Physical Gelation of Amphiphilic Poly(N‐isopropylacrylamide): Influence of the Hydrophobic Groups

The self‐assembling properties of hydrophobically modified (N‐isopropylacrylamide) have been investigated by dynamic light scattering and rheological measurements. Size of the globules and transmission of the solutions vary strongly in the same range of temperature. The presence of hydrophobic groups leads to contraction of the globules' size compared to poly(N‐isopropylacrylamide) (PNIPAM). The viscoelastic properties of the samples in aqueous solution have been investigated as a function of copolymer concentration, structure of the hydrophobic group (dodecyl or adamantyl group), substitution level (1–5%) and over a temperature range covering the lower critical solution temperature (LCST). At high concentration and high level of adamantyl substitution, gelation is observed several degrees before the phase transition. A physical network is formed due to the strong hydrophobic interactions, and this physical gel undergoes phase transition without macroscopic phase separation.

     

Poly(N‐isopropylacrylamide)‐Modified Styrene‐Butadiene Rubber as Thermoresponsive Material

Narrowly distributed (N‐isopropylacrylamide) (NIPAM) polymers are prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization. After successful cleavage of the trithiocarbonate end groups (thiol generation), they can be grafted to styrene‐butadiene rubber (SBR) by a radical thiol‐ene reaction leading to various grafted SBR‐copolymers. During the grafting reaction, no crosslinking or branching of the SBR can be observed. Measurements of the contact angle of water show that the lower critical solution temperature (LCST) properties of the PNIPAM fraction affect the SBR. Films of the graft‐copolymer exhibit a distinct hydrophilicity below the LCST, while they show hydrophobic behavior above the LCST. Rheological measurements reveal a physical crosslinking of the functionalized SBR due to nanophase separation of the PNIPAM chains (hard phase) in the unpolar SBR. Compared with blends of SBR and PNIPAM, the PNIPAM‐grafted SBR possesses a much finer distribution of the PNIPAM domains (10–30 nm) within the matrix. In addition, two novel difunctional chain‐transfer agents are used, leading to difunctional PNIPAM, enabling a covalent crosslinking of SBR.

     

Thermo‐Responsive Assembly of Chemically Reduced Graphene and Poly(N‐isopropylacrylamide)

A stable aqueous solution of reduced graphene is prepared by chemical reduction of GO in the presence of PNIPAM in water through the hydrophobic interaction between graphene plates and PNIPAM backbones. Thermosensitive solubility switching of the graphene/PNIPAM assembly was successfully demonstrated below or above the LCST, which is higher (up to 42 °C) than the LCST of pure PNIPAM (36 °C) because interacting PNIPAM chains on graphene plates are less mobile than free PNIPAM chains. The success of PNIPAM as stabilizer for reduced graphene solution can be explained by both efficient hydrophobic interaction with graphene surface and matching of surface tension of water (72.8 mJ · m^?2) with “graphene‐friendly surface tension” (40–50 mJ · m^?2) by the presence of PNIPAM in water (41.8 mJ · m^?2).

     

Hydrophobically Modified Poly(acrylic acid) Using 3‐Pentadecylcyclohexylamine: Synthesis and Rheology

Summary: Hydrophobically modified poly(acrylic acid) was synthesized using 3‐pentadecylcyclohexylamine (3‐PDCA), which was in turn synthesized from 3‐pentadecylphenol, one of the components of cashew‐nut shell liquid (CNSL), a renewable resource material. ¹H NMR spectra confirmed the incorporation of 3‐PDCA onto PAA and a series of HMPs with three different molar concentrations, viz ? 3, 5 and 7 mol‐% of 3‐PDCA, were synthesized. An increase in viscosity with increasing hydrophobic content was observed by rheological measurements. The critical association concentrations were determined using an Ubbelohde viscometer and a controlled stress rheometer. The stability of HMPs towards temperature and shear was studied. Rheological measurements showed that there was a steady increase in viscosity with increase in hydrophobe content due to the formation of reversible networks. These polymers exhibited gel‐like behavior at low concentrations (≥2 wt.‐%) with an apparent yield stress (ca. 10 Pa) and showed shear thinning properties (non‐Newtonian). However, below a critical concentration, c [η], they showed Newtonian behavior.

η_sp of unmodified and modified PAA‐Na at various polymer concentrations.     

Poly(N‐isopropylacrylamide) Brush Fabricated by Surface‐Initiated Photopolymerization and its Response to Temperature

A well‐defined, high‐density poly(N‐isopropylacrylamide) (PNIPAM) brush was fabricated through a novel and reliable strategy by the combination of the self‐assembly of a monolayer of dendritic photoinitiator and surface‐initiated photopolymerization. The whole fabrication process of the PNIPAM brush was followed by water contact angles, X‐ray photoelectron spectroscopy, and atomic force microscopy. Characterization of the PNIPAM brush, such as molecular weight and thickness determination, were measured by gel permeation chromatography, and ellipsometry, and the graft density was estimated. The temperature response of the PNIPAM brush was further investigated and the result verified the coil‐to‐globule transition of the PNIPAM chains in water from low to high temperature.

     

Self‐Assembly of Polyrotaxanes Synthesized Via Click Chemistry of Azido‐Endcapped PNIPAAm‐b‐Pluronic F68‐b‐PNIPAAm/γ‐CD with Propargylamine‐Substituted β‐CDs

A kind of γ‐(cyclodextrin) (γ‐CD)‐based polyrotaxane (PR) is synthesized via an aqueous click reaction between propargylamine‐substituted β‐CD and polypseudorotaxanes (PPRs) self‐assembled from azido‐endcapped PNIPAAm‐b‐Pluronic F68‐b‐PNIPAAm with a varying amount of γ‐CD. The evolution of the self assembly, dependent on the preparation process, is observable by X‐ray diffraction (XRD) and DSC analyses. The γ‐CD is able to be included and preferably entrapped on the PNIPAAm blocks, showing a unique loose‐fit aggregate structure after the click reaction. Most γ‐CDs gradually slip over to the middle PPG block of Pluronic F68, giving rise to a characteristic channel‐type crystal structure in the dialy­sis process. In addition, the lower critical solution temperature (LCST) is sharply enhanced due to the coverage of the remaining γ‐CDs hindering the thermally responsive aggregation of the PNIPAAm blocks.

     

Temperature and pH Dual‐Responsive Behavior of Dendritic Poly(N‐isopropylacrylamide) with a Polyoligomeric Silsesquioxane Core and Poly(2‐hydroxyethyl methacrylate) Shell

Novel temperature and pH dual‐responsive dendritic polyoligomeric silsesquioxane (POSS)–poly(N‐isopropylacrylamide) (PNIPAm)–poly(2‐hydroxyethyl methacrylate) (PHEMA) copolymers are prepared via atom transfer radical polymerization and click reactions. The cloud points (T_c) decrease with decreasing pH from 10.0 to 5.0 due to the weakened inter‐molecular interactions and enhanced intra‐molecular hydrogen bonding, whereas the T_c exhibits a small increase from pH 5.0 to 4.0 because of the better solvation of PHEMA at highly acidic conditions. The above findings are corroborated by the different sizes of aggregates observed by dynamic light scattering. The encapsulation of a fluorescent dye and stimulated release by temperature and pH changes are also demonstrated.     

Preparation and Characterization of the Crystalline Inclusion Complex between β‐Cyclodextrin and Poly(neopentyl glycol)

This work reports the preparation and characterization of the crystalline inclusion complex between polymeric guest, poly(neopentyl glycol) (PNPG), and small‐molecular host, β‐cyclodextrin (β‐CD). The crystalline inclusion complex was characterized with FTIR, TGA, X‐ray diffraction, ¹H NMR and ¹³C CP/MAS NMR spectroscopes. It was found that the crystalline inclusion complex has higher temperature stability than the pure β‐CD. The X‐ray powder diffraction patterns of the crystalline inclusion complex proved that it has a columnar structure. ¹³C CP/MAS NMR spectra of the crystalline inclusion complex indicate that CDs adopt a more symmetrical conformation in the complex, while pure CD assume a less symmetrical conformation in the crystal without a guest inside its cavity.     

Asymmetric Behavior of Temperature‐Responsive Poly(N‐isopropylacrylamide) Ultrathin Layers Observed by Atomic Force Microscopy

During characterization of a temperature‐responsive poly(N‐isopropylacrylamide) (PIPAAm) layer grafted onto a Si(100) substrate, atomic force microscopy (AFM) is able to probe the interactions between the microscope tip and the polymer. The modification of the AFM tip surface with octadecyltrichlorosilane (OTS) changes the interaction between the PIPAAm surface and the tip. Although a repulsive interaction is observed between a commercially available Si tip and the PIPAAm surface, a strong attractive interaction between the OTS‐modified Si tip and the surface is observed. Adhesion‐force analysis shows changes in the hydrophilic/hydrophobic character of ultrathin PIPAAm surfaces immediately after a change in temperature. The PIPAAm surface becomes hydrophobic less than 30 min after temperature increase, but requires 120 min to become hydrophilic after temperature reduction.

     

Thermo‐ and pH‐Sensitivities of Thiosemicarbazone‐Incorporated,Fluorescent and Amphiphilic Poly(N‐isopropylacrylamide)

Summary: Novel hydrophobic comonomer (p‐methacrylamido)acetophenone thiosemicarbazone was synthesized and polymerized with N‐isopropylacrylamide to get a series of amphiphilic copolymers. The self‐aggregation behavior and thermo‐sensitive character of the (co)polymers were confirmed by TEM observation, fluorescence spectra, and cloud point measurement. Fluorescence emission of copolymer was significantly strengthened or switched off at an excitation wavelength of 320 nm upon the addition of acid or base, respectively. Thermo‐sensitivity, pH‐sensitivity, and pharmacologically versatile thiosemicarbazone groups were integrated into these novel fluorescent and amphiphilic copolymers, which will develop the novel applications of amphiphilic copolymer and environment‐responsive materials.

Fluorescence intensity at 393 nm of polymer 2 in water at 18 °C excited at 320 nm upon addition of acid and base.     

Gel Formation and Molecular Characteristics of Poly(N‐isopropylacrylamide) Prepared by Free‐Radical Redox Polymerization in Aqueous Solution

The molecular characteristics of poly(N‐isopropylacrylamide) (PNIPA), prepared by free‐radical polymerization using an aqueous redox initiator and reaction conditions comparable to those used in the synthesis of nanocomposite gels, were investigated by altering the monomer concentration ([NIPA]) and the polymerization temperature (T_p) across the transition temperature (LCST). When T_p<LCST, there is a critical [NIPA] (=n*) above which PNIPA partially forms gels in the absence of a chemical crosslinker, and the gel fraction increases with increasing [NIPA] and decreasing T_p. In the range of n<n*, the molecular weight of soluble PNIPA correlated well with [NIPA]. When T_p>LCST, gels were not formed regardless of [NIPA]. The structure and mechanism of formation of self‐crosslinked PNIPA gels are discussed.

     

Synthesis and Properties of Hydrophilic Networks Based on Poly(ethylene glycol) and β‐Cyclodextrin

New hydrophilic networks combining poly(ethylene glycol) (PEG) and β‐cyclodextrin (β‐CD) have been prepared. Both components are linked by reacting PEG chains previously end‐capped with isocyanate groups and β‐CD, forming urethane links. Networks of molar compositions (β‐CD/PEG) ranging from 1/4 to 1/14, and with four different molar masses (400, 600, 900, and 1 350 g · mol^?1) of the end‐capped PEG precursor have been synthesized. The networks have good thermal stability and low glass transition temperatures. Crystallinity has only been detected for the two higher molar mass PEG precursors. The swelling properties of these hydrogels depend on the chain lengths of the PEG precursor and also on the temperatures.

     

Preparation and Properties of Degradable Shape Memory Material Based on Partial α‐Cyclodextrin–Poly(ε‐caprolactone) Inclusion Complex

A series of supramolecular degradable inclusion complex (IC) films were formed by threading α‐cyclodextrin (α‐CD) molecules over poly(ε‐caprolactone) (PCL) according to the designed ratio of α‐CD–PCL. Due to containing both α‐CD–PCL inclusion crystallites and uncovered PCL crystallites, the resulting supramolecular α‐CD–PCL IC partial films displayed a shape memory effect. The properties of the materials were investigated by ¹H NMR, X‐ray diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and swelling measurement. It was found that the casting temperature and solvent have great influence on the formation and properties of the α‐CD–PCL partial ICs. The modes of complexes on different conditions were proposed. In addition, the introduction of inclusion structure accelerates the degradation of materials strongly.

     

Synthesis and Characterization of PNIPAm Core Cross‐Linked Star Polymers and Their Functionalization with Cyclodextrin

Poly(N‐isopropylacrylamide) (PNIPAm) core cross‐linked star (CCS) polymers (s‐(PNIPAm)_n) are synthesized by arm‐first ATRP method. The related synthesis conditions are investigated and optimized. By varying cross‐linker N,N‐methylenebisacrylamide (BIS) concentration, PNIPAm CCS polymers with about 47, 86, and 211 arms are synthesized. Then, under ATRP condition, the “living” sites at the core of s‐(PNIPAm)_n reacting with a monovinyl β‐cyclodextrin (β‐CD) monomer afford β‐CD functionalized s‐(PNIPAm)_n (CDF‐SPNIPAm). The structures of the star polymers are characterized. The results indicate that in CDF‐SPNIPAm, the ratio of β‐CD units to PNIPAm arm numbers could be up to 0.6:1. The fluorescence spectra of star polymer/ANS (8‐­anilino‐1‐naphthalenesulfonic acid ammonium salt hydrate) systems prove that the β‐CD moieties of CDF‐SPNIPAm are available for including guest molecules. By using pH‐sensitive adamantyl (Ada)‐terminated poly(4‐vinylpyridine) (Ada‐P4VP) (synthesized by ATRP strategy) as a model guest macromolecule, the host–guest complexation between β‐CD units of CDF‐SPNIPAm and adamantyl groups of Ada‐P4VP is confirmed via 2D NOESY ¹H NMR and DLS measurements. The results indicate that the presence of the Ada‐P4VP arms provides temperature‐responsive star polymers with pH sensitivity. Therefore, the β‐CD‐functionalized star PNIPAm could provide host macromolecular platform for constructing novel miktoarm star polymers.

     

Conductive and Tough Smart Poly(N‐isopropylacrylamide) Hydrogels Hybridized by Green Deep Eutectic Solvent

Conductive smart hydrogels with several virtues such as similar characters to biological tissues, sensitive response to ambient variations, have shown their excellent talents in the field of flexible electrical sensors, biomedical devices and directional transportation. However, complex preparing approaches or the instable inner structures have not only been time‐consuming, but also broken up the performance and reliability of the smart hydrogel‐based devices. In this work, a facile one‐step method is put forward to synthesize a kind of conductive poly(N‐isopropylacrylamide) (PNIPAM) hydrogel doped by a new green solvent of deep eutectic solvent (DES) containing choline chloride (ChCl) and acrylic acid (AA). Through the copolymerization of AA and NIPAM, the mechanical strength of the DES‐doped PNIPAM hydrogels is drastically improved compared to the pure PNIPAM gels, and some doped hydrogels lost the typical phase transition temperature of PNIPAM. Moreover, due to the ionic property of DES, the hybrid hydrogels also present the thermal‐depending conductivity as well as sensitive deformation response, which can be used as a smart switch in a circuit or a sensing element with environmental response ability. The cost‐effective preparation and the attractive performance of the DES‐doped hydrogels offer a new avenue to construct multi‐functional materials.     

Synthesis and Properties of pH‐ and Temperature‐Sensitive Poly[(N‐isopropylacrylamide)‐co‐(2‐methylenebutane‐1,4‐dioic acid)] Hydrogels

Summary: Hydrogels of NIPA and MBDA were synthesized by free‐radical crosslinking copolymerization with different monomer ratios and with two concentrations of the crosslinking agent. The aim of this work was to study the swelling behavior of these gels that are both temperature and pH sensitive. PNIPA hydrogels are typical examples of thermo‐shrinking hydrogels with a LCST, T_C, around 31–34 °C. MBDA is a weakly ionizable monomer which imparts a pH sensitiveness to the copolymer hydrogels. The pH influence on the swelling behavior of the studied hydrogels was analyzed using deionized water and aqueous HCl and NaOH as swelling media. According to the results found in deionized water, the swelling processes of P(NIPA‐MBDA) hydrogels follow second‐order kinetics at 22 and 37 °C. The equilibrium water content, W_∞, and the rate constant, K, increased at greater concentrations of MBDA and decreased as the crosslinking agent concentration increased. As the MBDA content in the hydrogel increased, the collapsing of the hydrogels at higher temperatures than the LCST became of less importance. The degree of swelling of pure PNIPA hydrogels was not influenced by the pH of the swelling medium. However, this influence increased as the MBDA content increased. This was due to the fact that at low pH most of the MBDA units are in the protonated (neutral) form and at high pH in the ionized one.

Swelling isotherms of hydrogels with different copolymer compositions and with 1.5 wt.‐% of BIS at 22 °C in deionized water.     

Effect of Temperature on the Mobility of Core‐Shell‐Type Nanoparticles Composed of Poly(γ‐benzyl‐L‐glutamate) and Poly(N‐isopropylacrylamide)

Summary: Core‐shell‐type nanoparticles composed of PBLG and PNIPAAm were prepared in an attempt to study the effects of temperature on the dynamic behavior of temperature‐sensitive polymeric shell, PNIPAAm, in the nanoparticles by ¹H NMR spectroscopy. Spin‐lattice relaxation time (T₁) and line halfwidth in D₂O and CDCl₃ were measured to monitor the change of the chain mobility of PNIPAAm in the GN nanoparticles within the temperature range encompassing its LCST. The molecular motion of PBLG segment in GN nanoparticles in CDCl₃ was also examined and compared with that of the PNIPAAm. The morphology, size distribution, and effect of temperature on the sizes of the GN nanoparticles were also investigated. The temperature dependence of T₁ and line halfwidth suggests that the N‐isopropyl group turns gradually into the solid‐like aggregates at temperatures higher than the LCST of PNIPAAm due to the collapsed coil‐globule transition. T₁ values of N‐isopropyl groups decreased with increasing PBLG content in GN diblock copolymer, suggesting the mobility of PNIPAAm chain, as the shell, becomes more restricted at higher PBLG core content.

Changes in the mobility of PNIPAAm shell in the core‐shell‐type nanoparticles composed of PBLG and PNIPAAm.     

Coil‐to‐Globule Transition of Poly(N‐isopropylacrylamide) in Aqueous Solution: Kinetics in Bulk and Nanopores

Differential scanning calorimetry (DSC) is used to study the kinetics of the coil‐to‐globule transition in aqueous solutions of poly(N‐isopropoylacrylamide) (PNIPAM) prepared in the bulk (3 and 10 wt%) and nanoconfined (10 wt% inside 30 nm silica pores) forms. It is demonstrated that the kinetics can be described in terms of the classical nucleation model. The proposed treatment affords estimating the free‐energy barrier and pre‐exponential factor of the transition. The application of the nucleation model to the DSC data collected for the three systems studied provides physical insights into the effect of increasing the transition temperature due to dilution and nanoconfinement. Dilution appears to raise the free‐energy barrier, whereas nanoconfinement causes a decrease in the pre‐exponential factor.

     

Immiscible Poly(L‐lactide)/Poly(ε‐caprolactone) Blends: Influence of the Addition of a Poly(L‐lactide)‐Poly(oxyethylene) Block Copolymer on Thermal Behavior and Morphology

Summary: A binary blend of poly (L ‐lactide) (PLLA) and poly(ε‐caprolactone) (PCL) of composition 70:30 by weight was prepared using a twin screw miniextruder and investigated by differential scanning calorimetry (DSC), optical microscopy and scanning electron microscopy (SEM). Ternary 70:30:2 blends were also obtained by adding either a diblock copolymer of PLLA and poly(oxyethylene) (PEO) or a triblock PLLA‐PCL‐PLLA copolymer as a third component. Optical microscopy revealed that the domain size of dispersed PCL domains is reduced by one order of magnitude in the presence of both copolymers. SEM confirmed the strong reduction in particle size upon the addition of the copolymers, with an indication of an enhanced emulsifying effect in the case of the PLLA‐PEO copolymer. These results are analyzed on the basis of solubility parameters of the blend components.

Optical micrograph of M3EG2 blend melt quenched at 125 °C.     

Fullerene End‐Capped Biodegradable Poly(ε‐caprolactone)

Fullerene capped poly(ε‐caprolactone)s (PCLs), namely single‐ and double‐fullerene end‐capped PCLs with different fullerene content, were successfully synthesized. The effect of the fullerene end on the crystallization behavior and mechanical properties of the PCL was studied. The aggregation behavior of the fullerene moieties at the end of the PCL chain was also studied. It was found that the aggregated fullerenes have two kinds of effect on the crystallization behavior of the PCL i.e., confinement effect and nucleating effect. The fullerene content shows a certain balance between the confinement effect and the nucleating effect on the crystallization rate of PCL. It was also found that the mechanical properties of the fullerene end‐capped PCLs are strongly related to the content of fullerene and the mode of end‐capping style: either single or double end‐capping.