Semi-alicyclic Polyimides Research Articles

Polarization Analysis and Humidity Dependence of Dielectric Properties of Aromatic and Semialicyclic Polyimides Measured at 10 GHz

Polarization Analysis and Humidity Dependence of Dielectric Properties of Aromatic and Semialicyclic Polyimides Measured at 10 GHz

Chemically imidized semi-alicyclic polyimides: the effect of catalyst type and imidization temperature

AbstractPolyimides are a group of polymers with excellent thermal and mechanical properties. However, generally, they exhibit brown coloration due to charge transfer interactions between diamine donor and dianhydride acceptor moieties. In this study, semi-alicyclic polyimides derived from cyclohexane tetracarboxylic dianhydride and 4,4′-oxydianiline were prepared using a two-step method, where the imidization step proceeded via a chemical route. The effects of the catalyst type (quinoline, triethylamine, and 1,4-diazabicyclo(2.2.2)octane (DABCO)) and reaction temperature (120, 140, and 160 °C) on the imidization process were evaluated using infrared spectroscopy and nuclear magnetic resonance spectroscopy. The prepared polyimides' thermal, mechanical, and optical properties were compared with those synthesized via standard thermal imidization. Polyimide films possessing favorable mechanical properties, thermal stability, and good optical transparency were prepared via a simple preparation route based on chemical imidization using the triethylamine catalyst at the reaction temperature of 160 °C, which was shown to be a promising way for the PI preparation on an industrial scale. Graphical abstract

Preparation and Characterization of Light-Colored Polyimide Nanocomposite Films Derived from a Fluoro-Containing Semi-Alicyclic Polyimide Matrix and Colloidal Silica with Enhanced High-Temperature Dimensionally Stability.

Light-colored and transparent polyimide (PI) films with good high-temperature dimensional stability are highly desired for advanced optoelectronic applications. However, in practice, the simultaneous achievement of good optical and thermal properties in one PI film is usually difficult due to the inter-conflicting molecular design of the polymers. In the present work, a series of PI-SiO2 nanocomposite films (ABTFCPI) were developed based on the PI matrix derived from hydrogenated pyromellitic anhydride (HPMDA) and an aromatic diamine containing benzanilide and trifluoromethyl substituents in the structure, 2,2'-bis(trifluoromethyl)-4,4'-bis [4-(4-aminobenzamide)]biphenyl (ABTFMB). The inorganic SiO2 fillers were incorporated into the nanocomposite films in the form of colloidal nanoparticles dispersed in the good solvent of N,N-dimethylacetamide (DMAc) for the PI matrix. The derived ABTFCPI nanocomposite films showed good film-forming ability, flexible and tough nature, good optical transparency, and good thermal properties with loading amounts of SiO2 up to 30 wt% in the system. The ABTFCPI-30 film with a SiO2 content of 30 wt% in the film showed an optical transmittance of 79.6% at the wavelength of 400 nm (T400) with a thickness of 25 μm, yellow index (b*) of 2.15, and 5% weight loss temperatures (T5%) of 491 °C, which are all comparable to those the pristine ABTFCPI-0 matrix without filler (T400 = 81.8%; b* = 1.77; T5% = 492 °C). Meanwhile, the ABTFCPI-30 film exhibited obviously enhanced high-temperature dimensional stability with linear coefficients of thermal expansion (CTE) of 25.4 × 10-6/K in the temperature range of 50 to 250 °C, which is much lower than that of the AMTFCPI-0 film (CTE = 32.7 × 10-6/K).

Enhancing optical, dielectric, and thermal properties of bio-based polyimides incorporating isomannide with a bent and sterically constrained conformation

The optical, dielectric, and thermal properties of semi-alicyclic polyimides containing bio-based isosorbide moiety in the main chain were remarkably enhanced by incorporating 10–30 mol% of sterically constrained isomannide moiety.

Colorless, Low Dielectric, and Optically Active Semialicyclic Polyimides Incorporating a Biobased Isosorbide Moiety in the Main Chain

Colorless, Low Dielectric, and Optically Active Semialicyclic Polyimides Incorporating a Biobased Isosorbide Moiety in the Main Chain

Preparation of semi-alicyclic homo- and blended polyimide membranes using alicyclic dianhydrides with kink structures and their gas separation properties

Aromatic polyimides are promising membrane materials for gas separation due to their excellent gas separation properties. Herein, two soluble semi-alicyclic polyimides were synthesized via a one-step thermal imidization process with two semi-alicyclic dianhydrides possessing kink structures: bicyclo[2,2,2] oct-7ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA), and a flexible aromatic diamine: 4,4′-Oxydianiline (ODA). Their homo- and blended membranes were prepared in various mixing ratios (100/0, 75/25, 50/50, 25/75, and 0/100) and their gas permeation properties were investigated for five gases (H2, CO2, O2, N2, and CH4) and selectivity for five gas pairs (H2/CH4, H2/N2, CO2/CH4, CO2/N2, and O2/N2). The homopolyimides (BCDA-ODA, DOCDA-ODA) exhibited amorphous structure without crystallinity and good solubilities in the casting solvents. BCDA-ODA showed larger d-spacing/FFV values, higher gas diffusivities/gas solubilities than DOCDA-ODA, resulted in higher gas permeabilities and lower gas selectivity, which were remarkably affected by feed temperature. Also, the gas permeability and selectivity of the blended membranes were dependent upon the BCDA/DOCDA mole ratio. The good gas separation performances of homo- and blended membranes were observed for H2/CH4, H2/N2, CO2/CH4, and O2/N2, which are comparable to those of commercial membrane materials such as P84®, PSF, CA, Matrimid®, etc.

Enhancement of Ultraviolet Light Resistance of Colorless and Transparent Semi-Alicyclic Polyimide Nanocomposite Films via the Incorporation of Hindered Amine Light Stabilizers for Potential Applications in Flexible Optoelectronics.

Optically transparent polymer films with excellent thermal and ultraviolet (UV) resistance have been highly desired in advanced optoelectronic fields, such as flexible substrates for photovoltaic devices. Colorless and transparent polyimide (CPI) films simultaneously possess the good thermal stability and optical transparency. However, conventional CPI films usually suffered from the UV exposure and have to face the deterioration of optical properties during the long-term service in UV environments. In the current work, the commercially available hindered amine light stabilizers (HALS) were tried to be incorporated into the semi-alicyclic CPI matrix with the aim of enhancing the UV exposure stability. For this target, a CPI-0 film was first prepared from hydrogenated pyromellitic dianhydride (HPMDA) and 2,2′-dimethylbenzidine (DMBZ) via a one-step polycondensation procedure. Then, the commercially available HALS were incorporated into the CPI-0 (HPMDA-DMBZ) film matrix to afford four series of CPI/HALS composite films. Experimental results indicated that the Tinuvin® 791 HALS showed the best miscibility with the CPI-0 film matrix and the derived CPI-D series of composite films exhibited the best optical transmittances. The CPI-D nanocomposite films showed apparently enhanced UV exposure stability via incorporation of the 791 additives. For the pristine CPI-0 film, after the UV exposure for 6 h, the optical properties, including the transmittance at the wavelength of 350 nm (T350), lightness (L*), yellow indices (b*), and haze obviously deteriorated with the T350 values from 55.7% to 17.5%, the L* values from 95.12 to 91.38, the b* values from 3.38 to 21.95, and the haze values from 1.46% to 9.33%. However, for the CPI-D-10 film (791: CPI-0 = 1.0 wt%, weight percent), the optical parameters were highly maintained with the T350 values from 61.4% to 53.8%, the L* values from 95.46 to 95.36, the b* values from 1.84 to 1.51, and the haze values from 0.69% to 3.34% under the same UV aging conditions.

Electrospun Semi-Alicyclic Polyimide Nanofibrous Membrane: High-Reflectance and High-Whiteness with Superior Thermal and Ultraviolet Radiation Stability for Potential Applications in High-Power UV-LEDs.

Polymeric nanofibrous membranes (NFMs) with both high whiteness and high thermal and ultraviolet (UV) stability are highly desired as reflectors for ultraviolet light-emitting diodes (UV-LEDs) devices. In the current work, a semi-alicyclic and fluoro-containing polyimide (PI) NFM with potential application in such kinds of circumstances was successfully fabricated from the organo-soluble PI resin solution via a one-step electrospinning procedure. In order to achieve the target, a semi-alicyclic PI resin was first designed and synthesized from an alicyclic dianhydride, 3,4-dicarboxy-1,2,3,4,5,6,7,8-decahydro-1-naphthalenesuccinic dianhydride (or hydrogenated tetralin dianhydride, HTDA), and a fluoro-containing diamine, 2,2-bis[4-(4-amino-phenoxy)phenyl]hexafluoropropane (BDAF), via an imidization procedure. The derived PI (HTDA-BDAF) resin possessed a number-average molecular weight (Mn) higher than 33,000 g/mol and was highly soluble in polar aprotic solvents, such as N,N-dimethylacetamide (DMAc). The electrospinning solution was prepared by dissolving the PI resin in DMAc at a solid content of 25–35 wt%. For comparison, the conventional high-whiteness polystyrene (PS) NFM was prepared according to a similar electrospinning procedure. The thermal and UV stability of the derived PI and PS NFMs were investigated by exposure under the UV-LED (wavelength: 365 nm) irradiation. Various thermal evaluation results indicated that the developed PI (HTDA-BDAF) NFM could maintain both the high reflectance and high whiteness at elevated temperatures. For example, after thermal treatment at 200 °C for 1 h in air, the PI (HTDA-BDAF) NFM exhibited a reflectance at a wavelength of 457 nm (R457) of 89.0%, which was comparable to that of the pristine PI NMF (R457 = 90.2%). The PI (HTDA-BDAF) NFM exhibited a whiteness index (WI) of 90.88, which was also close to that of the pristine sample (WI = 91.22). However, for the PS NFM counterpart, the R457 value decreased from the pristine 88.4% to 18.1% after thermal treatment at 150 °C for 1 h, and the sample became transparent. The PI NFM maintained good optical and mechanical properties during the high dose (2670 J/cm2) of UV exposure, while the properties of the PS NFM apparently deteriorated under the same UV aging.

Preparation and properties of light-colored and transparent semi-alicyclic polyimide films with enhanced flame retardancy from alicyclic dianhydrides and aromatic diamine containing phenolphthalein unit

Preparation and properties of light-colored and transparent semi-alicyclic polyimide films with enhanced flame retardancy from alicyclic dianhydrides and aromatic diamine containing phenolphthalein unit

Preparation, characterization, and continuous manufacturing of nonflammable colorless and transparent semi-alicyclic polyimide film modified with phenoxy- phosphazene oligomer flame retardant

Preparation, characterization, and continuous manufacturing of nonflammable colorless and transparent semi-alicyclic polyimide film modified with phenoxy- phosphazene oligomer flame retardant

Surface alteration implications on potential use of semi-alicyclic polyimide as biomedical materials

A semi-alicyclic polyimide (PI) is tested for hemocompatibility and cell growth purposes. The PI configuration in the presence of the adhesion proteins and interaction energy were computed showing a different stability dictated by the protein structure. PI film surface was altered by roughening with sand paper and the morphology was examined by atomic force microscopy (AFM). The recorded images show a conversion of the initial isotropic peak-to-valley height on the surface of the PI film into an anisotropic one made of microgrooves. This is supported by the amplitude distribution function, which for the pristine sample has a narrow peak (a single morphological entity), while upon surface roughening, it has two peaks, associated with tracks valleys and top of the hills. The shape parameters (skewness and kurtosis) related to the asymmetry of the surface departure and spread of the height distribution are significantly changed after altering of the PI surface. The values of the surface functional indexes and functional volume parameters are increasing upon the PI surface roughening. The changes in random character of the initial PI are also evidenced by autocorrelation cross-section profile. The altered PI film surface determines an anisotropic character of adhesion or spreading of blood and fibroblasts.

Preparation and Characterization of Semi-alicyclic Polyimides Containing Trifluoromethyl Groups for Optoelectronic Application.

Transparent polyimides (PI) films with outstanding overall performance are attractive for next generation optoelectronic and microelectronic applications. Semi-alicyclic PIs derived from alicyclic dianhydrides and aromatic diamines have proved effective to prepare transparent PIs with high transmittance. To optimize the combined properties of semi-alicyclic PIs, incorporating bulky trifluoromethyl groups into the backbones is regarded as a powerful tool. However, the lack of fundamental understanding of structure–property relationships of fluorinated semi-alicyclic PIs constrains the design and engineering of advanced films for such challenging applications. Herein, a series of semi-alicyclic PIs derived from alicyclic dianhydrides and trifluoromethyl-containing aromatic diamines was synthesized by solution polycondensation at high temperature. The effects of alicyclic structures and bulky trifluoromethyl groups on thermal, dielectric and optical properties of PIs were investigated systematically. These PI films had excellent solubility, low water absorption and good mechanical property. They showed high heat resistance with Tg in the range of 294–390 °C. It is noted that tensile strength and thermal stability were greatly affected by the rigid linkages and alicyclic moieties, respectively. These films exhibited obviously low refractive indices and significantly reduced dielectric constants from 2.61 to 2.76, together with low optical birefringence and dielectric anisotropy. Highly transparent films exhibited cutoff wavelength even as low as 298 nm and transmittance at 500 nm over 85%, displaying almost colorless appearance with yellowness index (b*) below 4.2. The remarkable optical improvement should be mainly ascribed to both weak electron-accepting alicyclic units and bulky electron-withdrawing trifluoromethyl or sulfone groups. The present work provides an effective strategy to design molecular structures of optically transparent PIs for a trade-off between solution-processability, low water uptake, good toughness, high heat resistance, low dielectric constant and excellent optical transparency.

Reduced Coefficients of Linear Thermal Expansion of Colorless and Transparent Semi-Alicyclic Polyimide Films via Incorporation of Rigid-Rod Amide Moiety: Preparation and Properties

Semi-alicyclic colorless and transparent polyimide (CPI) films usually suffer from the high linear coefficients of thermal expansion (CTEs) due to the intrinsic thermo-sensitive alicyclic segments in the polymers. A series of semi-alicyclic CPI films containing rigid-rod amide moieties were successfully prepared in the current work in order to reduce the CTEs of the CPI films while maintaining their original optical transparency and solution-processability. For this purpose, two alicyclic dianhydrides, hydrogenated pyromellitic anhydride (HPMDA, I), and hydrogenated 3,3’,4,4’-biphenyltetracarboxylic dianhydride (HBPDA, II) were polymerized with two amide-bridged aromatic diamines, 2-methyl-4,4’-diaminobenzanilide (MeDABA, a) and 2-chloro-4,4’-diaminobenzanilide (ClDABA, b) respectively to afford four CPI resins. The derived CPI resins were all soluble in polar aprotic solvents, including N-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc). Flexible and tough CPI films were successfully prepared by casing the PI solutions onto glass substrates followed by thermally cured at elevated temperatures from 80 °C to 250 °C. The MeDABA derived PI-Ia (HPMDA-MeDABA) and PI-IIa (HBPDA-MeDABA) exhibited superior optical transparency compared to those derived from ClDABA (PI-Ib and PI-IIb). PI-Ia and PI-IIa showed the optical transmittances of 82.3% and 85.8% at the wavelength of 400 nm with a thickness around 25 μm, respectively. Introduction of rigid-rod amide moiety endowed the HPMDA-PI films good thermal stability at elevated temperatures with the CTE values of 33.4 × 10−6/K for PI-Ia and 27.7 × 10−6/K for PI-Ib in the temperature range of 50–250 °C. Comparatively, the HBPDA-PI films exhibited much higher CTE values. In addition, the HPMDA-PI films exhibited good thermal stability with the 5% weight loss temperatures (T5%) higher than 430 °C and glass transition temperatures (Tg) in the range of 349–351 °C.

Preparation and Characterization of Semi-Alicyclic Polyimide Resins and the Derived Alignment Layers for Liquid Crystal Display Technology.

Uniform alignment of rigid-rod liquid crystal (LC) molecules under applied voltage is critical for achievement of high-quality display for thin-film transistor-driven liquid crystal display devices (TFT-LCDs). The polymeric components that can induce the alignment of randomly aligned LC molecules are called alignment layers (ALs). In the current work, a series of organo-soluble polyimide (SPI) ALs were designed and prepared from an alicyclic dianhydride, hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA), and various aromatic diamines, including 4,4′-methylenedianiline (MDA) for SPI-1, 4,4′-aminodianiline (NDA) for SPI-2, 3,3′,5,5′-tetramethyl-4,4′-diaminodiphenylmethane (TMMDA) for SPI-3, and 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane (DMDEDA) for SPI-4. The derived SPI resins were all soluble in N-methyl-2-pyrrolidone (NMP). Four SPI alignment agents with the solid content of 6 wt.% were prepared by dissolving the SPI resins in the mixed solvent of NMP and butyl cellulose (BC) (NMP/BC = 80:20, weight ratio). Liquid crystal minicells were successfully fabricated using the developed SPI varnishes as the LC molecule alignment components. The SPI ALs showed good alignment ability for the LC molecules with the pretilt angles in the range of 1.58°–1.97°. The LC minicells exhibited good optoelectronic characteristics with voltage holding ratio (VHR) values higher than 96%. The good alignment ability of the SPI ALs is mainly attributed to the good comprehensive properties of the SPI layers, including high volume resistivity, high degree of imidization at the processing temperature (230 °C), good rubbing resistance, good thermal stability with glass transition temperatures (Tgs) higher than 260 °C, and excellent optical transparency with the transmittance higher than 97% at the wavelength of 550 nm.

Enhancement of Flame Retardancy of Colorless and Transparent Semi-Alicyclic Polyimide Film from Hydrogenated-BPDA and 4,4'-oxydianiline via the Incorporation of Phosphazene Oligomer.

Enhancement of flame retardancy of a colorless and transparent semi-alicyclic polyimide (PI) film was carried out by the incorporation of phosphazene (PPZ) flame retardant (FR). For this purpose, PI-1 matrix was first synthesized from hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and 4,4′-oxydianiline (ODA). The soluble PI-1 resin was dissolved in N,N-dimethylacetamide (DMAc) to afford the PI-1 solution, which was then physically blended with PPZ FR with the loading amounts in the range of 0–25 wt.%. The PPZ FR exhibited good miscibility with the PI-1 matrix when its proportion was lower than 10 wt.% in the composite films. PI-3 composite film with the PPZ loading of 10 wt.% showed an optical transmittance of 75% at the wavelength of 450 nm with a thickness of 50 μm. More importantly, PI-3 exhibited a flame retardancy class of UL 94 VTM-0 and reduced total heat release (THR), heat release rate (HRR), smoke production rate (SPR), and rate of smoke release (RSR) values during combustion compared with the original PI-1 film. In addition, PI-3 film had a limiting oxygen index (LOI) of 30.9%, which is much higher than that of PI-1 matrix (LOI: 20.1%). Finally, incorporation of PPZ FR decreased the thermal stability of the PI films. The 10% weight loss temperature (T10%) and the glass transition temperature (Tg) of the PI-3 film were 411.6 °C and 227.4 °C, respectively, which were lower than those of the PI-1 matrix (T10%: 487.3 °C; Tg: 260.6 °C)

Preparation and Characterization of Novel Preimidized Semi-alicyclic Polyimide Alignment Layers with Low Curing Temperature and High Voltage Holding Ratio for TFT-LCDs

Novel preimidized semi-alicyclic polyimide (PI) alignment layers with low curing temperature and high voltage holding ratio (VHR) have been successfully developed in order to meet the demands for l...

Semi-alicyclic polyimides as potential membrane oxygenators: Rheological implications on film processing, morphology and blood compatibility

Semi-alicyclic polyimides as potential membrane oxygenators: Rheological implications on film processing, morphology and blood compatibility

Electrospun polyimide ultrafine non-woven fabrics with high whiteness and good thermal stability from organo-soluble semi-alicyclic polyimides: Preparation and properties

Electrospun polyimide ultrafine non-woven fabrics with high whiteness and good thermal stability from organo-soluble semi-alicyclic polyimides: Preparation and properties

Highly transparent preimidized semi-alicyclic polyimide varnishes with low curing temperatures and desirable processing viscosities at high solid contents: preparation and applications for LED chip passivation

A series of semi-alicyclic polyimide (PI) resins with the number average molecular weights (Mn) in the range of 34901–74790 g/mol were prepared from a hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and various aromatic diamines by a high-temperature polycondensation procedure. For comparison, the analogous PI reference resins were prepared from hydrogenated 1,2,4,5-pyromellitic dianhydride (HPMDA) and the same aromatic diamines. The prepared PI resins were all soluble in polar aprotic solvents, such as N-methyl-pyrrolidinone (NMP) and N,N-dimethylacetamide (DMAc). Various PI varnishes with the solid contents as high as 35–45 wt% were successfully prepared by dissolving the PI resins in NMP. Some of the PI varnishes, including PI-3 derived from HBPDA and 1,3-bis(3-aminophenoxy)benzene (133APB), PI-5 from HBPDA and 2,2′-bis(trifluoromethyl)benzidine (TFMB), and PI-3′ from HPMDA and 133APB exhibited desirable processing viscosities at high solid contents. For example, when the solid content was 35 wt%, the PI varnishes showed absolute viscosities of 2144 mPa s for PI-3, 9971 mPa s for PI-5, and 3156 mPa s for PI-3′, respectively. The values were 6877 mPa s for PI-3, 42370 mPa s for PI-5, and 13700 mPa s for PI-3′, respectively when the solid contents of the PI varnishes increased to 40 wt%. This unique feature made the current PI varnishes good candidates as thick-film passivation layers for chip protection. Bare light emitting diodes chips were successfully passivated via once coating by using PI-5 (HBPDA–TFMB) varnish with a solid content of 35 wt%. The HBPDA–PI passivation layers exhibited good thermal stabilities with the glass transition temperatures (Tg) in the range of 171.5–296.3 °C and 5% weight loss temperatures higher than 470 °C. In addition, they showed good optical transparency with the transmittance higher than 72% at 450 nm at a thickness of 25 µm and low yellow indices and haze values.

Novel semi-alicyclic polyimide membranes: Synthesis, characterization, and gas separation properties

To develop membrane materials for gas separation, a series of semi-alicyclic polyimides was synthesized using one-step thermal solution imidization from an alicyclic dianhydride with non-planar twisted structure, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA). All synthesized polyimides exhibited amorphous structures and superior thermal stability, with high glass transition temperatures (242–288 °C) withstanding high operation temperature and pressure. They also showed excellent solubility in many polar organic solvents commonly used in the fabrication of gas separation membranes. The gas permeation properties of the polyimide membranes were measured for six representative gases (H2, CO2, O2, CO, N2, and CH4). The gas permeabilities and selectivities of polyimide membranes were significantly influenced by the chemical structure of the diamines, which could be explained reasonably by the kinetic diameter of gases, the fractional free volumes, and d-spacing values of the polyimides. Two DOCDA-based polyimides showed very high selectivities for H2/CH4 and CO2/CH4 and slightly low permeabilities for H2 and CO2, which performances were comparable to the commercial polyimide materials such as P84® and Matrimid® used in gas separation field.