We have compared the interactions between Polyquaternium 10-mixed surfactant micelle complexes of sodium dodecyl sulfate and Octoxynol with comparable complexes of mono-and diquaternary aminoalkylcarbamoyl cellulose derivatives. The methods utilized were precipitation studies, fluorescence, and dynamic light scattering. The results of the fluorescence study indicated that miceliar regions were formed in the polymer-mixed surfactant micelie complexes. Temperature studies indicated that the Polyquaternium 1 O-mixed surfactant micelie complex exhibits a different temperature response than complexes formed with polymers synthesized in our laboratories. JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS tion for the complex occurs near a stoichiometric charge neutralization (8-10). Addition of excess amount of anionic surfactant results in the resolubilization of the precipitated complex (8-10). The interaction between cationic hydroxyethyl cellulose derivatives and oppositely charged surfactants has been studied extensively (1,5-10,14-19). However, in previous studies, the cationic moiety is attached to poly(oxyethylene) spacer groups that provide flexibility independent of the cellulose chain (20). We have prepared new mono-and diquaternary aminoalkylcarbamoyl cellulose derivatives as graft copolymers having a defined charge density where the quaternary nitrogen is located at the sites of carboxymethylation of the starting polymer (21,22). The degree of substitution of the carboxymethylcellulose was 0.70 and the degree of substitution of the aminoamide derivative was 0.56 (23,24). These model polymers have been used to determine the behavior of complexes formed between the charged polymer and oppositely charged mixed surfactant micelies of sodium dodecyl sulfate (SDS) and Octoxynol. The interaction of these novel polymers with mixed surfactant micelies has been compared with the behavior of Polyquaternium 10. The results of these studies reveal the role of polymer charge density and graft length on the behavior of the polymer-mixed surfactant micelie complexes. EXPERIMENTAL MATERIALS The surfactants, sodium dodecyl sulfate (99%) and reduced Octoxynol {c•[4-(1,1,3,3,tetramethylbutyl)cyclohexyl]-co-hydroxypoly(oxy-1,2-ethanediyl)} (99%), were obtained from Sigma Chemical Company (St. Louis, MO) and Aldrich Chemicals (Milwaukee, WI), respectively. Polyquaternium 10, UCARE Polymer JR-400, was obtained from Amerchol Corporation (Edison, NJ). The aminoalkylcarbamoyl cellulosic derivatives (Figure 1), 2-trimethylammoniumethyl carbamoyl cellulose chloride (MQNNED) and 3-trimethylammonium-2-hydroxypropyl-N,N,-dimethylammoniumethyl carbamoylmethyl cellulose chloride (DQNNED), were prepared in our laboratories (21-24). Water was purified by reverse osmosis, deionization, and filtration (Osmonics, Inc.). Ultrapure water used in light-scattering experiments was obtained using a NANOpure system from Barnstead. METHODS Precipitation studies. Pseudo-phase diagrams were prepared for the following system: SDS/ polymer/water. The solutions were prepared by addition of a concentrated polymer solution (3%) to a solution of SDS. The samples were shaken, placed in an oven at 60øC for eight hours, and allowed to cool slowly. The appearance of the liquid and precipitate was judged visually following the method of Goddard and Hannan (8,10). Phase diagrams were also prepared for systems of 1% polymer/SDS/Octoxynol, varying the ratio of surfactants (1% total). The solutions were prepared in the same manner as previously described, varying the percentage of SDS from 0-1% (w/v) and maintaining a constant polymer concentration of 1% (w/v).

Polymers represent the second largest class of ingredients in cosmetics and personal care products. A diverse range of polymers are applied in this segment as film formers, fixatives, rheology modifiers, associative thickeners, emulsifiers, stimuli-responsive agents, conditioners, foam stabilizers and destabilizers, skin-feel beneficial agents, and antimicrobials. This chapter reviews recent advances in the use of polymers in personal care formulation. The drive to meet the requirements of the Clean Air Act have drawn polymeric materials into formulations that are low in volatile-organic compounds. This has resulted in aqueous-based thickeners that also form films and act as fixatives. The onset of free-radial living polymerization offers the prospect of custom-designing the morphology of products to meet the desired attributes. Complex coacervate mechanisms dominate the functioning of conditioning shampoos. Stimuli-responsive polymers are being directed towards applications from make-up that camouflages wrinkles to the facile processing of multiple emulsions, to thermally-responsive systems that respond to the surface of skin. The use of polymers in cosmetics is highly developed, and innovative advances in polymer science and nanoscience are driving the creation of scientifically sophisticated products.

Our goal is to select and develop stimuli-responsive interfacial coupling materials for nanocomposites that will enhance substrate mechanical properties during use but cause triggered disintegration when exposed to the appropriate aqueous environment. The study could potentially provide the scientific underpinning for the development of an interfacially interacting nanocomposite alloy capable of enhanced biodegradation in the aqueous environment. In the first stage of this study it was shown that quaternary ammonium polymers adsorbed on the faces of the montmorillonite platelets, non-ionic polyacrylamides adsorbed on the faces and edges by hydrogen bonding, and anionic polyelectrolytes, carboxylates and sulfonates, did not adsorb at all on the montmorillonite [R.

Pseudophase diagrams for the system cyclohexane-water-polymer were constructed and the compositional regions of emulsion stability and coalescence were identified. The polymeric stabilizers investigated were hydrophobically modified poly(acrylic acid) (HMPAA), hydrophobically modified hydroxyethyl cellulose (HMHEC) and analogous poly(acrylic acid) (PAA) and hydroxyethyl cellulose (HEC) as controls. The critical overlap concentration c* of these polymers and their interfacial activities at the cyclohexane/water interface were determined. In the case of the acrylic acid polymers, c* varied with pH but a critical condition for emulsion stability appeared to be the c* value of the unneutralized polymer (c&). It was found that when HMPAA was incorporated as the emulsifier the emulsions coalesced when the pH was greater than 6.5 and simultaneously the HMPAA concentration was less than c&.+ The emulsions were stable above C& at all pH values and below pH 6.5 when the polymer concentration was less than c&. On the basis of these results, it is postulated that stabilization in the lower concentration range occurs by an electrosteric stabilization mechanism and in the upper concentration range by trapping the discrete oil droplets in a continuum of hydrophilic polymer segments. PAA stabilizes only below pH 6.5 and below c&. Both HMHEC and HEC are ineffective below c* and only HMHEC is effective as an emulsifier above c*.

Acrylamide-based, hydrophobically modified (HM) polybetaines containing N-butylphenylacrylamide (BPAM) and varying amounts of the sulfobetaine monomer 3-(2-acrylamido-2-methylpropanedimethylammonio)-1-propanesulfonate (AMPDAPS) or the carboxybetaine monomer 4-(2-acrylamido-2-methylpropyldimethylammonio)butanoate (AMPDAB) were synthesized by micellar copolymerization. The corresponding control (co)polymers lacking BPAM or betaine comonomers were also prepared. The terpolymers were characterized by 13 C-NMR and UV spectroscopy, classical light scattering, and potentiometric titration. Low charge density polymers contained 3.9-8.6 mol % betaine, whereas the high charge density systems contained 17-25 mol % betaine; the HM polymers contained up to 1.0 mol % BPAM as the hydrophobe. The weightaverage molecular weights of the polymers ranged from 4.19 ϫ 10 5 to 1.29 ϫ 10 6 g/mol, and most HM polymers exhibited negative second virial coefficients. The pK a of the carboxybetaine moieties was found to increase with increasing levels of hydrophobic and betaine comonomer incorporation. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH and electrolyte concentration, was investigated using rheological analysis. The solution behavior of the polymers was characteristic of HM polyacrylamides and acrylamide-based polyzwitterions. The high charge density HM polycarboxybetaine exhibited unusual solution behavior that can be explained in terms of electrostatic, hydrophobic, and hydrogen-bonding associations.

The interactions of Surfactants sodium dodecyl sulfate (SDS), trimethyltetradecylammonium bromide (TTAB), and Triton X-100 with amphiphilic copolymers of acrylamide and dimethyldodecyl(2-acrylamidoethy1)ammonium bromide (DAMAB) have been investigated in aqueous solutions. The rheological properties of a copolymer/surfactant system are affected by both the microstructure of the copolymer and the nature of the surfactant. Addition of the nonionic surfactant, Triton X-100, resulted in a large increase in the reduced viscosity for the microblocky copolymers with 5 mol 76 D A W , while a random copolymer with the same composition exhibited a collapsed conformation in the presence of the cationic surfactant, TTAB. A strong viscosity enhancement was observed when SDS was added to the solution of a copolymer containing 0.32 mol 96 DAMAB. Evidence of mixed micelles formed by surfactant molecules and the hydrophobic groups of the copolymers was obtained utilizing surface tension, pyrene probe fluorescence, and viscometry.

The purpose of this thesis was to optimize a pre-existing vapor phase ethylbenzene process, and to develop a base case liquid phase ethylbenzene process. A brief introduction is included to present an overview of process optimization and suggest common strategies to employ. While optimizing the vapor phase process, discrete optimization was performed to determine the local optima for multiple unit operations by comparing their net present value to that of the base case. After optimization, an $81.5 million increase in net present value was obtained. When developing the liquid phase ethylbenzene process, Antoine’s Equation, Raoult’s Law, the first law of thermodynamics, and material and energy balances were used to create a base case for a process that produced 80,000 tonnes per year of 99.8 mol% ethylbenzene. This included the creation of a process flow diagram, equipment and utility tables, and stream tables containing temperature, pressure, and component molar flow rates. Explanat...