Preparation of Latexes with Poly(Methyl Methacrylate) Cores and Hydrophilic Polymer Shells Containing Amino Groups

Abstract

Functional latexes with poly(methyl methacrylate) (PMMA) cores and amino‐containing, water‐soluble polymer shells were synthesized via direct graft copolymerization of methyl methacrylate from water‐soluble polymers induced by a small amount of tert‐butyl hydroperoxide (TBHP) at 80°C for 2 h. Amphiphilic graft copolymers and PMMA homopolymers were generated concurrently to form highly monodispersed latexes. The effects of water‐soluble polymer containing different amino group, reaction temperature, TBHP concentration, molecular weight of the polymer and pH of the solution on conversion and grafting efficiency of the monomer and particle size were investigated. Transmission electron microscopic images of the PMMA/poly(ethyleneimine) (PEI) and PMMA/poly(allylamine) (PAA) particles clearly show well‐defined core‐shell morphologies, where PMMA cores are coated with either PEI or PAA shell. The amino‐containing polymer shells were also confirmed with zeta‐potential measurements. Furthermore, the amino‐containing latexes can be produced with a solids content up to 22 wt.%. Thus, this method provides a commercially viable route to functional latexes.     

Facile Synthesis of Novel Polyethylene‐Based A‐B‐C Block Copolymers Containing Poly(methyl methacrylate) Using a Living Polymerization System

Ethylene–propylene–methyl methacrylate (MMA) and ethylene–hexene–MMA A‐B‐C block copolymers with high molecular weight (>100 000) are synthesized using fluorenylamide‐ligated titanium complex activated by modified methylaluminoxane and 2,6‐di‐tert‐butyl‐4‐methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks.

     

Ultrasonic investigation of interpenetrating networks of poly(methyl methacrylate) and polyurethane

Interpenetrating networks are the most recent development in polymeric blend materials. Due to the crosslinking of both the continuous and dispersed phases, a high degree of molecular mixing is achieved in these materials. Notwith-standing that poly(methyl methacrylate)-polyurethane (PMMA-PUR) interpene-trating and semi-interpenetrating networks have been extensively investigated by Meyer et al., ultrasonic relaxation technique has been applied here for the first time. These materials were found to be highly ultrasound absorbing.It is observed that ultrasonic absorption has a peak at a particular composition of PMMA-PUR interpenetrating network. The absorption coefficient increases with frequencyf. The absorption is of relaxational nature and is not due to the scattering of ultrasonic waves by the domains of the dispersed phase. At every composition of the interpenetrating network, the/f ² vs.f curve indicates the presence of a relaxation frequency below 2 MHz and that the absorption increases with the temperature at some compositions which indicates the presence of thermal relaxation. An attempt is made to relate the absorption with the relaxation of pendent groups of polyurethane in the continuous phase.     

杂芳基硼化合物的合成

利用２－溴噻吩、镁屑、硼酸三正丁酯或三氟化硼乙醚室温下一锅反应分别合成了一噻吩基、二噻吩基硼酸,三噻吩基硼烷及其衍生物．利用５－甲基－２－呋喃基锂、２－苯并呋喃基锂与硼酸三正丁酯或三氟化硼乙醚低温下反应合成了几种含呋喃基硼化合物．利用烃基格氏试剂与噻吩基硼酸正丁酯低温下反应合成噻吩基烃基硼酸衍生物     

Role of N,N-dimethyl-para-toluidine and saccharin in the radical polymerization of methyl methacrylate initiated by a redox system. II. Cumene hydroperoxide/iron saccharinate

The role of N,N-dimethyl-p-toluidine (DMPT) and saccharin as accelerators in the polymerization of methyl methacrylate initiated by the redox decomposition of cumene hydroperoxide (CHP) in the presence of iron saccharinate has been kinetically investigated. DMPT reduces ferric ions to ferrous ions, so that an equilibrium is established between the two oxidation states. With the assumption of a steady-state concentration of propagating radicals, the rate of initiation was deduced from the rate of polymerization and the kinetic orders with respect to each compound involved in the initiation step have been determined. The reaction is first-order in CHP, iron saccharinate, and saccharine and second-order in DMPT. In a proposed scheme, Fe²⁺ ions, complexed by two DMPT molecules, are much more reactive than uncomplexed Fe²⁺ and saccharin activates the decomposition of CHP by protonation of the O? O bond. This mechanism, similar to that proposed in the case of copper saccharinate, explains the synergistic effect of both accelerators. © 1994 John Wiley & Sons, Inc.     

Stereoselective synthesis of 2,6-dideoxy-α-l-arabino-hexopyranoside of glycyrrhetic acid in the presence of iodine-containing promoters

Glycosylation of methyl glycyrrhetate withl-rhamnal acetate in the presence of iodine-containing promoters and subsequent hydrogenolysis yield 2,6-dideoxy--l-arabino-hexopyranoside of glycyrrhetic acid, an analog of glycyrrhizic acid, the natural glycoside of licorice root extract.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2993–2996, December, 1996.     

A parametric study on biphasic medium conditions for the enantioselective production of naproxen by <Emphasis Type="Italic">Candida rugosa</Emphasis> lipase

A parametric study to increase the enantioselectivity of Candida rugosa lipase (CRL) toward S-Naproxen production by the hydrolysis of racemic Naproxen methyl ester in an aqueous-organic biphasic batch system was carried out. Effects of organic solvent type, aqueous phase/organic solvent volume ratio, agitation rate, concentrations of the substrate and the enzyme, pH of the aqueous phase, and temperature on the en antiomeric excess for the product (ee_p), on the enantiomeric ratio (E) and on the conversion (x) were evaluated. Employing isooctane as the solvent resulted in higher ee_p, E, and x than those obtained in hexane, cyclohexane, and toluene. The higher the volume ratio of aqueous phase/organic solvent employed, the higher the conversion and enantioselectivity achieved. The increase in agitation rate increased the hydrolysis rate. Higher concentration of racemic Naproxen methyl ester than 10 mg/mL decreased both the conversion and enantioselectivity. The increase in crude CRL concentration resulted in enhancement of x, but the decrease of fee_p and E. Acidic pH led to higher conversion and enantioselectivity than the medium and alkaline pH values. A further increase in temperature to over 45°C decreased the conversion and enantioselectivity. The highest enantiomeric ratio achieved in the S-Naproxen production was E=171.1, with x=49.8% and ee_p=95.7%.     

鼓泡浆态反应器中低温甲醇合成的探索

为了开发低温液相甲醇合成新工艺，使用CuCr／CH3ONa催化体系，在直径40mm的鼓泡浆液反应器中考察了低温甲醇合成的反应性能。鼓泡浆液反应器使用的浆液由铜铬催化剂、甲醇钠溶液、乳化剂OP-10和液相介质二甲苯组成。实验结果表明在90℃～110℃、4．8MPa和操作气速0．2cm／s下，前9h的CO平均转化率达到78％。甲醇是反应的主要产物。与搅拌釜中的实验结果比较，鼓泡浆液反应器的反应效率为搅拌釜的80％。这是由于甲醇钠的消耗和乳化剂的负效应所致。实验结果示范了鼓泡浆态反应器中低温甲醇合成的可行性。     

Fingerprints of damped quantum rotation observed in solid-state proton NMR spectra.

(1)H NMR spectra of the methyl group in an oriented crystal sample of methylmalonic acid with all three non-methyl protons replaced by deuterons are interpreted in terms of the damped quantum rotation (DQR) theory of NMR line shapes. The DQR approach offers a perfect theoretical reproduction of the observed spectra while the conventional Alexander-Binsch line-shape model shows evident defects in the present case. The temperature trends of the quantities characterizing the coherent and incoherent dynamics of the methyl group in the DQR approach (the effective tunnelling frequency and two coherence-damping rates) derived from the spectra are fairly reproduced using a model reported previously. The present findings provide further evidence of limitations to the validity of the common belief that molecular rate processes in condensed phases are necessarily classical.     

A thermodynamic study of the inclusion processes of α- andβ-cyclodextrins with the acid forms of methyl orange and methyl yellow

The effect of temperature on the UV-visible spectra of the acid forms of methyl orange and methyl yellow in the presence of - and-cyclodextrins was analysed in terms of 1 : 1 inclusion processes. Three inclusion processes were considered for each azo dye/cyclodextrin system. The processes are the apparent inclusion process, the ammonium inclusion process, and the azonium inclusion process. The values of H ⁰ and S ⁰ are reported for each process. The inclusion complexes of the ammonium tautomer are more stable than those of the azonium tautomer and -cyclodextrin inclusion complexes are more stable than those of-cyclodextrin. The inclusion processes resulted in a shift in the position of the tautomeric equilibrium of an azo dye. A significant color fading was observed in -cyclodextrin/methyl yellow solutions. No measurable changes in the absorbances were observed in the case of azo dye solutions containing -cyclodextrin.