Xuan Liuab,
Ru Chengb,
Jianping Deng*a and
Youping Wu*b
aState Key Laboratory of Chemical Resource Engineering, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China. E-mail: dengjp@mail.buct.edu.cn; Tel: +86-10-6443-5128
bState Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China. E-mail: wuyp@mail.buct.edu.cn; Tel: +86-10-6444-2621
First published on 19th September 2014
A novel type of magnetic composite particles was constructed using helical poly(n-hexyl isocyanate) and Fe3O4. For this purpose, well-defined 4-ethynylbenzyloxy-terminal poly(n-hexyl isocyanate)s (PHIC–CCs) were synthesized via coordination polymerization by using an organotitanium catalyst. The PHIC–C
Cs were characterized by GPC, FT-IR and 1H NMR techniques. UV-vis absorption spectra demonstrated that the PHIC–C
Cs adopted dynamic helical structures in tetrahydrofuran. Azide-modified magnetic Fe3O4 nanoparticles (Fe3O4@N3 NPs) were prepared through the reaction between 3-azidopropyltrimethoxysilane and oleic acid-coated magnetic Fe3O4 NPs. The obtained clickable PHIC–C
C and Fe3O4@N3 NPs were subjected to the Cu-catalyzed azide/alkyne cycloaddition for synthesizing the anticipated Fe3O4@PHIC composite NPs. FT-IR, TGA and TEM techniques confirmed the formation of the magnetic composite nanoparticles. UV-vis absorption spectra demonstrated that the PHIC chains coated on the magnetic Fe3O4 NPs adopted dynamic helical structures. XRD measurements revealed that coating PHIC chains on Fe3O4 nanoparticles did not change the phase properties of Fe3O4 nanoparticles. The Fe3O4@PHIC composite NPs showed a saturation magnetization of 17.8 emu g−1 and the expected rapid magnetic responsivity.
Polyisocyanates18–21 have recently received much attention because of their unique features such as the ability to form helical22,23 and liquid crystalline24 structures. Isocyanate polymers can adopt a predominant helicity when prepared by utilizing chiral initiators,25 solvents26 or monomers.27 Helical polyisocyanates demonstrated the majority rule28 and the sergeant-and-soldiers principle,29,30 as originally discovered by Green et al. Because of their fascinating helical structures and appealing properties, polyisocyanates are recognized as good candidate materials for developing liquid crystals,24,31,32 optical switches,33 recognition devices27 and so forth.23,25,34–36 Novak group37 prepared alkoxytitanium catalysts that effectively catalyzed the polymerization of isocyanates. However, no report has been dedicated to the preparation of helical polyisocyanates grafted on the surface of nanoparticles. We reason that a judicious combination of helical polyisocyanates and Fe3O4 NPs will undoubtedly give rise to a number of unique functional materials. Such magnetic composite particles are expected to show not only the magnetic properties derived from Fe3O4, but also certain attractive properties from helical polyisocyanates. Moreover, this novel type of magnetic composite particles may find significant applications as smart materials, optical materials, etc. Herein, we report a facile synthesis of magnetic composite NPs consisting of Fe3O4 and poly(n-hexyl isocyanate) (PHIC). The reason for using PHIC as a model of synthetic polyisocyanates is that PHIC has been well investigated in literature18–21 and by our group.38 By following the same strategy, a significant number of other novel composite particles can be prepared next.
The next step was to extract Fe3O4@OA NPs from water into toluene. Briefly, to a 250 mL extractor, the magnetic Fe3O4 NPs water dispersion (50 mL) and toluene (50 mL) were mixed. Fe3O4@OA NPs were transferred into toluene phase by adding NaCl (0.2 g). Magnetic Fe3O4 NPs showed good dispersibility in toluene because of the protection of a single layer of OA. Finally, the toluene dispersion was refluxed to remove most of the water under a nitrogen atmosphere, and the resulting Fe3O4@OA was diluted with toluene to 10 mg mL−1.
Run | nHIC/ncatb (mol mol−1) | Polymer | |||||
---|---|---|---|---|---|---|---|
Sample code | Yieldc (%) | DPd | Mnd | Mne | PDId | ||
a [HIC]0 = 5 mol L−1; polymerization temperature, 30 °C; polymerization time, 24 h; solvent, CH2Cl2.b The monomer-to-catalyst ratio, in mole.c Determined gravimetrically.d DP, degree of polymerization; Mn, number-average molecular weight; PDI (Mw/Mn), polydispersity of molecular weight; determined by GPC in THF.e Determined by theoretical calculation, Mn = (nHIC/ncat) × MnHIC + Mncatalyst. | |||||||
1 | 23 | PHIC–C![]() |
63.2 | 32 | 4400 | 3200 | 1.16 |
2 | 34 | PHIC–C![]() |
54.7 | 42 | 5700 | 4600 | 1.15 |
3 | 47 | PHIC–C![]() |
47.3 | 59 | 7800 | 6300 | 1.27 |
Three PHIC–CCs were designed and successfully prepared in the present study, as presented in Table 1 and Fig. S1 (GPC elution profiles of the polymers, in ESI†). The data in Table 1 show that on increasing the monomer/catalyst molar ratio, there was an increase in the actual molecular weights of the PHIC–C
Cs. However, the measured molecular weights are much larger than the corresponding theoretical values. This could be explained as follows. Polyisocyanates could be regarded as rigid polymer chains. Accordingly, for the molecular weight obtained via GPC when calibrated by using polystyrenes as the standards, there is usually a large inflation between it and the absolute value.42,43 Table 1 also shows that the conversion percentage of HIC is not highly satisfactory. This is due to the reversibility of the polymerization reaction of HIC with organotitanium(IV) catalysts.37
Fig. 1 shows the FT-IR spectra of 4-ethynylbenzyl alcohol, HIC and PHIC–CC-1 (taken as an example of the PHIC–C
Cs). In the spectrum of 4-ethynylbenzyl alcohol, the broad band at 3500–3200 cm−1 is assigned to the –OH group, while the peaks around 2120 and 816 cm−1 are assigned to the alkynyl and phenyl groups, respectively. In the spectrum of HIC, the band at 2270 cm−1 is ascribed to the isocyanate group stretching vibration. For the polymer PHIC–C
C-1, the peak around 3300 cm−1, which is assigned to the hydroxyl groups of 4-ethynylbenzyl alcohol, disappeared completely. In addition, the absence of absorption at 2270 cm−1 indicates that the obtained polymers did not contain residual isocyanate groups, i.e., monomers. Nonetheless, the characteristic peak of alkynyl groups, which should appear at 2120 cm−1, could hardly be observed. This is because only one alkynyl group existed at the end of each polymer chain. The characteristic peaks of –C
O and –C–N around 1715 and 1179 cm−1 could also be clearly observed.38 The characteristic peak of phenyl group suffered a blue shift from 816 to 792 cm−1. All the observations aforementioned demonstrate the formation of PHIC–C
Cs.
The 1H NMR spectrum of PHIC–CC-1 (as a model) is shown in Fig. 2. CDCl3 was used as solvent for the NMR measurements. The peak at 2.13 ppm is assigned to the ethynyl proton in the chain end of the obtained PHIC–C
C-1 (Ha). The signals located at chemical shifts of 7.34–7.52 ppm correspond to the phenyl protons (Hb). The peak of the methylene protons adjacent to phenyl group was observed at 5.20 ppm (Hc). The broad band at 3.77 to 3.82 ppm is assigned to the methylene protons directly attached to the N atom of HIC (Hd). The signals located at 1.65 ppm are ascribed to the methylene protons of HIC (He). The peak at 0.88 ppm is due to the terminal methyl protons in HIC units (Hi). The peak at 1.28 ppm indicates the other methylene protons in HIC units (Hf, Hg, Hh). As described above, the characteristic resonances for all the protons of PHIC–C
C-1 can be clearly observed at their corresponding positions, as illustrated in Fig. 2, demonstrating the successful preparation of PHIC–C
C-1.
It is well known that polyisocyanates can form helical structures, according to the earlier studies.23,25,34,38,44–46 UV-vis and CD spectroscopy measurements could demonstrate this conclusion. Lee et al.25,34 reported that chiral PHIC macromonomers showed a positive cotton effect at 250 nm due to a characteristic n → π* transition of the polyisocyanate backbone. Therefore, the present PHIC–CCs were also subjected to UV-vis absorption and CD measurements. The CD spectra showed no CD signal as expected, because no chiral center was contained in the polymers. The three PHIC–C
Cs showed the same results, and here we consider PHIC–C
C-1 as an example to discuss the helical structures of the PHIC–C
Cs. Fig. 3A shows the UV-vis absorption spectra of PHIC–C
C-1 measured in THF solution at varied temperatures. PHIC–C
C-1 showed a strong UV-vis absorption around 250 nm. This is in good agreement with the results reported earlier by Lee et al.34 and by our group.38 Therefore, we conclude that the PHIC–C
Cs adopted helical conformations in THF. When the temperature was altered, the UV-vis absorption intensities of PHIC–C
C-1 showed a large difference. In detail, the UV-vis absorption decreased when temperature was increased from 20 to 60 °C. This observation demonstrates that the helical structures of PHIC–C
Cs were dynamic helices, as introduced by Okamoto et al.47
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Fig. 3 UV-vis absorption spectra of PHIC–C![]() |
In our research, we adopted a coprecipitation method by using OA as surfactant to acquire a stable colloidal dispersion of magnetic Fe3O4 NPs. By adding some salts such as NaCl, KCl, KI, or NaBr as an inducer, the magnetic Fe3O4 NPs were extracted into toluene.12 APTMS was prepared from the nucleophilic substitution reaction between sodium azide and 3-chloropropyltrimethoxysilane in DMF.41 In order to consume 3-chloropropyltrimethoxysilane completely, sodium azide was excessively loaded. Since only 3-chloropropyltrimethoxysilane and APTMS are soluble in DMF, the excessive sodium azide and the by-product could be easily removed by filtration. After that, Fe3O4@N3 NPs were obtained by replacing the OA layer by APTMS. Then, PHIC was grafted onto magnetic Fe3O4 NPs to fabricate Fe3O4@PHIC composite nanoparticles using the click reaction, Cu(I)-catalyzed 1,3-dipolar cycloaddition, between the Fe3O4@N3 NPs and the ethynyl-terminated PHIC.
The shape and size of the composite nanoparticles were characterized by TEM. Fig. 4 shows the typical TEM images of Fe3O4@OA, Fe3O4@N3 and Fe3O4@PHIC composite nanoparticles. The Fe3O4@OA NPs (Fig. 4A) show either a spherical or an ellipsoidal shape with some irregularities. The particle size distribution histogram of Fe3O4@OA NPs calculated from the TEM images is shown in Fig. 4B. It can be clearly seen that the Fe3O4@OA NPs had a narrow size distribution with an average particle size of 18 ± 1 nm (after analysis of over 100 nanoparticles). The OA layer on the surface of magnetic Fe3O4 NPs played an important role in improving the dispersion of magnetic Fe3O4 NPs.12 Fig. 4C and D show that the Fe3O4@N3 NPs possessed similar shape, size and size distribution to those of the Fe3O4@OA NPs (after analysis of over 50 nanoparticles). However, the Fe3O4@N3 NPs aggregated to some degree, because the OA layer was substituted by APTMS. The Fe3O4@PHIC composite nanoparticles (Fig. 4E) noticeably demonstrated a PHIC layer coated on the surface of the magnetic Fe3O4 NPs. Compared with the Fe3O4@N3 NPs, the Fe3O4@PHIC composite nanoparticles aggregated more noticeably. This could be explained by the interaction force among PHIC chains. Because of the noticeable aggregation of the Fe3O4@PHIC composite nanoparticles, it is difficult to obtain the particle size distribution histogram of Fe3O4@PHIC NPs, as can be seen in the TEM images. All the observations mentioned above indicate that PHIC was successfully attached on the surface of the magnetic Fe3O4 NPs. This hypothesis was further confirmed by the following characterizations.
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Fig. 4 TEM images of particles: (A) Fe3O4@OA, (C) Fe3O4@N3, and (E) Fe3O4@PHIC. Particle size distribution histograms of Fe3O4@OA (B) and Fe3O4@N3 (D) nanoparticles, calculated from the TEM images. |
The crystal phases of magnetic products were investigated by XRD analysis. Fig. 5 displays the XRD patterns of the Fe3O4@N3 NPs and Fe3O4@PHIC composite nanoparticles. These two sets of nanoparticles show similar diffraction peaks at 2θ = 18.4°, 30.1°, 35.6°, 37.2°, 43.1°, 53.5°, 57.1°, and 62.7°. These peaks correspond to the (111), (220), (311), (222), (400), (422), (511), and (400) lattice planes, respectively, which are in agreement with the literature data.11,12 All the observed peaks in the patterns can be indexed to the face centered cubic phase of Fe3O4.48 The results revealed that the chemical modification of Fe3O4 nanoparticles by PHIC did not change the phase properties of Fe3O4 nanoparticles.
All the samples of PHIC–CC, Fe3O4@N3 and Fe3O4@PHIC were characterized by FT-IR spectroscopy. The relevant spectra are illustrated in Fig. 6, with PHIC–C
C-1 as an example. The FT-IR spectrum of PHIC–C
C-1 has been discussed above. In the spectrum of Fe3O4@N3 NPs, the band at 2106 cm−1 is assigned to N
N
N antisymmetric stretching vibration in azide.49 The characteristic peak of Fe–O stretching vibration can be found at 590 cm−1.50 For the Fe3O4@PHIC composite nanoparticles, the band at 1545 cm−1 is assigned to 1,2,3-triazole.49 The bands for alkyne (2120 cm−1) and azide (2106 cm−1) cannot be observed in the samples, demonstrating the successful conversion of alkyne and azide groups to 1,2,3-triazole by the click reaction. Moreover, there are also bands at 1700 cm−1 due to the C
O stretching vibration in PHIC–C
C and 586 cm−1 due to the Fe–O stretching vibration in magnetic Fe3O4 NPs, which clearly demonstrates that PHIC was chemically grafted on the surface of magnetic Fe3O4 NPs through the click reaction.
As discussed in the synthesis of PHIC–CCs, we have demonstrated that UV-vis absorption spectroscopy is an effective means for identifying the helical structures of PHIC. The above-obtained Fe3O4@PHIC composite nanoparticles were also subjected to UV-vis spectroscopy measurements. Unfortunately, we cannot directly and quantitatively characterize the second structures of PHICs due to the particle state. The UV-vis spectra only provided qualitative information (Fig. 3B). Herein, we point out that, as discussed above, no CD effect was observed in the CD spectra of the Fe3O4@PHIC composite nanoparticles. Fig. 3B shows the UV-vis spectra of the Fe3O4@PHIC composite nanoparticles measured in THF solution at varied temperatures. The Fe3O4@PHIC composite nanoparticles showed a strong UV-vis absorption around 250 nm. In addition, the UV-vis absorption decreased when the temperature was increased from 30 to 60 °C. These results demonstrated the existence of dynamic helical structures in the PHIC chains forming the composite nanoparticles.
Magnetic properties are necessary for practical applications of magnetic materials. Field dependent magnetization measurements on the samples were conducted to study the magnetic behaviors. Fig. 7 shows the VSM magnetization curves of Fe3O4@OA, Fe3O4@N3 and Fe3O4@PHIC composite nanoparticles measured at room temperature. No obvious magnetic hysteresis loop was observed for any of the three samples. In other words, the remanence did not exist when the magnetic field was removed, indicating that all the particles possessed superparamagnetic features originating from the magnetite inner cores. The maximum saturation magnetization (MSM) of Fe3O4@OA, Fe3O4@N3 and Fe3O4@PHIC composite nanoparticles was 55.1, 57.9 and 17.8 emu g−1, respectively. The MSM of Fe3O4@OA was lower than that of Fe3O4@N3, since the content of OA was higher than that of APTMS. This was also observed from the TGA analysis, as discussed next. In addition, with the coating of the non-magnetic PHIC layers onto the magnetic Fe3O4 NPs, the MSM of the resulting Fe3O4@PHIC composite nanoparticles was remarkably reduced due to the decrease in the mass content of the magnetite component. The inset in Fig. 7 shows that the Fe3O4@PHIC composite nanoparticles dispersion in THF responded quickly to an external magnet. The time from state (A) to state (B) was within 25 s. When the external magnet was taken off, the aggregated particles could be re-dispersed in a solvent just by shaking. This quick responsivity of Fe3O4@PHIC composite nanoparticles is extremely important for practical applications, particularly in terms of recycling.
The thermal stability and the composition of the composite nanoparticles were explored by thermogravimetric analysis. Fig. 8 shows the TGA curves of Fe3O4@OA, Fe3O4@N3 and Fe3O4@PHIC nanoparticles. The weight loss in the Fe3O4@OA and the Fe3O4@N3 was 14.7% and 12.5%, respectively. Both the two kinds of nanoparticles exhibited a two-stage weight-loss process. The first loss until 255 °C was due to the evaporation of physically absorbed water or solvent, and the second major weight loss from 255 to 450 °C was due to the decomposition of the low molecular organics attached on the surface of magnetic Fe3O4 NPs (OA for Fe3O4@OA and APTMS for Fe3O4@N3). In addition, the weight loss in the Fe3O4@OA NPs was slightly higher than that in the Fe3O4@N3 NPs. This is because the content of OA was higher than that of APTMS, similar to the observation in VSM (Fig. 7). The Fe3O4@PHIC composite nanoparticles also decomposed in two stages. The first weight loss (about 5.2 wt%) till 250 °C was also due to the evaporation of physically absorbed water or solvent. About 59.3 wt% loss of weight occurred when temperature rose from 250 to 800 °C. During this stage, the PHIC component in the Fe3O4@PHIC composite nanoparticles disintegrated gradually. The TGA curve of the Fe3O4@PHIC composite nanoparticles exhibited a remarkably higher weight loss relative to the Fe3O4@N3 nanoparticles, which further demonstrated that PHIC was efficiently coated on the magnetic Fe3O4 NPs via click reaction.
Footnote |
† Electronic supplementary information (ESI) available: Synthesis of organotitanium(IV) catalyst and PHIC–C![]() ![]() |
This journal is © The Royal Society of Chemistry 2014 |