5919-74-4Relevant academic research and scientific papers
From a water-immiscible monomer to block copolymer nano-objects via a one-pot RAFT aqueous dispersion polymerization formulation
Ratcliffe,Ryan,Armes
, p. 769 - 777 (2013)
We describe the facile atom-efficient synthesis of diblock copolymer nano-objects via a one-pot RAFT aqueous dispersion polymerization protocol starting from a water-immiscible methacrylic monomer. More specifically, an aqueous emulsion of glycidyl methacrylate (GlyMA) is quantitatively converted into a 10% w/w aqueous solution of glycerol monomethacrylate (GMA) at 80 C in air within 9 h in deionized water. 1H NMR spectroscopy studies indicate no evidence for either methacrylic ester hydrolysis or polymerization during this ring-opening reaction. Kinetic analysis indicates that a significant rate acceleration occurs as the reaction mixture switches from a two-phase emulsion to a single aqueous phase. This observation is fully consistent with the GlyMA-GMA-water ternary phase diagram determined at 80 C. The 10% w/w aqueous solution of GMA can be polymerized using RAFT chemistry to produce a near-monodisperse PGMA macromolecular chain-transfer agent (macro-CTA), which indicates that relatively little dimethacrylate impurity is produced during the conversion of GlyMA into GMA. This PGMA macro-CTA can be subsequently chain-extended using 2-hydroxypropyl methacrylate (HPMA) via a RAFT aqueous dispersion polymerization formulation. The resulting PGMA-PHPMA diblock copolymers can form well-defined spheres, worms, or vesicles depending on the relative block compositions, since this dictates the copolymer curvature and hence the self-assembly behavior. Bearing in mind that GMA is a relatively expensive specialty monomer and GlyMA is a commodity monomer, this appears to be a highly cost-effective, purely aqueous one-pot route to diblock copolymer nano-objects.
A new design of cleavable acetal-containing amphiphilic block copolymers triggered by light
Huang, Yu,Thanneeru, Srinivas,Zhang, Qian,He, Jie
, p. 1815 - 1824 (2018)
We report a new design of photolabile acetal-containing amphiphilic block copolymers. Acetals as protecting groups for carbonyls or diols can be hydrolyzed under acidic condition but very stable with respect to hydrolysis at pH > 7. When combining light-capturing chromophores with acetals, the hydrolysis of acetals can be activated by light to design dual responsive acetal-containing polymers. Using acetalization reaction of 2,3-dihydroxypropyl methacrylate with benzaldehyde derivatives, two new acetal-containing photolyzable monomers have been designed. Comparable to commonly used photolabile monomers containing nitrobenzyl esters, the two acetal-containing monomers are easy to polymerize using atom transfer radical polymerization with excellent molecular weight and dispersity control. We studied the cleavage kinetics and mechanism of acetal groups in both monomers and polyethylene oxide (PEO)-containing amphiphilic block copolymers using 1H NMR and UV–vis spectroscopy. o-Nitrobenzaldehyde acetal showed a Norrish Type II rearrangement to form benzoic ester; while, 2,5-dimethoxy benzaldehyde acetal was photolabile to completely release 2,3-dihydroxypropyl methacrylate. The photocleavage of acetals is a zero-order reaction in regardless of molecular states of acetals; while, the acid-cleavage of acetals proves to be a first-order kinetics and the cleavage becomes much slower for polymers. The self-assembly of acetal-containing amphiphilic block copolymers and the acid-/light-controlled dissociation of their vesicles have been investigated. We demonstrate that those acetal-containing polymers are potentially useful as smart drug delivery systems where the release kinetics of payloads is tunable using light and pH as triggers.
Inverse high internal phase emulsion polymerization (i-HIPE) of GMMA, HEMA and GDMA for the preparation of superporous hydrogels as a tissue engineering scaffold
Nalawade, Archana C.,Ghorpade, Ravindra V.,Shadbar, Sadiqua,Qureshi, Mohammed Shadbar,Chavan,Khan, Ayesha A.,Ponrathnam
, p. 450 - 460 (2016)
A series of novel superporous hydrogels for regenerative medicine were prepared by oil-in-water (o/w) or inverse high internal phase emulsion (i-HIPE) copolymerization of glycerol monomethacrylate (GMMA), 2-hydroxy ethyl methacrylate (HEMA) and glycerol dimethacrylate (GDMA) as a cross-linker using a non toxic solvent and a redox initiator system at the physiological temperature (37 °C). The monomer GMMA was synthesized from glycidyl methacrylate (GMA) by an alternative facile method using Amberlyst-15. The described i-HIPEs showed a significantly wider stability window. The polyHIPE hydrogels were characterized by FTIR, BET method for surface area, mercury porosimetry, SEM, DSC, TGA, XRD, compressive strain and strain recovery. The swelling ratio of the hydrogels and their degradation in 0.007 M NaOH and lipase B (Candida antarctica) solutions were determined gravimetrically and the rate of degradation was explained in terms of the molecular structure of the hydrogels. The morphological studies showed that the pore diameter varied between 20 and 30 μm and the pore throats (interconnecting windows) diameter was in the range of 4-8 μm. The described polyHIPE hydrogels were found to have an open cell morphology and interconnected pore architecture, which are important characteristics for scaffold applications. The initial cytotoxicity study performed according to ISO-10993-5 indicated cytocompatibility (97% cell viability) and the subsequent cell seeding and proliferation study exhibited 55-88% cell viability (increased monotonously from GHG-1 to GHG-5), which could be attributed to modulation of the physical and chemical properties of the hydrogels. The described super porous hydrogels are considered as potential candidates for scaffold materials in tissue engineering applications.
Refractive index tuning of highly transparent bismuth containing polymer composites
Fritsch,Mansfeld,Mehring,Wursche,Grothe,Kaskel
, p. 3263 - 3268 (2011)
A new method for the preparation of transparent bismuth containing composites is reported. With the organic ligands 2,3-Dihydroxypropylmethacrylate (HMA) and 2-(Methacryloyloxy)-ethylacetoacetate (AcMA), bifunctional monomers with a functional group for metal complexation on the one hand and a reactive group for polymerization on the other hand were found. By integrating up to 20 wt-% bismuth in the monomer mixtures, an increase of the refractive index of 4.0% (n = 0.058) is determined. The metal complexation was observed via infrared spectroscopy (AcMA) and NMR spectroscopy (HMA). Subsequent addition of trimethylolpropane triacrylate (TMPTA) as cross-linking agent and 2,4,6-trimethyl-benzoyldiphenylphosphine oxide (TPO) as photoinitiator to the bismuth containing monomers Bi-HMA and Bi-AcMA lead to a UV-curable liquid. Photoinduced polymerization was used to generate transparent bismuth containing hybrid materials with increased refractive index. The polymers were characterized by UV/VIS spectroscopy, ellipsometry and DTA/TG. The materials show a high transmission (>80% in 2 mm thick plates) in the visible spectral range, and an increased refractive index with increasing bismuth content.
Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study
Natongchai, Wuttichai,Posada-Pérez, Sergio,Phungpanya, Chalida,Luque-Urrutia, Jesús Antonio,Solà, Miquel,D'Elia, Valerio,Poater, Albert
, p. 2873 - 2886 (2022/02/10)
Compared to metal-organic complexes and transition-metal halides, group I metal halides are attractive catalysts for the crucial cycloaddition reaction of CO2to epoxides as they are ubiquitously available and inexpensive, have a low molecular weight, and are not based on (potentially) endangered metals, especially for the case of sodium and potassium. Nevertheless, given their low intrinsic catalytic efficiency, they require the assistance of additional catalytic moieties. In this work, we show that by exploiting the high nucleophilicity of opportunely designed aminopyridines, catalytic systems based on alkaline metals can be formed, which allow the cycloaddition of CO2to epoxides to proceed under atmospheric pressure at moderate temperatures. Importantly, the aminopyridine nucleophiles can be applied in their heterogenized form, leading to a recyclable catalytic system. An investigation of the reaction mechanism by density functional theory calculations shows that metal halide complexes and nucleophilic pyridines can work as a dual cooperative catalytic system where the use of aminopyridines leads to lower energy barriers for the opening of the epoxide ring, and halide-adducts are involved in the subsequent steps of CO2insertion and ring closure.
Acrylate monomer having hydrophilic end group and a method for preparing the same
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Paragraph 0108-0110, (2021/11/02)
More particularly, the present invention relates to an acrylate monomer having a high-purity hydrophilic terminal group which does not contain unreacted 1 water or undesirable by-products, and a method for producing the acrylate monomer. These acrylate monomers are substantially free of polymerization inhibitors. Chemical Formula 1. In Chemical Formula 1, R. 1 Chem. R. 2 Chem. R. 3 May be H, or linear, branched or cyclic C, independently of each other. 1 -C12 alkyl group. R4 Is linear, branched or cyclic C. 1 -C12 alkyl Or C1 -C12 It is alkoxy group, wherein alkyl group carbon atoms can be unsubstituted or substituted with oxygen atoms, n Is an integer selected from 1 and 10.
METHOD FOR PRODUCING GLYCEROL MONO(METH)ACRYLATE
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Page/Page column 6-8, (2021/01/22)
The invention relates to a method for producing glycerol mono(meth) acrylate from 2,2-dimethyl-l,3-dioxolan-4-ylmethyl (meth)acrylate by acidic silica catalysed reaction with methanol.
Gel forming waterborne dispersion polymerization of sodium p-styrene sulfonate with glycidyl methacrylate
Dsouza, Roshan F.,Parthiban, Anbanandam
, p. 626 - 634 (2017/12/29)
Water soluble monomer like sodium p-styrene sulfonate (SSS) is copolymerized with hydrophobic and reactive monomer glycidyl methacrylate (GMA). The polymerization proceeds as dispersion and forms gels. The gel forming nature prevails even with other hydrophobic and hydrophilic monomers to form ternary polymeric systems. The swelling is dependent on polymer composition as well as the treatment history of polymers. SSS also induces ring opening of GMA to form 1,2-diols as confirmed independently by various model reactions. The ability of hydrogels to absorb various dyes indicates that owing to the anionic nature, hydrogels absorb cationic dyes nearly quantitatively. Because of their strong affinity to cationic species these hydrogel forming polymers are potentially useful in water purification applications as well as purification of proteins.
STIMULI RESPONSIVE COMPOSITIONS FOR IRON CHELATION
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Paragraph 0162; 0163; 0164; 0165, (2016/08/03)
The present technology provides new compositions comprising at least one cross-linked co-polymer. In some embodiments, the polyacrylamide co-polymer comprises water soluble subunits, cross-linking subunits, and iron chelating subunits. In other embodiments, the co-polymer comprises water soluble units, cross-linking subunits, and substituted subunits, which can be conjugated with iron-chelating agents. When these new particles are exposed to certain environments, such the presence of strong acids or oxidation agents, these particles are capable of breaking up so that the iron chelating agents can chelate iron or other metals from their environments. Methods to prepare these new compositions are also provided. These compositions or compositions comprising nanogels of the present technology may be used to treat metal overload conditions such as iron overload resulting from chronic transfusions.
GLYCERIN MONO (METH) ACRYLATE STORING METHOD AND PRODUCTION METHOD
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Paragraph 0039; 0040, (2016/12/01)
PROBLEM TO BE SOLVED: To provide a method for storing glycerin mono (meth) acrylate in which a 1,3-dihydroxypropyl (meth) acrylate which is one of the isomers of glycerin mono (meth) acrylate, can be held at a proportion that remains greater than the equilibrium state. SOLUTION: Provided is a method for storing glycerin mono (meth) acrylate comprising an isomer 1 (2,3-dihydroxypropyl (meth) acrylate) and an isomer 2 (1,3-dihydroxypropyl (meth) acrylate) represented by formula (2), and the storing method is characterized in storing glycerin mono (meth) acrylate that comprises isomer 2 at a proportion greater than the proportion of isomer 2 at equilibrium state, at a temperature of 40°C or less. (R is H or methyl group.). COPYRIGHT: (C)2015,JPOandINPIT
