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.

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.

The Heptacarboxylic Porphyrin of Various Types of Porphyria and the Melting-Point Curve of Methyl Esters of the I and III Isomers

1966 ◽  
Vol 12 (10) ◽  
pp. 647-658 ◽  
Author(s):  
T C Chu ◽  
Edith Ju-Hwa Chu
Keyword(s):  
Melting Point ◽  
South African ◽  
Porphyria Cutanea Tarda ◽  
Methyl Esters ◽  
Acute Intermittent Porphyria ◽  
Type I ◽  
X Ray Diffraction ◽  
Different Types ◽  
Composition Curve ◽  
Point Composition

Abstract The heptacarboxylic porphyrin (hepta) isolated from different types of porphyric urine samples contains different proportions of the isomers I and III. These were separated chromatographically. The hepta in congenital porphyria was found to contain 65% of Type I isomer and 35% of Type III; that in acute intermittent porphyria, 70-80% III and 20-30% I; and that in porphyria cutanea tarda, 80-90% III. Several other cases including 1 of coproporphyria, 1 of South African genetic porphyria, 1 of Bantu porphyria, 4 of hexachlorobenzene poisoning in Turkish individuals were also examined. From the X-ray diffraction pattern and long-column chromatography, the Hepta III prepared either from decarboxylation of Uroporphyrin III or by condensation of porphobilinogen revealed a more complex configuration than that isolated from porphyric materials. The natural hepta might be dominated by one of the four possible isomers of the III series. A melting-point composition curve of methyl esters of Hepta I and III was constructed, and its applicability was tested. The identity of the hepta isolated in porphyria cutanea tarda with "208" and "pseudouro" porphyrins is discussed, and the name "cutano-porphyrin" suggested.

Elastomeric Polycarbonate Block Copolymers

1965 ◽  
Vol 38 (2) ◽  
pp. 431-449
Author(s):  
Eugene P. Goldberg
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Bisphenol A ◽  
Flexural Modulus ◽  
Softening Temperature ◽  
Thermoplastic Elastomers ◽  
Partial Replacement ◽  
Initial Increase ◽  
Copolymer Composition ◽  
Moderate Degree

Abstract Polycarbonate block copolymers were prepared by phosgenating pyridine solutions of polyether glycol-bisphenol-A mixtures. Copolycarbonates derived from poly(oxyethylene) glycols (Carbowaxes) were studied in detail for property-structure effects as a function of glycol molecular weight (1000–20,000) and copolymer composition (5–70 weight per cent or 0.3–10.0 mole per cent of a 4000 molecular weight glycol). Remarkable strength (>7000 psi) and snappy elasticity (>90 per cent immediate recovery) were observed at poly(oxyethylene) block concentrations greater than 3 mole per cent. These thermoplastic elastomers also exhibited high softening temperatures (>180° C) and tensile elongations up to about 700 per cent. Both Tg and softening temperature varied linearly with comonomer mole ratio over the composition range studied, with Tg displaying much greater polyether concentration sensitivity. It is suggested that the observed property effects result to a large extent from the variation in poly(bisphenol-A carbonate) block length that accompanies the changing of copolymer composition. An initial increase in flexural modulus (stiffness) was observed at low polyether concentrations (0–1 mole per cent). This phenomenon is considered to be related to similar modulus effects found in plasticized rigid thermoplastics at low plasticizer concentrations. A moderate degree of molecular order, due to bisphenol carbonate segments rather than the normally crystalline polyether, was detected by x-ray analysis. Elastomeric carbonate-carboxylate tetrapolymers were also prepared by partial replacement of carbonate with isophthalate, terephthalate or adipate linkages in polyether-bisphenol systems. The dramatic softening temperature depression observed in this class of polymers is attributed to the disruption of long bisphenol carbonate block sequences that exist in the simpler polyether glycol-bisphenol carbonate copolymers.

Creation of Polymeric Nanostructures by Living Coordination Block Copolymerization of Allene Derivatives Having Fluoroalkyl Substituents Under Polymerization-induced Self-assembly Conditions and Their Application to Superhydrophobic Surface

2021 ◽  
Author(s):  
Yidan Cheng ◽  
Takeshi Wakiya ◽  
Shinsuke Inagi ◽  
Toshikazu Takata ◽  
Ikuyoshi Tomita
Keyword(s):  
Block Copolymers ◽  
Self Assembly ◽  
Superhydrophobic Surface ◽  
Block Copolymerization ◽  
Spontaneous Formation ◽  
Superhydrophobic Coatings

The spontaneous formation of polymeric nanostructures possessing outer fluorous segments by the living coordination block copolymerization and their application to the transparent superhydrophobic coatings are described. The block copolymers (BCPs)...

scholarly journals New Biodegradable Poly(l-lactide)-Block-Poly(propylene adipate) Copolymer Microparticles for Long-Acting Injectables of Naltrexone Drug

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 852 ◽  
Author(s):  
Stavroula Nanaki ◽  
Athina Viziridou ◽  
Alexandra Zamboulis ◽  
Margaritis Kostoglou ◽  
Georgios Z. Papageorgiou ◽  
...  
Keyword(s):  
Block Copolymers ◽  
Drug Release ◽  
Amorphous State ◽  
Copolymer Composition ◽  
Polymeric Matrices ◽  
Release Studies ◽  
Biodegradable Poly ◽  
Long Acting ◽  
Poly Propylene ◽  
Tga And Dsc

In the present study, novel block copolymers of poly(l-lactide)-block-poly(propylene adipate) (PLLA-b-PPAd) were synthesized in two ratios, 90/10 and 75/25 w/w and were further investigated as long-acting injectable (LAI) polymeric matrices in naltrexone base microparticle formulations. The synthesized polymers were characterized by 1H-NMR, 13C-NMR, FTIR, XRD, TGA and DSC. NMR and FTIR spectroscopies confirmed the successful synthesis of copolymers while DSC showed that these are block copolymers with well-defined and separated blocks. Microparticles were prepared by single emulsification method and were further characterized. Nanoparticles in the range of 0.4–4.5 μm were prepared as indicated by SEM, with copolymers giving the lowest particle size. By XRD and DSC it was found that naltrexone was present in the amorphous state in its microparticles. Dissolution study showed a drug release extending over seven days, indicating that these novel PLLA-b-PPAd copolymers could be promising matrices for naltrexone’s LAI formulations. It was evidenced that drug release depended on the copolymer composition. Model release studies showed that drug release is controlled by diffusion.

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.

scholarly journals Synthesis and Self-Assembly of Poly(N-Vinylcaprolactam)-b-Poly(ε-Caprolactone) Block Copolymers via the Combination of RAFT/MADIX and Ring-Opening Polymerizations

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1252
Author(s):  
Rodolfo M. Moraes ◽  
Layde T. Carvalho ◽  
Gizelda M. Alves ◽  
Simone F. Medeiros ◽  
Elodie Bourgeat-Lami ◽  
...  
Keyword(s):  
Block Copolymers ◽  
Ring Opening ◽  
Chain Transfer ◽  
Fluorescence Probe ◽  
Size Exclusion ◽  
Proton Nuclear Magnetic Resonance ◽  
Solution Temperature ◽  
Copolymer Composition ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry

Well-defined amphiphilic, biocompatible and partially biodegradable, thermo-responsive poly(N-vinylcaprolactam)-b-poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by combining reversible addition-fragmentation chain transfer (RAFT) and ring-opening polymerizations (ROP). Poly(N-vinylcaprolactam) containing xanthate and hydroxyl end groups (X–PNVCL–OH) was first synthesized by RAFT/macromolecular design by the interchange of xanthates (RAFT/MADIX) polymerization of NVCL mediated by a chain transfer agent containing a hydroxyl function. The xanthate-end group was then removed from PNVCL by a radical-induced process. Finally, the hydroxyl end-capped PNVCL homopolymer was used as a macroinitiator in the ROP of ε-caprolactone (ε-CL) to obtain PNVCL-b-PCL block copolymers. These (co)polymers were characterized by Size Exclusion Chromatography (SEC), Fourier-Transform Infrared spectroscopy (FTIR), Proton Nuclear Magnetic Resonance spectroscopy (1H NMR), UV–vis and Differential Scanning Calorimetry (DSC) measurements. The critical micelle concentration (CMC) of the block copolymers in aqueous solution measured by the fluorescence probe technique decreased with increasing the length of the hydrophobic block. However, dynamic light scattering (DLS) demonstrated that the size of the micelles increased with increasing the proportion of hydrophobic segments. The morphology observed by cryo-TEM demonstrated that the micelles have a pointed-oval-shape. UV–vis and DLS analyses showed that these block copolymers have a temperature-responsive behavior with a lower critical solution temperature (LCST) that could be tuned by varying the block copolymer composition.

Elastomeric Polyether-Ester Block Copolymers. I. Structure-Property Relationships of Tetramethylene Terephthalate/Polyether Terephthalate Copolymers

1977 ◽  
Vol 50 (4) ◽  
pp. 688-703 ◽  
Author(s):  
J. R. Wolfe
Keyword(s):  
Phase Separation ◽  
Melting Point ◽  
Block Copolymers ◽  
Low Temperature ◽  
Chain Length ◽  
Chemical Structure ◽  
High Water ◽  
Structure Property ◽  
Tear Strength ◽  
Structure Property Relationships

Abstract The properties of elastomeric tetramethylene terephthalate/polyether terephthalate copolymers have been related to the chemical structure, chain length, and concentration in the copolymers of the PTMEG-, PEG-, and PPG-derived polyether units. Low-temperature properties and tear strength are dependent on all three polyether-related variables. Melting point, hardness, and stress at 100% elongation appear to be independent of polyether structure. Polyether glycols of low MW volatilize during copolymer preparation. High-MW polyethers tend to crystallize when present in the copolymers. Polyether glycols of intermediate MW (∼ 1000) yield copolymers with the best resistance to low-temperature stiffening. Copolymer synthesis is most difficult with PPG as the polyether glycol. Inherent viscosities are low, and phase separation occurs at lower polyether MW than with PTMEG or PEG. The PEG-based copolymers exhibit high water swell, particularly at intermediate and high PEG MW. The PTMEG-based copolymers are easiest to synthesize and exhibit the best overall combination of properties.

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