Bis Monomers Research Articles

Michael Polyaddition Approach Towards Sulfur Enriched Nonaromatic Polymers with Fluorescence-Phosphorescence Dual Emission.

Nonaromatic photoluminescent polymers have attracted great attention due to their intriguing photophysical properties and promising implications in optoelectronic and biological areas. The luminescence from these nonconventional luminophores can be well rationalized by the clustering-triggered emission mechanism. Sulfur, although as an n-electron-rich element with big radius, is not been widely utilized in construction of nonconventional luminophores despite of its potential competitiveness in nonaromatic photoluminescent polymers. Herein, the "click" type Michael polyaddition is utilized to construct sulfur-bearing nonconventional luminophores, and two sulfur enriched nonaromatic poly(thioether sulfone)s (PES) are obtained, which demonstrate fluorescence-phosphorescence dual emission. More investigations concerning the monomer of bis(vinylsulfonyl)methane are further proceeded to support acquired results. Finally, the application of explosive detection by the prepared PES is also conducted.

New Strategy and Polymer Design to Synthesize Polyamide 66 (PA66) Copolymers with Aromatic Moieties from Recycled PET (rPET)

Recycling of poly(ethylene terephthalate) (PET) is considered to be a promising way to reduce environmental pollution. In this work, the valuable monomer bis(6-aminohexyl) terephthalamide (BAHT) co...

Circular recycling of polyester textile waste using a sustainable catalyst

A tremendous amount of polyester textile waste is discarded every year, which has caused a serious problem for the environment. In this study, the feasibility of circular recycling of polyester textile waste is investigated through a glycolysis process in the presence of environmentally friendly Mg–Al double oxides pellets as catalyst. Even though the catalytic performance of Mg–Al double oxides pellets is slightly lower than their granules at 240 °C, pellets were used as they benefit from a good recyclability. The pellet catalysts could be cycled three times without losing structural integrity or catalytic activity in the glycolysis of (poly(ethylene terephthalate)(PET)). However, to restore the catalytic activity after three cycles, the catalyst was regenerated through a heat treatment after the glycolysis reaction. After that the catalyst showed a comparable catalytic activity as that of virgin catalyst. In the glycolysis process, the monomer bis(hydroxyethyl) terephthalate (BHET) is generated and recovered. The molar yield of BHET was in the reaction over 80 mol%. From the recovered BHET, regenerated PET (r-PET) with an intrinsic viscosity (IV) of 0.67 was synthesized. The r-PET showed a very good spinnability in the melt spinning test. The quality of the obtained r-PET fibers was comparable to virgin PET fibers.

Fabrication of calcium hydroxyapatite incorporated polyurethane-graphene oxide nanocomposite porous scaffolds from poly (ethylene terephthalate) waste: A green route toward bone tissue engineering

Biodegradable porous polymeric scaffolds were prepared from Polyurethane (PU) for the purpose of osteoblast cells regeneration to utilize in the restoration of damage bone tissues. The PU was synthesized from post-consumer discarded Poly ethylene terephthalate (PET) waste by glycolysis method. The produced monomer bis(2-hydroxyethyl) terephthalate (BHET) was reacted with diisocynate and there after with selected chain extender glycol. In this study, graphene oxide (GO) was used as a polyol in the esterification reaction. Also, the GO acted as a nano filler that imparted the strength to the system along with antimicrobial activity. The various composites of PU-GO/hydroxyapatite (Hap) were prepared by varying the content of GO/Hap from 0 to 10% of total weight of the composite. The porous scaffolds were developed from composites by solvent casting/particulate leaching (SCPL) method. Furthermore, the physical, morphological, elemental, mechanical and thermo-mechanical properties of scaffolds were analyzed. The prepared scaffolds were subjected to U2OS human embryonic osteoblast cell line to analyze the response of osteoblast cells. In vitro studies such as cell growth, degradation, and cyto-compatibility were carried out. The outcomes of this study have asserted that the developed scaffolds are compatible for U2OS cells growth, thus can be used for bone tissue regeneration.

Facile synthesis of bio-based phosphorus-containing epoxy resins with excellent flame resistance

The development of high-performance biomass-derived epoxy thermosets with excellent flame resistance is vital to various applications (i.e., composites, coatings and adhesives). Herein, a difunctional epoxy monomer bis(2-methoxy-4-(oxiran-2-ylmethyl)phenyl) phenyl phosphate (BEU-EP) was synthesized from abundant and biobased eugenol. In addition, BEU-EP was cured by 4,4′-diaminodiphenyl methane (DDM) and the cured resin diglycidyl ether of bisphenol A (DGEBA)/DDM was used as a reference. Results indicated that BEU-EP/DDM not only showed a 58.1%, 28.8% and 35.1% increase in residual char (at 700 °C), flexural and storage modulus (at 30 °C) compared with DGEBA/DDM, but also exhibited excellent flame resistance and smoke suppression. BEU-EP/DDM passed V-0 rating (in UL-94 testing) with limiting oxygen index (LOI) of 38.4% and greatly decreased the peak heat release rate (pHRR) and total smoke production (TSP) by 84.9% and 80.5%, respectively. The mechanism analysis confirmed that the phosphorus-containing group and aromatic structure from BEU-EP contributed both the gas and condensed-phase flame retardation of BEU-EP/DDM network. This work provides an efficient and scalable route for synthesizing biobased epoxy thermosets with high integrated performance and superior flame resistance.

Degradation of poly(ethylene terephthalate) catalyzed by metal-free choline-based ionic liquids

Glycolysis of PET is a prospective way for degradation of PET to its monomer bis(hydroxyethyl)terephthalate (BHET) which can be polymerized again to form new qualified PET materials, and hence provides possibilities for a permanent loop recycling.

Model-based research toward design of innovative materials: molecular weight prediction of bridged polysilsesquioxanes.

Toward the design and manipulation of innovative materials, we propose a new concept called “model-based research (MBR)”. In MBR, measurable physical and chemical properties of materials are mathematically modelled by explanatory parameters obtained by computer simulation from an atomistic point of view. To demonstrate the potential of MBR, we modelled the molecular weights of a series of polysilsesquioxanes with respect to the H2O/silane molar ratio employed for the polymerization of monomers bis(triethoxysilyl)methane, ethane, ethylene, and acetylene (BTES-M, -E1, -E2, and -E3), as an example. The equation y = axn well reproduced the behaviour of the molecular weights of the BTES series, in which a and n were obtained using the calculated molecular parameters for monomers as the explanatory parameters. Detailed understanding and discussion were theoretically possible on the basis of the mathematical model. We predicted the molecular weights of polymers that would be obtained from monomers BTES-P and BTES-Ph with C3H6 and C6H4 as the spacer, respectively, using the mathematical model. Experimental validation of these polymers clearly showed the possibility of qualitative categorization. Our proposed concept, MBR, is a powerful tool to analyse materials science toward innovative materials design.

Evaluation of Physical Properties of Silica filled Resin Based Dental Composites

In this study, resin based dental composites were developed using monomers Bis GMA and TEGDMA, CQT and DMAEA. Silica were filled as filler material. After curing, the samples were tested for void content and water sorption and solubility. The results showed that as the void content increases, water sorption also increases in resin based dental composites. In brief, it can be stated through this experimental study that with the increase in silica filler upto 9 %wt, void content and water sorption both increases.

Ultrafast Homogeneous Glycolysis of Waste Polyethylene Terephthalate via a Dissolution-Degradation Strategy

Recycling of discarded polyethylene terephthalate (PET) is an important issue for both environmental protection and resource conservation purposes. In this work, a dissolution-degradation strategy has been developed for recycling PET by adding solvents such as aniline, nitrobenzene, 1-methyl-2-pyrrolidinone (NMP), or dimethyl sulfoxide (DMSO) into the traditional PET glycolysis system. The results show that the conversion of PET reaches 100% and the yield of monomer bis(hydroxyalkyl) terephthalate (BHET) reaches 82% during 1 min with zinc acetate as catalyst in DMSO at 463 K. Importantly, this strategy can be applied to a variety of catalysts. The simulation and in situ IR results indicate that the π–π interaction between PET and aromatic solvents plays a key role in PET dissolution, which leads to fast degradation. This promising dissolution-degradation strategy can improve the glycolysis efficiency of PET dramatically and may be applied to the degradation process of other polyesters.

Nano MgO catalyst for chemical depolymerization of polyethylene terephthalate (PET)

This paper focuses firstly on the production of monomers bis (2-hydroxyethyl) terephthalate (BHET) and oligomers by using two different form of MgO light active and Nano Magnesium oxide with different weight ratio (0.15, 0.25 and 0.5) by using chemical recycling glass condenser at 190 ˚C. The second purpose is to study the effect of catalyst ratio, time of reaction and yield of products of the product. Elemental analysis for Carbon –Hydrogen and Nitrogen (CHN), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) have been investigated. Results indicated the catalytic activity was found to correlate with surface area; however, LA MgO has shown an exceptional activity, still it is higher than Nano MgO in order to reduce the reaction time till 30 minutes instead of 7 hours without catalyst. The analysis of the thermograms has indicated the presence of various kinds of monomer, dimer and oligomers that are formed during the recycling; this is particularly evident due to new peaks indicating the formation of BHET monomer and oligomer of lower molecular masses.

Trace element determinations in uranium by Total reflection X-Ray Fluorescence spectrometry using a newly developed polymer resin for major matrix separation

Trace element determinations in uranium samples by Total reflection X-Ray Fluorescence (TXRF) spectrometry were carried out using a new polymer resin gel for uranium matrix elimination from the sample solutions. The resin was prepared by using the 1:1 mol proportion of monomers bis [2-(methacryloyloxy) ethyl] phosphate (bis-MEP) and 2-acrylamido-2-methyl propane sulfonic acid (AMPS). This new poly (bis-MEP-AMPS) resin has exhibited superior features for the trace element determinations in uranium matrix compared to the solvent extraction based methods, which could be attributed to its remarkable selectivity towards uranium in 4 M HNO3 medium without sacrificing its uptake efficiency (94%) just by simple equilibration of the resin in the solutions. The separation procedure is very simple and the polymer resin gel can be regenerated by sonicating in a 0.5 wt% Na2CO3 solution for one hour. This resin was successfully used for the trace elemental analysis in a certified reference material (CRM-IV) of uranium oxide by TXRF after separation of uranium from the sample matrix with satisfactory analytical results. Photoluminescence and FTIR studies were performed to understand the coordination of uranyl species with this polymer resin.

Preparation of photosensitive polyimides (PSPIs) and their feasible evaluation for lithographic insulation patterns (LIPs) of integrated circuits (ICs) without negative photoresists

A photosensitive polyimide (PSPI) with high glass transition temperature (Tg; 259 ℃), good inherent viscosity (I.V.; 0.31 dL/g), and superb decomposition temperature (Td; 368 ℃) has been manufactured by the appropriate prescription of diamine monomer (i.e. 2,2-bis (3-amino-4- hydroxyphenyl)-hexafluoropropane; APAF), dianhydride monomer (i.e. 4,4′-(4,4′- isopropylidenediphenoxy)bis(phthalic anhydride); BPADA), cyclodehydating agent (i.e. p-xylene), base (i.e. N,N,N-triethylamine; TEA), and photosensitive monomer (i.e. acryloyl chloride; AOC). In order to explore the applying feasibility, we have prepared lithographic insulation pattern resin (LIPR) of integrated circuit (IC) with PSPI (i.e. APAF/BPADA/AOC polyimide), solvent (i.e. N-methyl-2-pyrrolidone; NMP), photoinitiator (i.e. I-305), crosslinking agent (i.e. CLA-1), co-photoinitiator (i.e. I-309) as well as coupling agent (i.e. vinyltrimethoxysilane; VTES) and utilized it without negative photoreist by silicon wafer, i-line (wavelength: 365 nm; optical density: 1200 mW/cm2), and photomask. Experimental results reveal that lab-made LIPR of IC based on PSPI is a promising IC package material with high tensile strength of 106 MPa, excellent adhesion on silicon wafer (i.e. eligible of cross-cut examination), great coefficient of thermal expansion (CTE) of 17.9 ppm/℃, low dielectric constant (Dk) of 3.5, high surface electric resistance of 8.3 × 1011 Ω/sq., low dielectric loss (Df) of 0.01, moderate hygroscopicity of 2.9% (23 ℃, 24 h), and low residual stress of 32.0 MPa.

A new polymer field effect transistor based on fluorene derivative with fused furan rings

ABSTRACTComposed of novel monomer (10,10‐dihexyl‐10‐fluoreno[2,3‐b:7,6‐b′]difuran‐2,7‐diyl)bis(tri‐methylstannane) (DFF) and commercial 2,5‐di(2‐ethylhexyl)‐3,6‐di(5‐bromothiophen‐2‐yl)diketopyrrolopyrrole (DPP32), PDFFDPP32 is synthesized and systematically characterized by high‐temperature gel‐permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption, Fourier transform infrared spectroscopy, and cyclic voltammetry testing. The resulting polymer displays good hole transport behaviors in bottom gate/top contact organic field effect transistors (OFET) with hole mobility up to 6.42 × 10−3 cm2 V−1 s−1. The rough surface morphology of the polymer films is characterized by atomic force microscopy, and the polymer films are in an amorphous state, as demonstrated by X‐ray diffraction. The intra‐ and interchain O···S noncovalent interactions, as verified by X‐ray photoelectron spectroscopy, possibly endow the polymer with enhanced interactive forces among the polymeric chains. The results indicate that PDFFDPP32 has potential applications in OFET, and the novel monomer DFF has prospects for building high‐performance organic optoelectronic materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46865

Aromatic polyesters derived from 5,5′-disubstituted bis(m-phenylene) crown ethers

A new monomer of the AB type, 5-carboxy-1,3-phenylene-5′-hydroxy-1′,3′-phenylene-32-crown-10 (5), was synthesized. Direct polymerizations of bis(5-hydroxy-1,3-phenylene)-32-crown-10 (13), an AA diphenolic macrocyclic monomer, with BB diacid monomer bis(5-carboxy-1,3-phenylene)-26-crown-8 (14) and its larger analog bis(5-carboxy-1,3-phenylene)-32-crown-10 (16) were accomplished via the Higashi method. The resultant polyesters 15 and 17, which both contain two macrocycles per repeat unit, were soluble in common organic solvents such as chloroform and tetrahydrofuran, amorphous in nature and possessed high thermal stability (5% weight loss > 370 °C in air). Main chain poly(ester crown ether)s 18 and 19 based on bis(5-carboxy-1,3-phenylene)-32-crown-10 (16), and hydroquinone (HQ) and biphenol (BP), respectively, were synthesized; these two polyesters also possess high thermal stability (5% weight loss > 386 °C in air) and are amorphous. These polymacrocycles are suitable polytopic hosts for complexation with 4,4′-bipyridinium derivatives, as demonstrated by the binding of paraquat diol (21a) by polyester 20 with Ka = 2.0 (±0.7) x 102 M−1 (23 °C, 4:6 w:w CD3CN:CDCl3). Threading of the cyclic units in these polyesters by linear polymers such as polystyrene and PMMA leads to compatiblized blends via polypseudorotaxane formation; this methodology represents a new approach to compatibilization.

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

Fabrication of organic-inorganic bridged polysilsesquioxane (BPS) matrix containing polycarbonate diol (PCD) units for solid polymer electrolytes (SPEs)

ABSTRACTNew type of solid polymer electrolytes (SPEs) were synthesized by polycarbonate diol (PCD)-based bridged polysilsesquioxane (BPS) monomer and lithium bis(trifluoromethane)sulfonimidate (LiTFSI) via the sol-gel process. The ion conductivity of PCD-based BPS matrix was increased from 1.41 × 10−7 to 4.09 × 10−5 ((Ω · cm)−1) according to the amount of lithium salts at room temperature. The effect of lithium salts to the ion conductivity is attributed to the homogenous dispersion of lithium salts into the SPEs matrix. The thermal stability of PCD-based BPS matrix is higher than that of PCD oligomer and PCD-based BPS monomer in thermogravimetric analysis (TGA).

Crosslinking mechanisms, structure and glass transition in phthalonitrile resins: Insight from computer multiscale simulations and experiments

ABSTRACTThe influence of crosslinking process on the resulting structural properties of phthalonitrile matrices is studied through theoretical and experimental investigations. Multiscale procedure for generating fully atomistic phthalonitrile networks with simulation of radical polymerization reactions and specific reactions of triazine formation at the mesoscale level is presented and applied to the case of phthalonitrile resin based on low‐melting monomer bis(3‐(3,4‐dicyanophenoxy)phenyl)phenyl phosphate. The structural properties of the generated networks of various conversions and with various amount of triazine are analyzed using the dissipative particle dynamics and atomistic molecular dynamics. Triazine‐containing networks are much sparser in comparison with triazine‐free ones in terms of simple cycle size. The values of density, coefficients of linear thermal expansion and glass transition temperatures (Tgs) agree with obtained experimental data, and are very similar for different crosslinking mechanisms. The dependence of Tg on conversion correlates well with the sol–gel transition in network structure. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 362–374

Preparation and evaluation of waste PET derived polyurethane polymer modified bitumen through in situ polymerization reaction

Polymer modified bitumen (PMB) pavement have gained significant importance in the twentieth century and they now play a very crucial role in the field of road construction in every part of world. However, due to well-known difficulties related to the poor solubility of polymers, high temperature stability, sever manufacturing condition and high polymer cost restricts the use of polymer for bitumen modification. To overcome all these difficulties the present study has attempted to demonstrate a new approach where in situ polymerization of monomers bis(2-hydroxyethyl) terephthalamide (BHETA) (which is synthesized from aminolysis reaction of waste Poly Ethylene Terephthalate (PET)) with diphenylmethane-diisocyanate (MDI) in the body of bitumen for the development of polyurethane based Polymer modified bitumen (BHETA-PU). The resulting BHETA-PU product is comparable performance under laboratory condition with conventional styrene butadiene styrene (SBS) based PMB. To investigate the modifiedbitumen properties and mixture properties, conventional binder tests (Penetration, Softening Point, Marshall Stability, Hot water Stripping & short-term aging test) and Superpave binder tests (Rotational Viscosity, Dynamic Shear Rheometer (DSR), Bending Beam Rheometer (BBR) were carried out. The result reveals that BHETA-PU show significant improvement of antistripping as well as other physico-chemical properties and Marshall Stabilities. This research studies, therefore, suggests not only a new method for making PMB based on PET but also opens a new chapter for the recycling of waste PET in bitumen concrete roads which may help in easy disposal of waste PET polymer.

The One‐Stage Synthesis of Hyperbranched Polyimides by (A2+B4) Scheme in Catalytic Solvent

New tetraamine monomer bis(2,3‐diaminophenoxy)benzene (BDAPB) was synthesized by reducing corresponding precursor bis(2,3‐dinitrophenoxy)benzene with hydrazine hydrate. Hyperbranched polyimide with terminal amino groups was synthesized by means of the one‐stage high temperature polycondensation of BDAPB with 2,2‐propylidene‐(1,4‐phenyleneoxy)diphthalic acid in catalytically active solvent – molten benzoic acid at 140°C by the scheme A2+B4. Examples of polymer‐analog transformations were shown of terminal amino groups to form acetamide and phthalimide derivatives.

Nano ZnO Catalyst for Chemical Recycling of Polyethylene terephthalate (PET)

This paper is focused firstly on production of monomers bis (2-hydroxyethyl) terephthalate (BHET) and oligomers by using Nano zinc oxide with different particle size (55&94) nm with different weight ratio (0.05, 0.15 and 0.5) by using chemical recycling glass condenser at 190˚C. The second purpose is to study the effect of catalyst ratio, time of reaction and yield of products of the product. Elemental analysis for Carbon –Hydrogen and Nitrogen (CHN), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) have been investigated. Results indicated the catalytic activity was found to correlate with surface area; however, Nano ZnO (55) nm has shown an exceptional activity, still it is higher than Nano ZnO (94) nm in order to reduce the reaction time until 60 minutes instead of 7 hours without catalyst. The analysis of the thermograms has indicated the presence of various kinds of monomer, dimer and oligomers that are formed during the recycling; this is particularly evident due to new peaks indicating the formation of BHET monomer and oligomer of lower molecular masses.