Tough, Stretchable, and Thermoresponsive Smart Hydrogels.

Self-healing, thermoresponsive hydrogels with a triple network (TN) were obtained by copolymerizing N-isopropyl acryl amide (NiPAAm) with polyvinyl alkohol (PVA) functionalized with methacrylic acid and N,N'-methylene bis(acryl amide) crosslinker in the presence of low amounts (<1 wt.%) of tannic acid (TA). The final gels were obtained by crystalizing the PVA in a freeze-thaw procedure. XRD, DCS, and SEM imaging indicate that the crystallinity is lower and the size of the PVA crystals is smaller at higher TA concentrations. A gel with 0.5 wt.% TA has an elongation at a break of 880% at a tension of 1.39 MPa. It has the best self-healing efficiency of 81% after cutting and losing the chemical network. Step-sweep strain experiments show that the gel has thixotropic properties, which are related to the TA/PVA part of the triple network. The low amount of TA leaves the gel with good thermal responsiveness (equilibrium swelling ratio of 13.3). Swelling-deswelling loop tests show enhanced dimensional robustness of the hydrogel, with a substantial constancy after two cycles.

Fabrication of Thermo-Responsive Controllable Shape-Changing Hydrogel.

Temperature response double network (DN) hydrogels comprising a network formed by polymerization of methacrylic acid (MA) modified PVA, N,N'-methylene bis(acrylamide), N-isopropylacryl amide (NIPAM), and one formed from crystalline polyvinyl alcohol (PVA) are prepared in a 3D printed tailor-made mold. The (PVA-MA)-g-PNIPAAm thermoset intermediate is formed in water by a radical, photo-initiated process, and in the presence of dissolved PVA polymers. A subsequent freezing-thawing sequence induces the crystallization of the PVA network, which forms a second network inside the thermoset NIPAM polymer. The prepared hydrogel is thermoresponsive by the phase transition of PNIPAAm segments (T ≈ 32 °C) and has good mechanical properties (tensile strength 1.23 MPa, compressive strength 1.47 MPa). Thermal cycling between room temperature at 40 or 50 °C shows the product converses from a virgin-state to a steady-state, which most likely involves the reorganization of PVA crystals. The swelling-deswelling cycles remain clear at a length change of about 13%.

Catalytic Chain Transfer Copolymerization of Propylene Oxide and CO2 using Zinc Glutarate Catalyst.

Oligo and poly(propylene ether carbonate)-polyols with molecular weights from 0.8 to over 50 kg/mol and with 60-92 mol % carbonate linkages were synthesized by chain transfer copolymerization of carbon dioxide (CO2) and propylene oxide (PO) mediated by zinc glutarate. Online-monitoring of the polymerization revealed that the CTA controlled copolymerization has an induction time which is resulting from reversible catalyst deactivation by the CTA. Latter is neutralized after the first monomer additions. The outcome of the chain transfer reaction is a function of the carbonate content, i. e. CO2 pressure, most likely on account of differences in mobility (diffusion) of the various polymers. Melt viscosities of poly(ether carbonate)diols with a carbonate content between 60 and 92 mol % are reported as function of the molecular weight, showing that the mobility is higher when the ether content is higher. The procedure of PO/CO2 catalytic chain copolymerization allows tailoring the glass temperature and viscosity.

Synthesis of poly(ε-caprolactone)-grafted guar gum by surface-initiated ring-opening polymerization.

This study reports the grafting of poly(ε-caprolactone) (PCL) on guar gum (GG) by in-situ ring-opening polymerization using tetra(phenylethynyl)tin (Sn(C≡CPh)4) as catalyst. The hydroxyl groups of guar gum act as initiators for ε-caprolactone ring-opening polymerization and the resulting poly(ε-caprolactone) binds covalently to the polysaccharide. The highest stability of Sn(C≡CPh)4 allows the reaction in open-air, thereby reducing the cost of the synthesis and provides polymers with high molar mass. Fourier transform infrared (FTIR) and the long-term stability of the suspension PCL-g-GG in dichloromethane confirmed the effectiveness of grafting of PCL into GG. The size exclusion chromatography (SEC) results show that the molar masse of grafted PCL could be modulated by varying the amount of guar gum. From thermogravimetric analysis and differential scanning calorimetry results the thermal stability of PCL-g-GG is greatly improved with different content of guar gum, also the melting temperature and crystallinity increased by increasing the GG content. The scanning electron microscopy (SEM) analyses showed the good adhesion between GG and PCL with 5% of GG contents. It was also revealed by contact angle measurements that the grafting of PCL to GG leads to a decrease of hydrophobicity of PCL. The micro-indentation hardness properties of the prepared PCL-g-GG were significantly improved, as compared to neat PCL.

Viscoelastic properties of aqueous guar gum derivative solutions under large amplitude oscillatory shear (LAOS).

The industrial relevant nonlinear viscoelastic properties of aqueous carboxymethyl hydroxypropyl guar gum (CMHPG) and non-ionic hydroxypropyl guar gum (HPG) solutions between semi-dilute and concentrated solution state were investigated by large amplitude oscillatory shear flow (LAOS). Aqueous CMHPG and HPG solutions enter the nonlinear flow regime at deformations γ0>100%. The nonlinear stress waveforms were analyzed by FT-rheology and orthogonal stress decomposition along the MITlaos framework. A rheological fingerprint is generated (Pipkin space) showing that the guar gum derivative solutions undergo a shear-thinning at high strains, which is preceded by a thickening above a minimum strain rate at intermediate strains. The influence and breakup of superstructures/aggregates gives a "rheological fingerprint", a function of the applied deformation and time scale (Pipkin space). A characteristic process time was found that scales exponentially with the overlap parameter with an exponent of 4/2, and is proposed to represent the relaxation process of the superstructure in solution.

Extensional flow behavior of aqueous guar gum derivative solutions by capillary breakup elongational rheometry (CaBER).

The extensional rheological properties of aqueous ionic carboxymethyl hydroxypropyl guar gum (CMHPG) and non-ionic hydroxypropyl guar gum (HPG) solutions between the semi-dilute solution state and the concentrated network solution state were investigated by capillary breakup elongational rheometry (CaBER). Carboxymethylated guar gum derivatives show an instable filament formation in deionized water. The ratio of elongational relaxation time λE over the shear relaxation time λS follows a power law of λE/λS∼(c · [η])(-2). The difference of the relaxation times in shear and elongation can be related to the loss of entanglements and superstructures in elongational flows at higher strains.

Structure-property relationships of carboxymethyl hydroxypropyl guar gum in water and a hyperentanglement parameter.

The viscoelastic properties of carboxymethyl hydroxypropyl guar gum (CMHPG) in aqueous solution were determined as function of concentration and of molecular weight, using SEC/MALLS/dRI and viscometry. The chain is more rigid as in native guar as was deduced from the molecular parameter in dilute solution. Superstructures are formed in moderately concentrated solutions as is shown from the comparison of steady state shear and small amplitude oscillatory shear (SAOS) experiments. The shear rate dependent viscosity of CMHPG can satisfactorily be described by the Carreau-Yasuda model with the rheological parameters (η0, λ0, n, b) obtained from the evaluation of viscosity data. A quantitative hyperentanglement parameter is introduced to account for the differences in responses in shear and SAOS experiments.

Toward Self-Healing Hydrogels Using One-Pot Thiol-Ene Click and Borax-Diol Chemistry.

Intrinsic self-healing soft materials such as hydrogels are especially promising for a variety of medical applications. Multistep preparation of starting functional polymer precursors and the expensive stock materials such as tetra-polyethylene glycol are one of the factors that limit the wider use of self-healing hydrogels. Herein, we reported a facile one-pot approach to prepare PEG based self-healing hydrogels from inexpensive commercially available components: polyethylene glycol diacrylate and dithiothreitol. For the first time, borax was used as the catalyst for a thiol-ene Michael-type polyaddition of PEG gels. Borax as the catalyst is quite efficient, allowing rapid gelation (from 40 s to 2 min) under ambient conditions and at room temperature. Essentially, as one catalyst, borax induces the formation of two classes of bonds, covalent thioether and transient boronate ester bonds, were formed at the same time. The storage modulus of the afforded PEG gel (87.5% water) reached up to 104 Pa, making the mechanical performance comparable with permanently cross-linked PEG gels. Additionally, the dynamic nature of the boronate ester linkages imparts the gel with self-healing properties, and the obtained gels can be healed within 30 min without external stimulus. Further, the transparent hydrogel is pH and thermal responsive. We believe that the manifold impacts of borax can open a new route to prepare hydrogels with intriguing properties, which find potential application as gel sealant, biosensors, or regenerative medicines.

On the formation of aliphatic polycarbonates from epoxides with chromium(III) and aluminum(III) metal-salen complexes.

A DFT-based description is given of the CO2/epoxide copolymerization with a catalyst system consisting of metal (chromium, iron, titanium, aluminum)-salen complexes (salen = N,N'-bis(3,5-di-tert-butylsalicyliden-1,6-diaminophenyl) in combination with either chloride, acetate, or dimethylamino pyridine (DMAP) as external nucleophile. Calculations indicate that initiation proceeds through nucleophilic attack at a metal-coordinated epoxide, and the most likely propagation reaction is a bimolecular process in which a metal-bound nucleophile attacks a metal-bound epoxide. Carbon dioxide insertion occurs at a single metal center and is most likely the rate-determining step at low pressure. The prevalent chain terminating/degradation-the so-called backbiting, a reaction leading to formation of cyclic carbonate from the polymer chain-would involve attack of a carbonate nucleophile rather than an alkoxide at the last unit of the growing chain. The backbiting of a free carbonato chain end is particularly efficient. Anion dissociation from six-coordinate aluminum is appreciably easier than from chromium-salen complexes, indicating the reason why in the former case cyclic carbonate is the sole product. Experimental data were gathered for a series of chromium-, aluminum-, iron-, and zinc-salen complexes, which were used in combination with external nucleophiles like DMAP and mainly (tetraalkyl ammonium) chloride/acetate. Aluminum complexes transform PO (propylene oxide) and CO2 to give exclusively propylene carbonate. This is explained by rapid carbonate anion dissociation from a six-coordinate complex and cyclic formation. CO2 insertion or nucleophilic attack of an external nucleophile at a coordinated epoxide (at higher CO2 pressure) are the rate-determining steps. Catalysis with [Cr(salen)(acetate/chloride)] complexes leads to the formation of both cyclic carbonate and polypropylene carbonate with various quantities of ether linkages. The dependence of the activity and selectivity on the CO2 pressure, added nucleophile, reaction temperature, and catalyst concentration is complex. A mechanistic description for the chromium-salen catalysis is proposed comprising a multistep and multicenter reaction cycle. PO and CO2 were also treated with mixtures of aluminum- and chromium-salen complexes to yield unexpected ratios of polypropylene carbonate and cyclic propylene carbonate.

Mechanistic aspects of the metal catalyzed alternating copolymerization of epoxides and carbon monoxide.

The cobalt-catalyzed alternating copolymerization of epoxides and CO is a novel, direct approach to aliphatic polyesters, such as poly(hydroxybutyrate) (PHB). This reaction was found to be catalyzed by Ph3Si[Co(CO)4] (4) and pyridine affording in a first step the stable mono-insertion product Ph3Si-O-CH(CH3)-CH2-CO-Co(CO)4 (5). However, a profound mechanistic understanding, especially of the role of pyridine as the key component for the polymerization reaction was missing. ATR-IR online monitoring under catalytic conditions and DFT calculations were used to show that an acylpyridinium cation is formed by cleavage of the cobalt-acyl bond of 5 in the presence of pyridine. The Lewis acid thus generated activates the next incoming epoxide monomer for ring opening through [Co(CO)4]-. The catalytic cycle is completed by a subsequent CO insertion in the new cobalt-alkyl bond. The calculations are used to explore the energetic hypersurface of the polymerization reaction and are complemented by extended experimental investigations that also support the mechanistic hypotheses.

Multisite catalysis: a mechanistic study of beta-lactone synthesis from epoxides and CO--insights into a difficult case of homogeneous catalysis.

Carbonylation of epoxides with a combination of Lewis acids and cobalt carbonyls was studied by both theoretical and experimental methods. Only multisite catalysis opens a low-energy pathway for trans opening of oxirane rings. This ring-opening reaction is not easily achieved with a single-site metal catalyst due to structural and thermodynamic constraints. The overall reaction pathway includes epoxide ring opening, which requires both a Lewis acid and a tetracarbonylcobaltate nucleophile, yielding a cobalt alkyl-alkoxy-Lewis acid moiety. After CO insertion into the Co-C(alkyl) bond, lactone formation results from a nucleophilic attack of the alkoxy Lewis acid entity on the acylium carbon atom. A theoretical study indicates a marked influence of the Lewis acid on both ring-opening and lactone-formation steps, but not on carbonylation. Strong Lewis acids induce fast ring opening, but slow lactone formation, and visa versa: a good balance of Lewis acidity would give the fastest catalytic cycle as all steps have low barriers. Experimentally, carbonylation of propylene oxide to beta-butyrolactone was monitored by online ATR-IR techniques with a mixture of tetracarbonylcobaltate and Lewis acids, namely BF(3), Me(3)Al, Et(2)Al(+).diglyme, and a combination of Me(3)Al/dicobaltoctacarbonyl. We found that the last two mixtures are extremely active in lactone formation.

Variation in the Mode of Coordination of Aryl Sulfonates to Zirconocene in the Solid State.

The solid-state structures of three zirconocene aryl sulfonates were determined. In Cp(2)Zr(OSO(2)C(6)H(5))(2) (1), one of the sulfonate ligands is monodentate, the other bidentate coordinated. Cp(2)Zr(OSO(2)-4-C(6)H(4)Cl)(2) (2) and Cp(2)Zr(OSO(2)-3,4-C(6)H(3)Cl(2))(2) (3) are dimers of pentacoordinated zirconocenes with two monodentate sulfonates and a double bridge of &mgr;-O,&mgr;-O'-sulfonates. A possible explanation for the formation of the solid-state structures is offered in terms of differences in electron density of the sulfonate oxygen atoms. 1: C(22)H(20)O(6)S(2)Zr, a = 8.062(2) Å, b = 14.502(3) Å, c = 19.623(4) Å, alpha = 90.91(1) degrees, beta = 101.78(1) degrees, gamma = 106.00(2) degrees, triclinic, P&onemacr;, Z = 4. 2: C(22)H(18)Cl(2)O(6)S(2)Zr, a = 7.9669(8) Å, b = 11.0816(12) Å, c = 13.4056(10) Å, alpha = 79.944(7) degrees, beta = 75.009(7) degrees, gamma = 84.647(9) degrees, triclinic, P&onemacr;, Z = 2. 3: C(22)H(16)Cl(4)O(6)S(2)Zr, a = 7.7574(7) Å, b = 12.1124(12) Å, c = 13.4613(11) Å, alpha = 85.343(7) degrees, beta = 76.653(6) degrees, gamma = 79.880(8) degrees, triclinic, P&onemacr;, Z = 2.