BIPHENYL AND VARIOUS AROMATIC DIANHYDRIDES

An aromatic diamine monomer,4,4'-bis(3-amino-5-trifluoromethyl phenoxy)-biphenyl (TFBPDA),wassynthesized via the nucleophilic displacement reaction of 3,5-dinitrobenzotrifluoride and 4,4'-biphenol.The monomer wasreacted with various aromatic dianhydrides via the high temperature polycondensation procedure to provide a series ofpolyimides.The polyimides,PI-1 to PI-4,show good solubility not only in aprotic solvents,such as N-methyl-2-pyrrolidinone and N,N-dimethylacetamide,but also in many common solvents,such as m-cresol,chloroform andcyclopentanone.PI-4,derived from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride and TFBPDA,was even soluble intoluene.Moreover,PI films exhibit good thermal stability,outstanding transparency in the visible light region and acceptablemechanical and electrical properties.The excellent combined properties of the polyimides make them as a good candidate forfabricating microelectronics.

NEW OPTICALLY ACTIVE AROMATIC POLYIMIDES Ⅱ: SYNTHESIS AND PROPERTIES OF OPTICALLY ACTIVE AROMATIC POLYIMIDE BASED ON (R)-(+)-2, 2′-BIS (2-TRIFLUORO-4-AMINOPHENOXY)-1, 1′-BINAPHTHYL

Optically active (R)-(+)-2, 2' -bis(2 -trifluoro-4 -aminophenoxy)- 1, 1' -binaphthyl was prepared from1, 1'-bi-2-naphthol. The optically active aromatic polyimide was also successfully synthesized. This newpolymer has good solubility, thermal stability etc. Its specific rotation was found to be +174°, and itschiroptical property was also studied.

Synthesis of novel aromatic polyimides containing bulky side chain for vertical alignment liquid crystals

In this study, a novel 4-（4-octyloxybenzoyloxy）biphenyl-3′,5′-diaminobenzoate and polyimides based on it were synthesized. The polyimide with mesogenic unit side chain exhibited excellent vertical alignment for nematic liquid crystal （LC）. The pretilt angles of LCs above 89° were kept after the rubbing process with 220 mm rubbing strength. The polyimide films as the alignment layer were baked at 120℃ for 12 h, the vertical alignment of LCs was still uniform and stable. Meanwhile, the UV-vis spectra of the noyel polyimide films showed the high transparency in a visible wave length.

Resolution of 3,3'-Dioxo-1,1'(3H,3(H)spirobi[isobenzofuran] -5,6,5'6'-tetracarboxylic acid and Optically active Polyimides thereof

3,3`-Dioxo-1,1'(3H,3'H)spirobi[isobenzofuran]-5,6,5',6'-tetracarboxylic acid 1 was resolved successfully and the corresponding optically active polyimides PI were synthesized. The properties of the optically active PI and the racemic one were investigated. The results showed that the specific rotation of (-)-PI was about two times to that of the (+)-PI, and the regularity of the optically active PI was higher than that of the racemic one.