Property and quantum chemical investigation of poly(ethyl α-cyanoacrylate)
Introduction
Poly(ethyl α-cyanoacrylate) play an important role in biomedical applications [1], [2] such as in controlled drug delivery, stopping internal bleeding, joining ruptured tissue, etc. due to their biocompatibility and biodegradability. Therefore, much attention has been paid to poly(ethyl α-cyanoacrylate) about synthesis, properties and degradation mechanism.
In anionic polymerization, ethyl α-cyanoacrylate is very active for their strong electronic drawing group. It can be polymerized by weak initiator such as water and alcoholate at room temperature [3], [4]. Therefore, an attempt has been made to understand the nature of poly(ethyl α-cyanoacrylate).
Here we report the anionic polymerization of EtCNA is initiated by water or water with catalyzing by sodium hydroxide under the conditions of no additives and the quantum chemical calculation results so as to deepen researches on the relationship between structure and properties.
Section snippets
Main reagents
Ethyl α-cyanoacrylate (C.R., Beijing Chemical Plant, China) was purified by decompressed distilling before using. Sodium hydroxide (NaOH, A.R., Nanjing Chemical Plant, China) was used as received. Cyclohexane (A.R., Nanjing Chemical Plant, China) was disposed by 4A molecular sieve and decompressed distilling. Argon (99.99%) was disposed by drier. Double distilled water was used in our experiments.
Polymerization by water
Ethyl α-cyanoacrylate was polymerized with water as initiator. In a dry four-necked flask with
Spectral analyses
In IR spectrum, ascription of characteristic absorbing peak of composed PEtCNA is showed as Fig. 1(a) and (b). There exist obvious strong spectrum strips around 2991.2(m, CH2), 1750(vs, CO), 1254(vs, C–O) and 2249(m, CN) cm−1, but none at 3129(m, CH2), 1665 cm−1(w, CC).
In 1HNMR spectrum as Fig. 2(a) and (b) of CDCl3 solution, proton peak of methylene of main chain is δ=2.5 (theoretically calculated value δ=1.9); proton peak of methylene in ester is δ=4.3 (theoretically calculated value δ=4.1);
Conclusion
We synthesize the poly(ethyl α-cyanoacrylate) and measure its IR, 1HNMR and molecular weight distribution. Using the density function theory DFT-B3LYP method, on the level of 6-31+G* group, we completely optimize and calculate molecular geometry, electronic structure, IR spectrum and thermodynamic property of reactant and transition state on the reaction potential energy level of ethyl α-cyanoacrylate and hydroxyl for the first time, and obtain the order 1010 s−1 of rate constant in gas phase.
Acknowledgement
We greatly appreciate the support of this work by the National Natural Science Foundation of China (No. 50372028).
References (11)
Prog. Polym. Sci.
(2003)- et al.
J. Tianjin Univ.
(2001) - et al.
J. Appl. Sci.
(1999) - et al.
Theory and Application of Anionic Polymerization
(1990) Macromolecular Chemistry
(1996)
Cited by (20)
Conformal poly(ethyl α-cyanoacrylate) nano-coating for improving the interface stability of LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf>
2017, Electrochimica ActaCitation Excerpt :The LiNi0.5Mn1.5O4 powder coated with polymer molecule showed similar XRD patterns to that of pristine LiNi0.5Mn1.5O4, indicating the polymer layer coating process did not alter the crystal structure of the LiNi0.5Mn1.5O4 cathode [28]. The FTIR peaks (Fig. 1b) at about 1745 cm−1 (vs, CO) and 1250 cm−1 (vs, C-O) could be attributed to the characteristic absorption of PECA [36]. Compared with the FTIR spectrum of ECA monomer, the disappeared strong peak at 1618 cm−1 (s, CC) of PECA polymer indicated the complete polymerization reaction initiated by moisture in air.
Reactivity of novel ethyl cyanoacrylate and 6-hydroxyhexyl acrylate adhesive mixtures and their influence on adhesion and thermal stability
2017, European Polymer JournalCitation Excerpt :Thus, depending on the reaction conditions, the polymerization of the cyanoacrylates takes place through three mechanisms: anionic [7], zwitterionic [8], and radical [9]. Anionic polymerization of the cyanoacrylates is the most studied mechanism and it is initiated by inorganic bases such as water [10], alcohols [11], or blood [12]. While the zwitterionic polymerization of the cyanoacrylates can be initiated with neutral nucleophiles, such as tertiary amines or phosphines, the radical polymerization requires a radical initiator, such as azobisisobutironitrile [9] or peroxides such as benzoyl peroxide [13].
Synthesis and degradation behavior of poly(ethyl cyanoacrylate)
2008, Polymer Degradation and StabilityCitation Excerpt :FT-IR spectra of the monomer ECA, bulk-polymerized sample using 0.2 μL of DMPT, and the same sample after 2 weeks of degradation in d-acetone are presented in Fig. 7(a)–(c), respectively. The observed FT-IR spectra of ECA and PECA are similar to those of the reported typical ECA and PECA [28,29]. Our particular interests are in the peaks of CC bond, because this functional group is only observed in the monomer and disappear in the polymer due to the formation of polymer chain as suggested in Fig. 1.
Rapid coating of millimeter-scale hydrogel capsules with interfacial polymerization
2024, Journal of Applied Polymer Science