scholarly journals Ethylene Glycol Dicyclopentenyl (Meth)Acrylate Homo and Block Copolymers via Nitroxide Mediated Polymerization

Materials ◽  
2019 ◽  
Vol 12 (9) ◽  
pp. 1547
Author(s):  
Alexandre Maupu ◽  
Yara Kanawati ◽  
Adrien Métafiot ◽  
Milan Maric
Keyword(s):  
Ethylene Glycol ◽  
Random Copolymer ◽  
Chain Extension ◽  
Butyl Methacrylate ◽  
Block Copolymerization ◽  
Molecular Weights ◽  
High Dispersity ◽  
High Fraction ◽  
Succinimidyl Ester ◽  
Nitroxide Mediated Polymerization

Nitroxide-mediated polymerization (NMP), (homo and block copolymerization with styrene (S) and butyl methacrylate/S) of ethylene glycol dicyclopentenyl ether (meth)acrylates (EGDEA and EGDEMA) was studied using BlocBuilder alkoxyamines. EGDEA homopolymerization was not well-controlled, independent of temperature (90–120 °C), or additional free nitroxide (0–10 mol%) used. Number average molecular weights (Mn) achieved for poly(EGDEA) were 4.0–9.5 kg mol−1 and were accompanied by high dispersity (Ð = Mw/Mn = 1.62–2.09). Re-initiation and chain extension of the poly(EGDEA) chains with styrene (S) indicated some block copolymer formation, but a high fraction of chains were terminated irreversibly. EGDEA-stat-S statistical copolymerizations with a low mol fraction S in initial feed, fS,0 = 0.05, were slightly better controlled compared to poly(EGDEA) homopolymerizations (Ð was reduced to 1.44 compared to 1.62 at similar conditions). EGDEMA, in contrast, was successfully polymerized using a small fraction of S (fS,0 ~ 10 mol%) to high conversion (72%) to form well-defined EGDEMA-rich random copolymer (molar composition = FEGDEMA = 0.87) of Mn = 14.3 kg mol−1 and Ð = 1.38. EGDEMA-rich compositions were also polymerized with the unimolecular succinimidyl ester form of BlocBuilder initiator, NHS-BlocBuilder with similar results, although Ðs were higher ~1.6. Chain extensions resulted in monomodal shifts to higher molecular weights, indicating good chain end fidelity.

“Nascent” Fe(0)-mediated living radical copolymerization of styrene and acrylonitrile

e-Polymers ◽  
2014 ◽  
Vol 14 (3) ◽  
pp. 187-192
Author(s):  
Guo-Xiang Wang ◽  
Mang Lu ◽  
Zhao-Hui Hou ◽  
Xue-Hui Zhan ◽  
Yong Gao ◽  
...  
Keyword(s):  
Gel Permeation Chromatography ◽  
Random Copolymer ◽  
Monomer Conversion ◽  
Radical Copolymerization ◽  
Chain Extension ◽  
Molar Ratio ◽  
Molecular Weights ◽  
H Nmr ◽  
First Order Kinetics

AbstractIn this work, we reported the synthesis of copolymers of poly(styrene-co-acrylonitrile) via single-electron transfer-living radical polymerization using CCl4 as an initiator and Zn(0)/2,2′-bipyridine (Bpy)/FeCl2 as catalyst complexes. The polymerization was carried out at 25°C. The polymerization proceeded in a living fashion based on “nascent” Fe(0) as the source of the transition metal, which was prepared by Zn(0)/FeCl2 in situ. The kinetic experimental results showed that the copolymerization is first-order kinetics. The molecular weights increased linearly with respect to monomer conversion, and narrow polydispersity index values were obtained. The effect of the molar ratio of [Zn(0)]0/[FeCl2]0 on polymerization was investigated. In addition, the polymerization carried out in different solvents was also investigated. The obtained random copolymer was characterized by 1H NMR and gel permeation chromatography. The living characteristic was demonstrated by chain extension experiment.

Immuno-compatibility of desaminotyrosine and desaminotyrosyl tyrosine functionalized star-shaped oligo(ethylene glycol)s with different molecular weights

2015 ◽  
Vol 1718 ◽  
pp. 97-102 ◽  
Author(s):  
Toralf Roch ◽  
Konstanze K. Julich-Gruner ◽  
Axel T. Neffe ◽  
Nan Ma ◽  
Andreas Lendlein
Keyword(s):  
Aqueous Solution ◽  
Ethylene Glycol ◽  
Average Molecular Weight ◽  
Molecular Weights ◽  
Immunological Effects ◽  
Microbial Products ◽  
Low Levels ◽  
Chain Lengths ◽  
Immunological Evaluation

ABSTRACTPolymer-based therapeutic strategies require biomaterials with properties and functions tailored to the demands of specific applications leading to an increasing number of newly designed polymers. For the evaluation of those new materials, comprehensive biocompatibility studies including cyto-, tissue-, and immunocompatibility are essential. Recently, it could be demonstrated that star-shaped amino oligo(ethylene glycol)s (sOEG) with a number average molecular weight of 5 kDa and functionalized with the phenol-derived moieties desaminotyrosine (DAT) or desaminotyrosyl tyrosine (DATT) behave in aqueous solution like surfactants without inducing a substantial cytotoxicity, which may qualify them as solubilizer for hydrophobic drugs in aqueous solution. However, for biomedical applications the polymer solutions need to be free of immunogenic contaminations, which could result from inadequate laboratory environment or contaminated starting material. Furthermore, the materials should not induce uncontrolled or undesired immunological effects arising from material intrinsic properties. Therefore, a comprehensive immunological evaluation as perquisite for application of each biomaterial batch is required. This study investigated the immunological properties of sOEG-DAT(T) solutions, which were prepared using sOEG with number average molecular weights of 5 kDa, 10 kDa, and 20 kDa allowing analyzing the influence of the sOEG chain lengths on innate immune mechanisms. A macrophage-based assay was used to first demonstrate that all DAT(T)-sOEG solutions are free of endotoxins and other microbial contaminations such as fungal products. In the next step, the capacity of the different DAT(T)-functionalized sOEG solutions to induce cytokine secretion and generation of reactive oxygen species (ROS) was investigated using whole human blood. It was observed that low levels of the pro-inflammatory cytokines interleukin(IL)-1β and IL-6 were detected for all sOEG solutions but only when used at concentrations above 250 µg·mL-1. Furthermore, only the 20 kDa sOEG-DAT induced low amounts of ROS-producing monocytes. Conclusively, the data indicate that the materials were not contaminated with microbial products and do not induce substantial immunological adverse effectsin vitro,which is a prerequisite for future biological applications.

Smart control of cotton fabric comfort by cross-linking thermo-responsive poly(2-(2-methoxyethoxy) ethoxyethyl methacrylate-co-ethylene glycol methacrylate)

2016 ◽  
Vol 87 (13) ◽  
pp. 1620-1630 ◽  
Author(s):  
Yangyi Chen ◽  
Jie An ◽  
Qi Zhong ◽  
Peter Müller-Buschbaum ◽  
Jiping Wang
Keyword(s):  
Ethylene Glycol ◽  
Cotton Fabric ◽  
Random Copolymer ◽  
Cotton Fabrics ◽  
Molar Ratio ◽  
Cross Linking ◽  
Glycol Methacrylate ◽  
Moisture Permeability ◽  
Smart Control ◽  
Fabric Comfort

The smart control of cotton fabric comfort by cross-linking thermo-responsive random copolymer is investigated. The monomers 2-(2-methoxyethoxy) ethoxyethyl methacrylate (MEO2MA) and ethylene glycol methacrylate (EGMA) with a molar ratio of 17:3 are selected to synthesize the thermo-responsive random copolymer poly(2-(2-methoxyethoxy) ethoxyethyl methacrylate- co-ethylene glycol methacrylate), abbreviated as P(MEO2MA- co-EGMA). By using citric acid as a cross-linking agent, the obtained P(MEO2MA- co-EGMA) is successfully immobilized onto cotton fabrics. Smart control is achieved from the thermo-responsive behavior of the copolymer. Cross-linked P(MEO2MA- co-EGMA) will collapse when the ambient temperature exceeds its transition temperature. Therefore, the formerly compact P(MEO2MA- co-EGMA) layer will switch to a porous structure, and the air/moisture permeability of the textiles is enhanced. As the comfort of the textiles is closely related to the air/moisture permeability, a smart control of the cotton fabric comfort can be realized. In addition, the softness of cotton fabrics with and without thermo-responsive polymers does not show a prominent change, even when the applied solution concentration is as high as 16% (wt%). On the contrary, the stiffness of the cotton fabric coated with poly( N-isopropylacrylamide) (PNIPAM) is significantly higher than the original cotton fabric, indicating that homo PNIPAM is less suitable for textiles used in daily lives. Moreover, the whiteness and mechanical properties are studied and stay unchanged after cross-linking. As a consequence, the introduction of P(MEO2MA- co-EGMA) into textiles can provide textiles with smart control of cotton comfort, and it will not influence the wearabilities of the textiles.

scholarly journals A ring to rule them all: a cyclic ketene acetal comonomer controls the nitroxide-mediated polymerization of methacrylates and confers tunable degradability

2015 ◽  
Vol 51 (64) ◽  
pp. 12847-12850 ◽  
Author(s):  
Vianney Delplace ◽  
Elise Guégain ◽  
Simon Harrisson ◽  
Didier Gigmes ◽  
Yohann Guillaneuf ◽  
...  
Keyword(s):  
Ethylene Glycol ◽  
Methyl Ether ◽  
Ketene Acetal ◽  
Nitroxide Mediated Polymerization ◽  
Glycol Methyl Ether

2 Methylene-4-phenyl-1,3-dioxolane (MPDL) was used as a controlling comonomer in NMP with oligo(ethylene glycol) methyl ether methacrylate (MeOEGMA) to prepare well-defined and degradable PEG-based P(MeOEGMA-co-MPDL) copolymers.

scholarly journals ffects of Poly{Carboxylate–g–(Ethylene Glycol)Methyl Ether} on the Physical Properties of Cement Paste

2016 ◽  
Vol 7 (1) ◽  
pp. 47 ◽  
Author(s):  
Heon-Young Cho ◽  
Jung-Mok Suh ◽  
Jin-Man Kim
Keyword(s):  
Ethylene Glycol ◽  
Cement Paste ◽  
Methyl Ether ◽  
Optimal Range ◽  
Molecular Weights ◽  
Testing Method ◽  
Super Plasticizer ◽  
Optimum Formulation ◽  
The Relationship ◽  
Glycol Methyl Ether

<p>The comb type poly{carboxylate–g–(ethylene glycol)methyl ether} (P(C–g–E)) copolymers were synthesized at different monomer ratios. The relationship between the synthetic conditions, the molecular weights<br />(Mp, Mn, Mw, Mz and Mw/Mn) and the dispersion ability of these copolymers in cement paste has been established. The molecular weights of P(C–g–E)s were analyzed by GPC. The dispersion abilities and the dispersion stabilities of P(C–g–E)s in cement paste were tested by mini slump testing method. The optimum formulation for P(C–g–E) synthesis was found to be P23MM 17 mol.%: SMS 10 mol.%: MA 8 mol.%: SMA 65 mol.%: APS 0.2 mol.%. The key components in P(C–g–E) synthetic formulation for cement super-plasticizer are SMA and P23MM. The SMA/P23MM in P(C–g–E) synthetic formulation is related to the dispersion ability and stability of P(C–g–E) in cement paste. The SMA/P23MM in P(C–g–E) synthetic formulation also influences the molecular weights and the polydispersity of P(C–g–E). The optimal range of SMA/P23MM in the formulation as a cement superplasticizer is 3.50~5.50. The dispersion ability of cement paste added with the optimum P(C–g–E) is increased more 3 times than those of the others.</p>

scholarly journals Sizing and Thermal Stability of Prepared Tetraaminophthalocyaninatocopper(II) Derivatives-grafted Polymers

2016 ◽  
Vol 13 (2) ◽  
pp. 221-234
Author(s):  
Baghdad Science Journal
Keyword(s):  
Thermal Stability ◽  
Ethylene Glycol ◽  
Group Analysis ◽  
Condensation Polymerization ◽  
Grafted Polymers ◽  
Poly Ethylene Glycol ◽  
Molecular Weights ◽  
Poly Ethylene ◽  
Thermal Stability Of ◽  
End Group

Different polymers were prepared by condensation polymerization of sebacic anhydride and adipic anhydride with ethylene glycol and poly(ethylene glycol). Their number average molecular weights were determined by end group analysis. Then, they were grafted on the prepared phthalocyaninatocopper(II) compounds with the general formula (NH2)4PcCu(II) having amino groups of 3,3',3'',3'''- or 4,4',4'',4'''- positions. All prepared polymers, compounds, and phthalocyaninatocopper(II)-grafted polymers were characterized by FTIR. The sizing measurements were carried out in 3,3',3'',3'''- (NH2)4PcCu(II) and 4,4',4'',4'''- (NH2)4PcCu(II) compounds with and without grafting polymers. The results showed that the grafting process led to decreasing in particle size and increasing in surface area. The grafting process was reflected positively on the thermal degradation of 3,3',3'',3'''- (NH2)4PcCu(II) and 4,4',4'',4'''- (NH2)4PcCu(II) grafted polymers. They had higher thermal stability accompanied with higher char residue and T50% weight loss with 3,3',3'',3'''-(NH2)4PcCu(II) and their grafted polymers being the best.

scholarly journals Effect of Graphene oxide or Functionalized Graphene Oxide on the Copolymerization Kinetics of Styrene/n-butyl Methacrylate

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 999 ◽  
Author(s):  
Ioannis Tsagkalias ◽  
Afrodite Vlachou ◽  
George Verros ◽  
Dimitris Achilias
Keyword(s):  
Graphene Oxide ◽  
Radical Copolymerization ◽  
Butyl Methacrylate ◽  
Side Reactions ◽  
Hydroxyl Groups ◽  
Functionalized Graphene ◽  
Functionalized Graphene Oxide ◽  
Molecular Weights ◽  
Diffusion Controlled ◽  
Kinetic Rate Constants

Nanocomposite materials based on copolymers of styrene and n-butyl methacrylate with either graphene oxide (GO) or functionalized graphene oxide (F-GO) were synthesized using the in-situ bulk radical copolymerization technique. Reaction kinetics was studied both experimentally and theoretically using a detailed kinetic model also taking into account the effect of diffusion-controlled phenomena on the reaction kinetic rate constants. It was found that the presence of GO results in lower polymerization rates accompanied by the synthesis of copolymers having higher average molecular weights. In contrast, the presence of F-GO did not seem to significantly alter the conversion vs time curves, whereas it results in slightly lower average molecular weights. The first observation was attributed to side reactions of the initiator primary radicals with the hydroxyl groups on the surface of GO, resulting in lower initiator efficiency, whereas the second to grafted structures formed from copolymer macromolecules on the F-GO surface. The copolymerization model predictions including MWD data were found to be in satisfactory agreement with the experimental data. At least four adjustable parameters were employed and their best-fit values were provided.

scholarly journals Naturally-Derived Amphiphilic Polystyrenes Prepared by Aqueous Controlled/Living Cationic Polymerization and Copolymerization of Vinylguaiacol with R–OH/BF3·OEt2

Polymers ◽  
2018 ◽  
Vol 10 (12) ◽  
pp. 1404 ◽  
Author(s):  
Hisaaki Takeshima ◽  
Kotaro Satoh ◽  
Masami Kamigaito
Keyword(s):  
Molecular Weight ◽  
Ferulic Acid ◽  
Cationic Polymerization ◽  
Living Polymerization ◽  
Block Copolymerization ◽  
Molecular Weights ◽  
Molecular Weight Distributions ◽  
Living Cationic Polymerization ◽  
Naturally Occurring ◽  
Weight Distributions

In this study, we investigated direct-controlled/living cationic polymerization and copolymerization of 4-vinylguaiacol (4VG), i.e., 4-hydroxy-3-methoxystyrene, which can be derived from naturally-occurring ferulic acid, to develop novel bio-based amphiphilic polystyrenes with phenol functions. The controlled/living cationic polymerization of 4VG was achieved using the R–OH/BF3·OEt2 initiating system, which is effective for the controlled/living polymerization of petroleum-derived 4-vinylphenol in the presence of a large amount of water via reversible activation of terminal C–OH bond catalyzed by BF3·OEt2, to result in the polymers with controlled molecular weights and narrow molecular weight distributions. The random or block copolymerization of 4VG was also examined using p-methoxystyrene (pMOS) as a comonomer with an aqueous initiating system to tune the amphiphilic nature of the 4VG-derived phenolic polymers. The obtained polymer can be expected not only to be used as a novel styrenic bio-based polymer but also as a material with amphiphilic nature for some applications.

Sign in / Sign up

Export Citation Format

Share Document