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Group transfer polymerization was employed for the preparation of six amphiphilic terpolymer networks comprising the hydrophilic, pH-responsive 2-(dime- thylamino)ethyl methacrylate (DMAEMA), the neutral hydrophilic methoxy hexa (ethylene glycol) methacrylate (HEGMA), and the hydrophobic n-butyl methacrylate (BuMA). 1,4-Bis(methoxytrimethylsiloxymethylene)cyclohexane was used as a bifunc- tional initiator, whereas ethylene glycol dimethacrylate served as the crosslinker to interconnect the linear terpolymer precursors to three-dimensional terpolymer net- work structures. Five of the terpolymer networks were model, with linear chains between crosslinks of precise length. Four of the five model networks were based on ABCBA pentablock terpolymers with theoretical structure DMAEMA5-b-BuMAn/2-b- HEGMA10-b-BuMAn/2-b-DMAEMA5 with n values equal to 5, 10, 20, and 30. The model network based on the equimolar statistical terpolymer and the nonmodel ran- domly crosslinked terpolymer network were also prepared. The molecular weights and compositions of the linear pentablock terpolymer precursors to the networks were found to be close to the theoretically expected, while the network sol fractions were found to be relatively low. The degrees of swelling of the networks in water were found to decrease with increasing the hydrophobic content, whereas those in THF exhibited the opposite trend. Small-angle neutron scattering in deuterium oxide indicated structural organization in the most hydrophobic pentablock terpolymer net- works. V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4420-4432, 2008

This study presents the preparation and characterization of double networks (DN) based on a first amphiphilic polymethacrylate conetwork (APCN) and a second polyacrylamide network. The APCN first network comprised interconnected "in-out" star copolymers of 2-(dimethylamino)ethyl methacrylate (DMAEMA, hydrophilic ionizable monomer) and 2-ethylhexyl methacrylate (EHMA, hydrophobic comonomer) or lauryl methacrylate (LauMA, second hydrophobic comonomer), synthesized using group transfer polymerization, following one-pot, sequential, monomer, and hydrophobic cross-linker (ethylene glycol dimethacrylate, EGDMA) additions. The second network was prepared by the aqueous photopolymerization of acrylamide (AAm) at two different concentrations, 2 and 5 M, and N,N′-methylenebis(acrylamide) cross-linker in the presence of the fully ionized (via HCl addition) APCN. After synthesis, all DNs and single (first and second) (co)networks, equilibrium-swollen in water, were characterized in terms of their mechanical properties in compression. The DNs exhibited improved mechanical properties (stress and strain at break, and elastic modulus) compared to the corresponding single networks. Better reinforcement was achieved in the DNs whose APCN first networks bore a lower hydrophobic content and whose hydrophobic monomer was EHMA rather than LauMA. The best DN exhibited stress at break above 8 MPa and strain at break nearly 80%, close to the values of the best DNs in the literature. Nanoindentation studies were also performed on selected DNs which proved again the enhanced mechanical properties of the present DNs, manifested as high resistance to penetration and low creep displacement. Small-angle X-ray scattering (SAXS) indicated a broad correlation peak for all APCN first networks, suggestive of microphase separation with short-range order, arising from the presence of the hydrophobic segments. The single correlation peak was preserved in the SAXS profiles of the DNs, which was, however, shifted to lower q-values, consistent with further network swelling. Despite the SAXS evidence for only weak phase separation on the nanoscale in the DNs, half of the water-swollen DNs (the ones with a 5 M AAm concentration in the second network) exhibited strong birefringence which probably arose from the stretching of the charged DMAEMA segments rather than the presence of anisotropic nanophases. © 2016 American Chemical Society. 49 5 1731 1742 Cited By :12

The association ability of model amphiphilic polyelectrolytes with multi-block architecture, i.e. ABA, BABAB, ABABABA and BABABABAB (A hydrophobic, B polyelectrolyte block) was studied in aqueous media. The gelation efficiency of these multiblock copolymers in semidilute aqueous solutions with variable molecular weights, hydrophobic content, topology and length of the associative stickers has been investigated by rheological measurements, light scattering and transmission electron microscopy (TEM). The behaviour of these associative polyelectrolytes seems to be governed by the interplay of the hydrophobic attractive interactions of the A blocks and the electrostatic repulsive interactions of the B blocks. Rheological results showed that only the copolymers bearing hydrophobic end-blocks are able to form hydrogels at relatively low copolymer concentrations. Therefore the topology of the A blocks and the degree of ionization of the B blocks influence significantly the gelation efficiency of these polymeric materials. Comparing the rheological behavior of multiblocks of the same topology (heptablock) it was observed that small differences in the degree of polymerization of the building blocks result in remarkably different rheological properties. © 2010 The Royal Society of Chemistry. 6 21 5417 5424 Cited By :16