New comonomer synthesis from thiophene-2-carbonyl chloride and cyclohexanone formaldehyde resin

2015 ◽  
Vol 44 (2) ◽  
pp. 79-86 ◽  
Author(s):  
Esin Ateş ◽  
Nilgün Kizilcan ◽  
Merve İstif
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Chemical Oxidation ◽  
Esterification Reaction ◽  
Formaldehyde Resin ◽  
Hydroxyl Groups ◽  
Content Type ◽  
Carbonyl Chloride ◽  
Oxidation System

Purpose – The purpose of this paper is to synthesise an electro-active monomer containing ketonic resins and then to investigate the redox reaction between Fe+3 and bound thiophene in comonomer. First, thiophene-functionalised ketonic resins were synthesised by esterification reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of cyclohexanone formaldehyde resin (CFR). Thiophene-containing cyclohexanone formaldehyde resin (Th-CFR) was then polymerised by ferric salt. The structures of the specimens were characterised by means of Fourier transform infrared and Proton – Nuclear Magnetic Resonanse (1H-NMR) spectroscopy. Thermal properties of the samples were determined with differential scanning calorimeter. Molecular weights of the specimens were determined by gel permeation chromatography. The obtained samples were also characterised morphologically by scanning electron microscope. Design/methodology/approach – Synthesis of Th-CFR comonomers by a combination of condensation polymerization and chemical oxidation polymerisation processes is described. First, Th-CFR units were prepared by direct condensation reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of CFR. Then, the chemical oxidation (CO) of Th-CFR in the presence of anhydrous iron (III) chloride salt (FeCl3) was performed in chloroform (CHCl3)/acetonitrile mixture solutions at room temperature. Findings – The important structural factor determined quantitatively for Th-CFR is the CFR/ThCCl ratio after reaction. The effect of the mole ratio effect of ThCCl and ketonic resin on the solubility, molecular weight, Tm and Tg values of the comonomers (Th-CFRs) were investigated. Research limitations/implications – The ferric ion (Fe+3) has a standard oxidation potential. Furthermore, FeCl3 can react with thiophene to produce a cation radical. FeCl3 cannot react with hydroxyl groups of ketonic resins. When ferric is used for in situ chemical oxidation application at relatively low temperatures (e.g. < 20°C), the oxidation reactions are usually less aggressive. Practical implications – This work provides technical information for the synthesis of conducting block copolymer and for the synthesis of chain-extended resins. The modified resins contain electro-active monomer as thiophene. The chemical oxidation system has been used to polymerise these thiophene groups and resins with much higher molecular weight might be produced. These resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating. Social implications – This will be used for the preparation of AB- and ABA-type block copolymers. These block copolymers may exhibit different properties due to incorporation of monomer into the block copolymer structure. Originality/value – Novel Th-CFR comonomers were synthesised. These comonomers have higher glass transition temperature (Tg) and melting temperature (Tm) value than CFR alone. The chemical oxidation system has been used to polymerise these thiophene-functionalised ketonic resins.

Novel comonomer synthesis from thiophene-2-carbonyl chloride and polydimethylsiloxane modified cyclohexanone formaldehyde resin

2014 ◽  
Vol 43 (5) ◽  
pp. 277-284 ◽  
Author(s):  
Nilgun Kizilcan ◽  
Merve Istif
Keyword(s):  
Molecular Weight ◽  
Chemical Oxidation ◽  
Proton Nuclear Magnetic Resonance ◽  
Esterification Reaction ◽  
Formaldehyde Resin ◽  
Resonance Spectroscopy ◽  
Hydroxyl Groups ◽  
Content Type ◽  
Carbonyl Chloride ◽  
Oxidation System

Purpose – The purpose of this paper is to produce an electroactive monomer containing ketonic resins and then to investigate redox reaction between Fe+3 and bounded thiophene in comonomers. First, thiophene functionalised ketonic resins (Th-CFPDMSR) were synthesised by esterification reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of cyclohexanone formaldehyde resin (CFR). Th-CFPDMSR was then polymerised by ferric salt. Thiophene modified ketonic resins (Th-CFPDMSR) as comonomers were characterised by common techniques such as gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimeter and scanning electron microscope. Design/methodology/approach – Th-CFPDMSR comonomers were synthesised by esterification reaction of ThCCl and hydroxyl groups of ketonic resins. Then, the in-situ chemical oxidation (ISCO) of ThC-CFR in the presence of iron (III) chloride salt (FeCl3) was accomplished in chloroform/acetonitrile mixture solutions at room temperature. Findings – Important structural factor determined quantitatively for Th-CFPDMSR is the CFPDMS/TCCl ratio after reaction. The mole ratio effect of TCCl and ketonic resin on the solubility, molecular weight, melting temperature (Tm) and glass transition temperature (Tg) values of the comonomers (TCCl-CFPDMSR) was investigated. Research limitations/implications – The ferric ion (Fe+3) has a standard oxidation potential. Furthermore, FeCl3 can react with thiophene to produce a cation radical. FeCl3 cannot react with hydroxyl groups of ketonic resins. When ferric is used for ISCO application at relatively low temperatures (e.g. < 20°C), the oxidation reactions are usually less aggressive. Practical implications – This work provides technical information for the synthesis of conducting block copolymer and for the synthesis of chain-extended resins. The modified resins contain thiophene. The chemical oxidation system has been used to polymerise these thiophene groups, and resins with much higher molecular weight might be produced. The resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating. Originality/value – Novel Th-CFPDMSR comonomers were synthesised. These comonomers have higher Tg and Tm values than CF-PDMSR alone. The chemical oxidation system has been used to polymerise these thiophene functionalised ketonic resins.

Novel phenylacetylene based ketonic resins

2015 ◽  
Vol 44 (4) ◽  
pp. 198-204 ◽  
Author(s):  
N. Kizilcan ◽  
B. Erson
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Technical Information ◽  
Fluorescence Properties ◽  
Formaldehyde Resin ◽  
Step Method ◽  
Content Type ◽  
Naoh Solution ◽  
Copolymer Structure

Purpose – This paper aims to report the synthesis of resins having fluorescence properties, with the help of phenylacetylene (PhAc) by one-step method of in situ modification of ketonic resin. Cyclohexanone-formaldehyde resin (CFR) and acetophenone formaldehyde resin (AFR) were in situ modified with PhAc, in presence of sodium hydroxide (NaOH) by condensation polymerisation. Design/methodology/approach – Ketone, formalin and phenylacetylene were mixed and then 20% aqueous NaOH solution was added to produce the phenylacethylene modified ketonic resin. The solubility, molecular weight and thermal properties of the products were investigated. Findings – These new PhAc-modified ketonic resins (PAc-CFR and PAc-AFR) have fluorescence properties. Research limitations/implications – This study focuses on obtaining a fluorescence resin using a cyclohexanone, acetophenone and PhAc monomer which is an insulator. Practical implications – This study provides technical information for the synthesis of fluorescence comonomers. The modified resins contain acetylene groups. A chemical redox or radical system can be used to polymerise these acetylene groups and resins with much higher molecular weight. The resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating. Social implications – The resins will be used for the preparation of AB- and ABA-type block copolymers. These block copolymers may exhibit different properties due to incorporation of monomer into the block copolymer structure. Originality/value – PAc-CFR and PAc-AFR have been synthesised in the presence of a basic catalyst. Higher solubility and fluorescence intensity of the modified ketonic resins may increase their applications in the field of electroactive polymers and open new areas. These comonomers have fluorescence property.

The Chemistry of Phenol-Formaldehyde Resin Vulcanization of EPDM: Part I. Evidence for Methylene Crosslinks

1995 ◽  
Vol 68 (5) ◽  
pp. 717-727 ◽  
Author(s):  
Martin van Duin ◽  
Aniko Souphanthong
Keyword(s):  
Molecular Weight ◽  
Phenol Formaldehyde ◽  
Polymer System ◽  
Phenol Formaldehyde Resin ◽  
Formaldehyde Resin ◽  
Low Molecular Weight ◽  
Hydroxyl Groups ◽  
Reaction Products ◽  
Cure Reaction ◽  
Weight Model

Abstract The application of phenol-formaldehyde resins as crosslinking agents is increasing in importance due to the good high temperature properties of the corresponding vulcanizate and the use in thermoplastic vulcanizates. With respect to the chemistry of phenol-formaldehyde cure (reaction mechanism and structure of crosslink) there are still problems that have to be resolved. The reaction products of the phenol-formaldehyde resin curing of EPDM, contain 2-ethylidene norbornene (ENB) as the third monomer, have been studied. Since such an investigation is rather difficult to perform for the polymer system, a low molecular weight model for EPDM was used: 2-ethylidene norbornane (ENBH). Reaction of ENBH and a resole results in scission of the dimethylene ether bridges, i.e. in degradation of the resole into mono-, bis- and terisooctylphenol units. These are consequently converted into products, consisting of two ENBH molecules linked by mono-, bis- and terisooctylphenol units. The solid resole seems to be a technological solution for storing phenol in combination with formaldehyde. These results support the use of 2-hydroxymethylphenol (HMP) as a low molecular weight model for the resole. At low temperatures and/or short reaction times HMP oligomers (= resoles) and HMP oligomers linked to one ENBH molecule are formed, which are converted into ENBH/HMP (1:1) condensation products. The reaction products of ENBH with both the resole and HMP are shown to contain methylene linked structures, as demonstrated by the formation of monisooctylphenol crosslinks and the presence of residual unsaturation and hydroxyl groups, besides chroman linked structures. This is the first experimental evidence that during phenol-formaldehyde resin cure of rubber, formation of methylene bridges occurs.

Self-Assembly of Block Copolymers for Photonic-Bandgap Materials

MRS Bulletin ◽  
2005 ◽  
Vol 30 (10) ◽  
pp. 721-726 ◽  
Author(s):  
Jongseung Yoon ◽  
Wonmok Lee ◽  
Edwin L. Thomas
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Photonic Crystals ◽  
Liquid Crystalline ◽  
Photonic Bandgap ◽  
Photonic Bandgap Materials ◽  
Periodic Microstructures ◽  
Self Assembled ◽  
Bandgap Materials

AbstractSelf-assembled block copolymer systems with an appropriate molecular weight to produce a length scale that will interact with visible light are an alternative platform material for the fabrication of large-area, well-ordered photonic-bandgap structures at visible and near-IR frequencies.Over the past years, one-, two-, and three-dimensional photonic crystals have been demonstrated with various microdomain structures created through microphase separation of block copolymers. The size and shape of periodic microstructures of block copolymers can be readily tuned by molecular weight, relative composition of the copolymer, and blending with homopolymers or plasticizers.The versatility of photonic crystals based on block copolymers is further increased by incorporating inorganic nanoparticles or liquid-crystalline guest molecules (or using a liquid-crystalline block), or by selective etching of one of the microdomains and backfilling with high-refractive-index materials. This article presents an overview of photonic-bandgap materials enabled by self-assembled block copolymers and discusses the morphology and photonic properties of block-copolymer-based photonic crystals containing nanocomposite additives.We also provide a view of the direction of future research, especially toward novel photonic devices.

Compatibility of Copolymers with Corresponding Homopolymers

1969 ◽  
Vol 42 (2) ◽  
pp. 447-461 ◽  
Author(s):  
G. Riess ◽  
J. Kohler ◽  
C. Tournut ◽  
A. Banderet
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Impact Strength ◽  
Methyl Methacrylate ◽  
Polymer Solutions ◽  
Random Copolymers ◽  
Ternary Diagrams ◽  
Two Systems

Abstract Since incompatibility of two homopolymers is the rule, it was of interest to see if mixing a corresponding copolymer (graft, block, or random) with a mixture of two incompatible homopolymers would bring about compatibility. For this study we limited ourselves to two systems of atactic polymers: polystyrene/poly (methyl methacrylate), and polystyrene/cis-l,4-polyisoprene since, in these systems, no crystallization occurs at normal temperatures. Investigation of these systems in the solid state—i.e., as films, prepared from polymer solutions by evaporation, enabled us to establish compatibility limits with considerable accuracy. The most important parameters for compatibility of homopolymer-copolymer mixtures seem to be, among other things: composition, molecular weight, and structure of the copolymers. Ternary diagrams for a mixture of two homopolymers and a copolymer show quite plainly that only block copolymers induce a certain compatibility. This is especially true when the polymer proportion in the block copolymers is approximately 50/50, and molecular weight of the homopolymers is substantially lower than that of the copolymer. Graft and random copolymers have little or no effect at all, upon compatibility. We also examined the relation between compatibility and impact strength for the system: polystyrene/polyisoprene/block copolymer.

scholarly journals Synthesis and Properties of Bioresorbable Block Copolymers of l-Lactide, Glycolide, Butyl Succinate and Butyl Citrate

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 214 ◽  
Author(s):  
Natalia Śmigiel-Gac ◽  
Elżbieta Pamuła ◽  
Małgorzata Krok-Borkowicz ◽  
Anna Smola-Dmochowska ◽  
Piotr Dobrzyński
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Biomedical Applications ◽  
Chain Growth ◽  
Hydroxyl Groups ◽  
Butylene Succinate ◽  
Branched Copolymers ◽  
Ultrahigh Molecular Weight ◽  
Biological Tests ◽  
Polymerization Mixture

The paper presents the course of synthesis and properties of a series of block copolymers intended for biomedical applications, mainly as a material for forming scaffolds for tissue engineering. These materials were obtained in the polymerization of l-lactide and copolymerization of l-lactide with glycolide carried out using a number of macroinitiators previously obtained in the reaction of polytransesterification of succinic diester, citric triester and 1,4-butanediol. NMR, FTIR and DSC were used to characterize the materials obtained; wettability and surface free energy were assessed too. Moreover, biological tests, i.e., viability and metabolic activity of MG-63 osteoblast-like cells in contact with synthesized polymers were performed. Properties of obtained block copolymers were controlled by the composition of the polymerization mixture and by the composition of the macroinitiator. The copolymers contained active side hydroxyl groups derived from citrate units present in the polymer chain. During the polymerization of l-lactide in the presence of polyesters with butylene citrate units in the chain, obtained products of the reaction held a fraction of highly branched copolymers with ultrahigh molecular weight. The reason for this observed phenomenon was strong intermolecular transesterification directed to lactidyl side chains, formed as a result of chain growth on hydroxyl groups related to the quaternary carbons of the citrate units. Based on the physicochemical properties and results of biological tests it was found that the most promising materials for scaffolds formation were poly(l-lactide–co–glycolide)–block–poly(butylene succinate–co–butylene citrate)s, especially those copolymers containing more than 60 mol % of lactidyl units.

Intensely phosphorescent block copolymer micelles containing gold(i) complexes

Soft Matter ◽  
2018 ◽  
Vol 14 (18) ◽  
pp. 3521-3527 ◽  
Author(s):  
Pingxia Guo ◽  
Qun He ◽  
Chen Wang ◽  
Zaili Hou ◽  
Bingran Yu ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Luminescence Enhancement ◽  
Block Copolymer Micelles ◽  
Copolymer Micelles ◽  
Cationic Gold

Micellization of anionic block copolymers with cationic gold(i) complexes induces remarkable phosphorescence enhancement in solution. The extent of the luminescence enhancement increases with increasing molecular weight of the anionic block.

Cationic polymerization of 1,3-dioxolane and 1,3-dioxepane. Application to graft and block copolymer synthesis

1985 ◽  
Vol 63 (1) ◽  
pp. 264-269 ◽  
Author(s):  
Léonard C. Reibel ◽  
Claude P. Durand ◽  
Emile Franta
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Cationic Polymerization ◽  
Weight Control ◽  
Graft Copolymers ◽  
Living Conditions ◽  
Molecular Weight Control ◽  
Central Block ◽  
Living Polymers

The cationic polymerization of 1,3-dioxolane and 1,3-dioxepane has been investigated to prepare "living" polymers and then to use them for copolymerization. Carbenium hexafluoroantimonate salts that are good initiators for tetrahydrofuran polymerization have been tested but produce unsatisfactory results with these acetals. In contrast, triflic anhydride, another good initiator for tetrahydrofuran polymerization, allows molecular weight control. Attempts to prepare block copolymers of two acetals by adding the second one to the first one under living conditions were unsuccessful because of randomization through transacetalization. Block copolymers containing a central block of polydioxepane and outer blocks of 1,2-dimethoxyethylene could be prepared by addition of the latter to living polydioxepane. Active polydioxolane reacts readily with polystyrene and leads to the formation of graft copolymers in the absence of gel.

scholarly journals Block Copolymer Synthesis by the Combination of Living Cationic Polymerization and Other Polymerization Methods

2021 ◽  
Vol 9 ◽  
Author(s):  
Asmita Dey ◽  
Ujjal Haldar ◽  
Priyadarsi De
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Cationic Polymerization ◽  
Chemical Properties ◽  
Good Control ◽  
Vital Role ◽  
Living Cationic Polymerization ◽  
Wide Range ◽  
Post Modification

The foremost limitation of block copolymer synthesis is to polymerize two or more different types of monomers with different reactivity profiles using a single polymerization technique. Controlled living polymerization techniques play a vital role in the preparation of wide range of block copolymers, thus are revolutionary techniques for polymer industry. Polymers with good control over molecular weight, molecular weight distribution, chain-end functionality and architectures can be prepared by these processes. In order to improve the existing applications and create new opportunities to design a new block copolymer system with improved physical and chemical properties, the combination of two different polymerization techniques have tremendous scope. Such kinds of macromolecules may be attended by combination of homopolymerization of different monomers by post-modification techniques using a macroinitiator or by using a dual initiator which allows the combination of two mechanistically distinct techniques. This review focuses on recent advances in synthesis of block copolymers by combination of living cationic polymerization with other polymerization techniques and click chemistry.

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