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 of Fluorinated Amphiphilic Block Copolymers Based on PEGMA, HEMA, and MMA via ATRP and CuAAC Click Chemistry

2014 ◽  
Vol 2014 ◽  
pp. 1-11 ◽  
Author(s):  
Fatime Eren Erol ◽  
Deniz Sinirlioglu ◽  
Sedat Cosgun ◽  
Ali Ekrem Muftuoglu
Keyword(s):  
Block Copolymer ◽  
Block Copolymers ◽  
Amphiphilic Block Copolymers ◽  
Random Copolymers ◽  
Side Chain ◽  
Dipolar Cycloaddition ◽  
Controlled Synthesis ◽  
H Nmr ◽  
Ft Ir ◽  
Click Coupling

Synthesis of fluorinated amphiphilic block copolymers via atom transfer radical polymerization (ATRP) and Cu(I) catalyzed Huisgen 1,3-dipolar cycloaddition (CuAAC) was demonstrated. First, a PEGMA and MMA based block copolymer carrying multiple side-chain acetylene moieties on the hydrophobic segment for postfunctionalization was carried out. This involves the synthesis of a series of P(HEMA-co-MMA) random copolymers to be employed as macroinitiators in the controlled synthesis of P(HEMA-co-MMA)-block-PPEGMA block copolymers by using ATRP, followed by a modification step on the hydroxyl side groups of HEMA via Steglich esterification to afford propargyl side-functional polymer, alkyne-P(HEMA-co-MMA)-block-PPEGMA. Finally, click coupling between side-chain acetylene functionalities and 2,3,4,5,6-pentafluorobenzyl azide yielded fluorinated amphiphilic block copolymers. The obtained polymers were structurally characterized by1H-NMR,19F-NMR, FT-IR, and GPC. Their thermal characterizations were performed using DSC and TGA.

Aromatic thioketone-mediated radical polymerization of methacrylates and the preparation of amphiphilic quasi-block copolymers

2020 ◽  
Vol 11 (18) ◽  
pp. 3251-3259
Author(s):  
Haoyu Yu ◽  
Jianwei Shao ◽  
Dong Chen ◽  
Li Wang ◽  
Wantai Yang
Keyword(s):  
Block Copolymer ◽  
Block Copolymers ◽  
Methyl Methacrylate ◽  
Radical Polymerization ◽  
Control Radical Polymerization ◽  
Strong Ability

TfXT exhibits strong ability to control radical polymerization of methyl methacrylate and has been used in preparing amphiphilic quasi-block copolymer.

Synthesis and thermal properties of triblock copolymers of methyl methacrylate using combination of anionic and controlled radical polymerization: Poly(methyl methacrylate) center block bearing different microstructures

e-Polymers ◽  
2012 ◽  
Vol 12 (1) ◽  
Author(s):  
Zhengji Song ◽  
Carole Pelletier ◽  
Yinghua Qi ◽  
Jasim Ahmed ◽  
Sunil K. Varshney ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Thermal Properties ◽  
Block Copolymers ◽  
Methyl Methacrylate ◽  
Radical Polymerization ◽  
Triblock Copolymers ◽  
Controlled Radical Polymerization ◽  
Alkyl Methacrylate ◽  
Poly Methyl Methacrylate ◽  
H Nmr

AbstractABA and/or ABC type triblock copolymers were synthesized by living anionic and controlled radical polymerization in which poly(methyl methacrylate) was used as central block. The structural composition of these block copolymers were determined by 1H NMR. The block length/molecular weight and microstructure of these polymers were measured by SEC. The microstructure of resultant central alkyl methacrylate block can be tailored from highly syndiotactic to highly isotactic structure by varying the solvent and/or initiator. The thermal and rheological properties of center poly(methyl methacrylate) block and poly(styreneb- methyl methacrylate-b- styrene) tri block copolymers were studied in detail.

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.

Synthesis of acrylic hot-melt adhesive based on poly(methyl methacrylate)-b-poly(2-ethylhexyl acrylate) copolymer using atom transfer radical polymerization for a nylon fabric bonding system

2019 ◽  
Vol 89 (23-24) ◽  
pp. 5177-5186
Author(s):  
Chung-Feng Jeffrey Kuo ◽  
Jiong-Bo Chen ◽  
Po-Yen Chen ◽  
Garuda Raka Satria Dewangga
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Methyl Methacrylate ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Atom Transfer ◽  
Poly Methyl Methacrylate ◽  
Bonding System ◽  
Nylon Fabric ◽  
Hot Melt

Adhesives, such as hot-melt adhesives (HMAs), are widely used in the textile industry for bonding layers of materials and have replaced traditional sewing methods. The block copolymer is a common type of HMA that provides excellent physical features and mechanical properties compared with others. Acrylate-based monomers, methyl methacrylate (MMA), and 2-ethylhexyl acrylate (2-EHA) were used as ingredients to form a linear block copolymer using atom transfer radical polymerization. MMA provides excellent cohesive strength, while 2-EHA provides good adhesion properties. An end-brominated poly(methyl methacrylate) (PMMA-Br) macroinitiator was synthesized from a MMA monomer and initiator, with the best composition obtained by the addition of a 0.6 mol initiator. The macroinitiator had the lowest molecular weight with highest conversion (97%). The addition of a 0.3 mol macroinitiator showed the lowest molecular weight with the highest conversion of acrylic copolymer PMMA- b-poly(2-ethylhexyl acrylate) (PEHA). The glass transition temperature increased with the addition of the macroinitiator concentration, from −43.7℃ to −37.6℃. The thermal stability was reduced with the addition of macroinitiator content, from 332.37℃ to 286.81℃. The shear strength and peel strength of the PMMA- b-PEHA HMAs on nylon fabrics were enhanced from 11.24 to 16.92 kg cm−2 and from 0.29 to 0.61 kg cm−1, respectively, and did not change significantly after being washed 50 times and then kept in low-temperature storage, with the addition of the macroinitiator concentration. The block copolymer PMMA- b-PEHA prepared in this study could be used as a HMA for nylon fabric bonding systems.

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.

Synthesis of poly(methyl methacrylate) and block copolymers by semi-batch nitroxide mediated polymerization

2016 ◽  
Vol 7 (45) ◽  
pp. 6964-6972 ◽  
Author(s):  
N. Ballard ◽  
A. Simula ◽  
M. Aguirre ◽  
J. R. Leiza ◽  
S. van Es ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Methyl Methacrylate ◽  
Polymer Structure ◽  
Solution Polymerization ◽  
Poly Methyl Methacrylate ◽  
Nitroxide Mediated Polymerization

The limits of control of the molecular weight and polymer structure in the semi-batch solution polymerization of methyl methacrylate by NMP are explored.

Preparation and Properties of Condensation Block Copolymers

1957 ◽  
Vol 30 (1) ◽  
pp. 283-295 ◽  
Author(s):  
D. H. Coffey ◽  
T. J. Meyrick
Keyword(s):  
Melting Point ◽  
Block Copolymers ◽  
Impact Strength ◽  
Hexamethylene Diisocyanate ◽  
Random Copolymers ◽  
Copolymer Composition ◽  
Block Copolymerization ◽  
Random Arrangement ◽  
Composition Curve ◽  
Point Composition

Abstract By using diisocyanates to link together two different polyesters having terminal hydroxyl or carboxyl groups, copolymers have been obtained in which the two repeating units occur in blocks and not in the random arrangement obtained by normal methods of preparing copolymers. Melting points have been measured by a penetrometer method and the effects of copolymer composition on melting point determined. In a series of crystalline copolymers made by linking various amounts of polyethylene sebacate and polyethylene adipate with hexamethylene diisocyanate, a step-shaped melting point-composition curve is obtained. Copolymers containing up to about 40 per cent of polyethylene adipate have the same melting point as that of polyethylene sebacate. Further increase in the polyethylene adipate content results in a rapid drop in melting point until the melting point of polyethylene adipate is reached. Thereafter increasing amounts of polyethylene adipate do not alter the melting point. Random copolymers of ethylene adipate and ethylene sebacate give a V-shaped melting point-composition curve. The step-shaped curve of block copolymers is almost identical with the melting point-composition curve of melt blends of the two polymers. Stress-strain characteristics and impact strengths of the block copolymers have been measured. In the polyethylene adipate/polyethylene sebacate/ hexamethylene diisocyanate series no great differences are found between random and block copolymers. If, however, the crystalline polyethylene adipate is replaced by the noncrystalline polypropylene adipate, then block copolymers containing 15–30 per cent of polypropylene adipate have outstanding impact strength. Similar high impact strength is obtained by using a compatible rubbery polymer as an external plasticizer with hexamethylene diisocyanate modified polyethylene sebacate. This method of block copolymerization has an advantage over random copolymerization in that a crystalline copolymer can be modified without reduction of its melting point, and by suitable selection of a second component it affords a means of “building in” a plasticizer.

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