Monomer reactivity ratios and glass‐transition temperatures of copolymers based on dimethyl amino ethyl methacrylate and two structural hydroxy‐functional acrylate isomers

Martín‐Gomis, Luis; Cuervo-Rodríguez, Rocío; Fernández‐Monreal, M. C.; Madruga, Enrique López

doi:10.1002/pola.10811

Cited by 15 publications

(22 citation statements)

References 36 publications

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“…Three hydrogels PDH- x were obtained with the following mole ratios of DMAEMA/HEMA: 5:95, 25:75 and 50:50. With the increase of the DMAEMA ratio in PDH, the PDH-50/50 tended to be macroscopically heterogeneous (Figure S2a) due to the disproportional monomer reactivity . The successful synthesis of PDH-5/95 and PDH-25/75 was characterized by FT-IR and 13 C NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Self-Assembled Injectable Nanocomposite Hydrogels Coordinated by in Situ Generated CaP Nanoparticles for Bone Regeneration

Kuang

et al. 2019

ACS Appl. Mater. Interfaces

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Due to the great similarity to the natural extracellular matrix and minimally invasive surgeries, injectable hydrogels are appealing biomaterials in cartilage and bone tissue engineering. Nevertheless, undesirable mechanical properties and bioactivity greatly hamper their availability in clinic applications. Here, we developed an injectable nanocomposite hydrogel by in situ growth of CaP nanoparticles (ICPNs) during the free-radical polymerization of dimethylaminoethyl methacrylate (DMAEMA) and 2-hydroxyethyl methacrylate (HEMA) matrix (PDH) for bone regeneration. The ICPNs are self-assembled by incorporation of poly-l-glutamic acid (PGA) with abundant carboxyl functional groups during the formation of carboxyl–Ca2+ coordination and further CaP precipitation. Furthermore, the carboxyl groups of PGA could interact with the tertiary amines of DMAEMA fragments and thus improve the mechanical strength of hydrogels. Upon mixing solutions of DMAEMA and HEMA bearing PGA, Ca2+, and PO4 3–, this effective and dynamic coordination led to the rapid self-assembly of CaP NPs and PDH nanocomposite hydrogels (PDH/mICPN). The obtained optimal nanocomposite hydrogels exhibited suitable injectable time, an enhanced tensile strength of 321.1 kPa, and a fracture energy of 29.0 kJ/m2 and dramatically facilitated cell adhesion and upregulated osteodifferentiation compared to hydrogels prepared by blending ex situ prefabricated CaP NPs. In vivo experiments confirmed the promoted osteogenesis, which shows a striking contrast to pure PDH hydrogels. Additionally, the methacrylate groups on the monomers could easily be functionalized with aptamers and thereby facilitate recognition and capturing of bone marrow stromal cells both in vitro and in vivo and strengthen the bone regeneration. We believe that our conducted research about in situ self-assembled CaP nanoparticle-coordinated hydrogels will open a new avenue for bone regeneration in the future endeavors.

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Section: Resultsmentioning

confidence: 99%

Self-Assembled Injectable Nanocomposite Hydrogels Coordinated by in Situ Generated CaP Nanoparticles for Bone Regeneration

Kuang

et al. 2019

ACS Appl. Mater. Interfaces

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“…Fevotte et al40 suggested a model to predict/control the T g s of free radical copolymers in 1998, whereas their model was failed to predict the chain structure due to the application of conventional free radical polymerization. Martin‐Gomis et al41 investigated the T g of copolymers based on dimethyl amino ethyl methacrylate and two structural hydroxy‐functional acrylate isomers (HEMA and EHMA), along with the intramolecular and intermolecular structure and Johnston Equation, enabled a description of the experimental variations of the copolymer T g . Liu et al42 proposed a equation to predict the T g of sequence distribution‐copolymers based on the extended Gibbs‐DiMarzio equation in view of bond rotation flexibility and additivity of the corresponding stiff energies.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of gradient copolymers with simultaneously tailor‐made chain composition distribution and glass transition temperature by semibatch ATRP: From modeling to application

Zhou

Luo

2012

J. Polym. Sci. A Polym. Chem.

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Recent studies have demonstrated that gradient copolymers exhibit unique thermal properties. Although these properties can be determined by copolymer composition, other factors such as chain and sequence lengths and their distributions can also influence them. Accordingly, the synthesis of gradient copolymers requires simultaneously tailor-made chain structure and thermal properties. In this work, we carried out a systematic study on the preparation of poly(methyl methacrylate-grad-2-hydroxyethyl methacrylate) [poly(MMA-grad-HEMA)] with synchronously tailor-made chain composition distribution and glass transition temperature (Tg) through semibatch atom transfer radical polymerization. First, a comprehensive model for simultaneously predicting gradient copolymer microstructure and Tg was presented using the concept of pseudo-kinetic rate coefficients and Johnston equation. The model was validated by comparing simulation results with the classical reference data. Furthermore, the model was used to guide the experimental synthesis of the poly(MMA-grad-HEMA) gradient copolymers potentially as excellent damping material. The thermal properties of these gradient copolymer samples were evaluated. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012National Natural Science Foundation of China [20406016, 21076171

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“…In several studies the monomer reactivity ratios for copolymerization of DMAEM with methyl methacrylate (MMA) in bulk as well as in dioxane and chloroform solutions were reported 11–13. Copolymerizations with a few other methacrylates were also investigated, namely 2‐hydroxyethyl methacrylate, ethyl‐α‐hydroxymethyl acrylate, (2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methyl methacrylate and tert ‐butyl methacrylate 12, 14, 15. Furthermore, the effect of the polarity of different solvents on the reactivity ratio values in the free radical copolymerization of DMAEM with N ‐vinylcarbazole has been described 16.…”

Section: Introductionmentioning

confidence: 99%

Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

Šoljić

Jukić

Janović

2009

Polymer International

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BACKGROUND: The properties of copolymers depend strongly on their composition; therefore in order to tailor some for specific applications, it is necessary to control their synthesis, and, in particular, to know the reactivity ratios of their constituent monomers. Free radical copolymerizations of N,N‐dimethylaminoethyl methacrylate (DMAEM) with styrene (ST) and methyl methacrylate (MMA) in toluene solution using 1‐di(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane as initiator at 70 °C were investigated. Monomer reactivity ratios were determined for low conversions using both linear and nonlinear methods. RESULTS: For the DMAEM/ST system the average values are r1 = 0.43 and r2 = 1.74; for the DMAEM/MMA system the average values are r1 = 0.85 and r2 = 0.86. The initial copolymerization rate, Rp, for DMAEM/ST sharply decreases as the content of ST in the monomer mixture increases up to 30 mol% and then attains a steady value. For the DMAEM/MMA copolymerization system the composition of the feed does not have a significant influence on Rp. The glass transition temperatures (Tg) of the copolymers were determined calorimetrically and calculated using Johnston's sequence length method. A linear dependence of Tg on copolymer composition for both systems is observed: Tg increases with increasing ST or MMA content. CONCLUSION: Copolymerization reactivity ratios enable the design of high‐conversion processes for the production of copolymers of well‐defined properties for particular applications, such as the improvement of rheological properties of lubricating mineral oils. Copyright © 2009 Society of Chemical Industry

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Monomer reactivity ratios and glass‐transition temperatures of copolymers based on dimethyl amino ethyl methacrylate and two structural hydroxy‐functional acrylate isomers

Cited by 15 publications

References 36 publications

Self-Assembled Injectable Nanocomposite Hydrogels Coordinated by in Situ Generated CaP Nanoparticles for Bone Regeneration

Self-Assembled Injectable Nanocomposite Hydrogels Coordinated by in Situ Generated CaP Nanoparticles for Bone Regeneration

Synthesis of gradient copolymers with simultaneously tailor‐made chain composition distribution and glass transition temperature by semibatch ATRP: From modeling to application

Free radical copolymerization of N,N‐dimethylaminoethyl methacrylate with styrene and methyl methacrylate: monomer reactivity ratios and glass transition temperatures

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