Yuqiong
Zhu
a,
Sihan
Li
a,
Huaqing
Liang
a,
Xiuli
Xie
a and
Fangming
Zhu
*ab
aGDHPPC Lab, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, 510275, China. E-mail: ceszfm@mail.sysu.edu.cn; Fax: +86-20-84114033; Tel: +86-20-84113250
bKey Lab for Polymer Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China
First published on 27th August 2019
The [OSSO]-type bis(phenolate) titanium complex 1 activated by methylaluminoxane (MAO) was tested as a homogeneous catalyst for ethylene coordination copolymerization with protected vinyl polar monomer of p-tert-butyl-dimethylsilyloxystyrene (p-TBDMSOS). The results showed that the active species were almost not poisonous to the catalyst by the protected vinyl polar monomer. Moreover, the composition and sequence length as well as sequence distribution in the copolymers were investigated by theoretical calculation and 13C nuclear magnetic resonance (13C NMR) characterization. Especially, the incorporation ratio of p-TBDMSOS into the polyethylene chain could be controlled by changing p-TBDMSOS concentration in the feed. Interestingly, an approximate alternating copolymer of poly(E-alt-(p-TBDMSOS)) could be formed when the p-TBDMSOS feed concentration increased to 1.0 mol L−1. Subsequently, the poly(ethylene-co-(p-hydroxystyrene)) (poly(E-co-(p-HOS))) could be prepared by a facile deprotection in terms of desilylation of tert-butyldimethylsilyl ether. The hydrophilicity of poly(E-co-(p-HOS)) films were investigated by water contact angle measurements.
Especially, it is considerably difficult to accomplish directly coordination polymerization of vinyl polar monomers promoted by titanium-based catalysts in consequence of the poisoning effect of active species by polar group. Consequently, these vinyl polar monomers were generally protected using bulky groups before polymerization.24–32 As reported by Kawabe et al.33,34 and Kim et al.,35 when the bulky tert-butyl(dimethyl)silyl protective group was used, the isotactic or syndiotactic poly(p-hydroxystyrene) (poly(p-HOS)) as well as styrene-based copolymers could be synthesized based on coordination polymerization with titanium-based complexes and methylaluminoxane (MAO). To best of our knowledge, the copolymerization of ethylene with vinyl polar monomer or protected vinyl polar monomer is less reported with titanium-based catalysts.24,36 Wu and his co-workers exhibited copolymerization of ethylene with 10-undecen-1-ol, 10-undecenoic acid, and 5-hexen-1-ol using triisobutylaluminum as a protection reagent catalyzed by phenoxy-imine (FI) titanium catalysts. Nevertheless, the incorporation ratio of polymers was less than 7 wt%.36 In this contribution, we demonstrated ethylene copolymerization with vinyl polar monomer on the basis of the strategy of group protection catalyzed by 1,4-dithiabutandiyl-2,2′-bis(6-cumenyl-4-methylphenoxy) titanium dichloride37 (complex 1) in the presence of MAO. Consequently, the poly(E-co-(p-HOS)) with controllable incorporation ratio of p-HOS into polyethylene chains by changing concentrations in the feed could be prepared by shielding hydroxyl group with tert-butyldimethylsilyl ether as a comonomer (p-tert-butyldimethylsilyloxystyrene (p-TBDMSOS)) used for ethylene coordination copolymerization and subsequent deprotection to form p-HOS units.38,39 Note that the introduction of p-HOS units could tremendously improve the surface hydrophilicity of the resultant copolymer films.
Scheme 1 The synthesis routes for poly(ethylene-co-(p-TBDMSOS)) and deprotection of hydroxyl groups to form poly(ethylene-co-(p-HOS)) catalyzed by complex 1 and MAO. |
Under 1.2 atm of ethylene pressure, the influences of different p-TBDMSOS concentrations in toluene in the feed on the copolymerization behaviours, structure parameters and thermal properties of the resultant copolymers were summarized in Table 1. To avoid the formation of PE homopolymer after p-TBDMSOS was entirely consumed at low p-TBDMSOS feed concentrations, the copolymerization reactions were stopped after 3 min.
Run | p-TBDMSOS (mol L−1) | Yield (g) | Activity b | TOF × 10−4c | M w d × 10−4 | M w/Mnd | T m or Tge (°C) | Conv. (%) | Incrop.f (mol%) | |
---|---|---|---|---|---|---|---|---|---|---|
E | p-TBDMSOS | |||||||||
a Polymerization conditions: titanium complex 1, 2.0 μmol; ethylene pressure, 1.2 atm; polymerization time, 3 min; toluene as solvent, total volume = 20 mL; Al/Ti = 1200; polymerization temperature, 30 °C. b Catalyst activity in 106 g (polymer) (mol Ti)−1 h−1. c TOF = mol of polymer consumed per mol catalyst per h (mol P mol−1 Ti h−1). d Determined by GPC in 1,2,4-trichlorobenzene (TCB) at 150 °C and in THF at 40 °C with polystyrene standards. e Determined by DSC. f Determined by 1H NMR. | ||||||||||
1 | 0.00 | 0.15 | 1.5 | 5.36 | — | 0.86 | 1.69 | 118.1 | — | 0 |
2 | 0.039 | 0.30 | 3.0 | 6.00 | 0.73 | 1.23 | 1.41 | −25.9, 5.9 | 83.4 | 10.9 |
3 | 0.058 | 0.38 | 3.8 | 6.09 | 0.91 | 1.24 | 1.51 | −19.4, 19.0 | 77.7 | 13.0 |
4 | 0.078 | 0.43 | 4.3 | 5.92 | 1.24 | 1.30 | 1.54 | −13.5, 28.2 | 74.8 | 17.3 |
5 | 0.10 | 0.56 | 5.6 | 6.20 | 1.66 | 1.39 | 1.54 | −9.9, 38.4 | 82.4 | 21.1 |
6 | 0.20 | 0.96 | 9.6 | 7.05 | 3.27 | 2.43 | 1.84 | 7.1 | 80.9 | 31.7 |
7 | 1.0 | 2.61 | 26.1 | 9.90 | 10.3 | 3.92 | 2.37 | 43.4 | 49.7 | 50.9 |
The complex 1/MAO presented a good catalyst system for ethylene homopolymerization and copolymerization with p-TBDMSOS. The catalytic activity gradually increased with the increase of the p-TBDMSOS concentrations in the feed resulting from the much higher molecular weight of p-TBDMSOS unit than that of ethylene unit. Moreover, the polymerization activity of monomers was also expressed as turnover frequency (TOF). The TOF of ethylene was nearly uninfluenced while the TOF of p-TBDMSOS increased by changing the p-TBDMSOS feed concentrations ranging from 0.039 to 1.0 mol L−1 at 30 °C, revealing that active species were almost not poisoned by the protected vinyl polar monomer. Consequently, the catalyst exhibited good catalytic behaviour for copolymerization of p-TBDMSOS with ethylene.
Note that p-TBDMSOS concentration gradually decreased as p-TBDMSOS was continuously consumed during the copolymerization process. Accordingly, the copolymerization products displayed two glass transition temperature (Tg) when the p-TBDMSOS feed concentration was less than 0.20 mol L−1 (Runs 2–5 in Fig. 1), indicating that they mainly consisted of two parts. The copolymer with higher Tg presents higher fraction of p-TBDMSOS units at the early stage, and the copolymer with lower Tg indicates that the sequence lengths of ethylene increased at the late stage. It is a remarkable fact that only a single Tg at higher p-TBDMSOS feed concentrations of Runs 6 and 7 were observed respectively (Fig. 1), which is probable that the concentration of p-TBDMSOS could maintain a relatively high value during the copolymerization process.
Fig. 1 DSC profiles of copolymerization products obtained from Runs 2–7 in Table 1. |
In order to analysis the distribution of ethylene units and p-TBDMSOS units in the copolymer chains, the reactivity ratios of ethylene (rE) and p-TBDMSOS (rp-TBDMSOS) were calculated by means of the Fineman–Ross equation.
The carbon terminology follows that of Carman and Wilkes,43 where S and T refer to the secondary (methylene) and tertiary (methine) carbons of the main chain, respectively. The position of carbon atom relative to its nearest T groups was labeled by two Greek subscripts where δ indicates all T carbons four or farther than four bonds away from the S carbon as shown in Scheme 2. Fig. 3 shows the aliphatic regions of 13C NMR spectra of poly(E-co-(p-TBDMSOS)) with different incorporation ratios of p-TBDMSOS. The absence of signal δ 42.0 ppm attributed to Tαα of the S°S° (S° = p-TBDMSOS) sequences suggesting that the ethylene sequences in the copolymer are separated by isolated p-TBDMSOS units at lower comonomer feed concentrations (Runs 2–6). Moreover, the ethylene sequence lengths are shortened as evidenced by the signal at δ 30 ppm, attributed to the presence of long ethylene sequences (EEE), dropping distinctly with the increase of the initial p-TBDMSOS feed concentrations (Runs 5–7).44
Fig. 3 Aliphatic regions of 13C NMR spectra of poly(E-co-(p-TBDMSOS)) with different incorporation ratios of p-TBDMSOS 10.9 mol% (Table 1, Run 2), 17.3 mol% (Run 4), 21.1 mol% (Run 5), 31.7 mol% (Run 6) and 50.9 mol% (Run 7). |
In addition, let PEE be the probability that a growing chain active species (E*) will add to monomer ethylene (ME). To a good approximation the only two possible fates of E* are addition of ME or addition of monomer p-TBDMSOS (Mp-TBDMSOS). Hence, it is possible to write this probability as
Therefore, in consideration of the relationship between PEE and rE, the average sequence lengths of ethylene units (lE) can be calculated as
Similarly, the average sequence lengths of p-TBDMSOS units (lp-TBDMSOS) is given by
The value of lE increases, while the value of lp-TBDMSOS decreases as result of the constant ethylene pressure in combination with the continuous reduction of p-TBDMSOS concentration during copolymerization process. Furthermore, the calculation results indicate that even though the value of lp-TBDMSOS is approaching to 1 whereas the value of lE is much larger than 2 in Runs 2–6, which in accordance with the observation of 13C NMR that the ethylene sequences are separated by isolated p-TBDMSOS units at lower p-TBDMSOS feed concentrations. On the other hand, 49.7% of p-TBDMSOS was consumed as result of copolymerization for 3 min (Run 7), corresponding to a p-TBDMSOS concentration ranging from 1.0 to 0.5 mol L−1. Therefore, the values of lE and lp-TBDMSOS were changed from 1.3 to 1.5 and 1.1 to 1.0, respectively, indicating the formation of approximate alternating copolymer of poly(E-alt-(p-TBDMSOS)) with a Tg of 43.4 °C. As a consequence, there is a strong tendency of the complex 1/MAO catalyst to produce alternating ES°E (E = ethylene, S° = p-TBDMSOS) sequences in the copolymers with comonomer concentration as evidenced by the presence of the Sββ methylene carbon relative to the alternating sequences in the Run 7 with p-TBDMSOS feed concentration of 1.0 mol L−1.
Poly(E-co-(p-TBDMSOS)) was easily deprotected by desilylation based on acidification so as to from poly(E-co-(p-HOS)).45Fig. 4 displays the typical 13C NMR spectra of poly(E-co-(p-TBDMSOS)) from Run 5 in Table 1 and poly(E-co-(p-HOS)) in terms of desilylation. The absence of characteristic peaks at −4.55, 17.99 and 25.63 ppm attributed to the tert-butyldimethylsilyl group after deprotection. We further confirmed the resulting polymers by IR spectra. As mentioned in Fig. 4a, the high peak at 1257 cm−1 and 917 cm−1 were corresponding to the symmetric deformation vibration of methyl of Si–CH3 and the stretching vibration of Si–C, respectively. The disappear of these peaks in Fig. 4b and the forming of a new peak at 1238 cm−1 attributed to the C–O stretching vibration of phenol also confirmed the success of deprotection and the formation of P(E-co-(p-HOS)), which was in line with the NMR analyses.
Fig. 4 The 13C NMR spectra of poly(E-co-(p-TBDMSOS)) (a) in CDCl3 and poly(E-co-(p-HOS)) (b) in DMSO-d6 and FT-IR for Run 5 in Table 1. |
Note that the introduction of p-HOS into polyethylene back-bone could dramatically improve its hydrophilicity.46Fig. 5 displays the representative photographs of a water droplet on polyethylene and poly(E-co-(p-HOS)) films at 25 °C. The water contact angle (θ) on polyethylene film is about 110°, indicating polyethylene is a hydrophobic material. Nevertheless, when the incorporation ratio was 13.0 mol%, the WCA exhibited a rapid decline to 85.6°. Furthermore, the contact angle decreases strikingly with increasing the incorporation of p-HOS units in poly(E-co-(p-HOS)).
Fig. 5 The photographs of water contact angle on polyethylene films and poly(E-co-(p-HOS)) films containing different incorporation ratios of p-HOS of 13.0 mol%, 21.1 mol% and 31.7 mol% at 25 °C. |
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9ra06271h |
This journal is © The Royal Society of Chemistry 2019 |