Chemistry of alkenyl azlactones. IV. Preparation and properties of telechelic acrylamides derived from amine-terminated oligomers

The ring-opening, nucleophilic addition of amine-terminated oligomers to alkenyl azlactones was exploited to prepare reactive, that is, in free radical polymerizations, oligomers that could be used in 100% solids resin systems. Acrylamide-functional oligomers resulted from the reaction that used 2-vinyl-4,4-dimethylazlactone, whereas methacrylamide-functional oligomers were produced with 2-isopropenyl-4,4-dimethylazlactone. The overall reaction took place under mild conditions, for example, a few hours at room temperature, and was particularly free of side reactions. Examination of reaction rates with the two alkenyl azlactones revealed that the 2-vinyl derivative reacted ca. four times faster. The (meth)acrylamide-terminated resins were characterized by IR, NMR, and molecular weight analyses.     

Chemistry of alkenyl azlactones. VII. Preparation and properties of multiazlactones derived from mercaptan-functional compounds and oligomers

The reaction of polymercaptans and 2-alkenyl azlactones has been further investigated, and several new multiazlactones which are liquids at room temperature have been prepared and characterized. Michael addition yielding the multiazlactones was found to take place slowly in the absence of and rapidly in the presence of acid catalysts. If basic impurities capable of forming mercaptide ion were present, however, the reaction underwent a substantially different course producing primarily ring-opened products. A source of these basic impurities was determined to be the method of preparation of the alkenyl azlactone itself. When the azlactone was prepared from its acyclic N-substituted aminoacid precursor by cyclodehydration by use of ethyl chloroformate and triethylamine, a small amount of triethylamine remained that dramatically altered the course of reaction. Nonbasic cyclodehydration agents such as dicyclohexylcarbodiimide were effective at eliminating this side reaction, as well as was the practice of adding excess acid to the reaction system to neutralize the basic impurities.     

Chemistry and technology of 2‐alkenyl azlactones

The chronology of 2‐alkenyl azlactone research at 3M is discussed in terms of its origination; consideration of economics, overall safety, and opportunities for patent protection; elaboration of the chemistry; and, finally, applying lessons learned toward the development of commercial technologies. The chemistry is dominated by the presence of three electrophilic reaction centers and a readily polymerizable 2‐alkenyl group. Technological development has been focused in four general areas: acrylamide monomers, acrylamide materials, azlactone materials, and polymer modification. Application areas disinclude lithographic printing plates, contact lens materials, adhesives, dispersants for printing inks, and supports for immobilizing enzymes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3655–3677, 2001     

Block copolymers derived from polyisobutylene oligomers

The synthesis of polyvalent functionalized polyisobutylene (PIB) oligomers containing multiple polar groups via radical polymerization is described. Polymerizations from PIB macroinitiators via alkylborane intermediates can form block copolymers but the polar block is consistently larger than the PIB block and unless a hydrophobic monomer is used, the products are insoluble in alkanes. Block copolymer products from ATRP macroinitiators are formed with more control over the degree of polymerization of a polar block from a 1000 Da PIB starting material but are still alkane insoluble because the degree of polymerization of the polar block was consistently equal to or greater than the degree of polymerization of the PIB block. RAFT polymerization using 5 mol % of azoisobutyronitrile relative to a PIB macroinitiator however was successful in producing acceptable yields of alkane soluble block copolymers using a 1000 Da PIB starting material and monomers like methyl methacrylacrylate, ethyl methacrylate, N,N‐dimethylacrylamide, and N‐isopropylacrylamide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1860–1867     

Unexpected remarkable stability of primary ozonides derived from alkenyl stannanes. One-pot synthesis of 1,2-diols from alkynes

Primary ozonides derived from alkenyl stannanes display an unusual stability and can be transformed into 1,2-diols by treatment with dimethyl sulfide and borane-methyl sulfide complex. This observation has been incorporated into the development of a novel one-pot strategy for the conversion of alkynes into 1,2-diols.     

Chemistry of geminal-dithiolates derived from cyano-substituted tetrathiafulvalenes

Tetracyanotetrathiafulvalene reacts with two equivalents of thiol salts (RS^?) to give 1,2-dicyano-1,2-di RS ethene and a geminal dithiolate intermediate which reacts with a variety of reagents to provide novel tetrathioethene derivatives, such as reaction with 3-chloro-2-butanone and acid to give dimethyldicyanotetrathiafulvalene.     

New ketone homoenolate anion equivalents derived from (alkenyl)pentamethyl phosphoric triamides

Lithiated ambident anions derived from (1-alkyl-2-propenyl)- or (1-phenyl-2-propenyl)-pentamethyl phosphoric triamides undergo regioselectively γ-reaction with various alkylating reagents and isobutyraldehyde. Further hydrolysis of adducts releases the ketone under acid conditions. Number of synthetic applications clearly show the ketone homoenolate behaviour of these new carbanions.     

Chemistry of thienopyridines. XLII. Three novel compounds derived from thienopyridine N-oxides

Extension of the Reissert-Henze reaction to treatment of thieno[2,3-b]pyridine 7-oxide with potassium thiocyanate and benzoyl chloride in water-methylene chloride gives a 2% yield of bis(6-thieno[2,3-b]pyridyl) disulfide. Peroxidation of 5-ethylthieno[2,3-b]pyridine ( 4 ) forms the 7-oxide 5 (53%), converted to a monopicrate 5a . Picrate 5a undergoes N-deoxygenation to 4 -picrate on drying at 78° in vacuo, but shows the expected additive mass spectrum of 5 (thermally stable) and picric acid. Nucleophilic displacement of chloride ion from 7-chlorothieno[3,2-b]pyridine (derived, in turn, from thieno[3,2-b]pyridine 4 -oxide) by the anion from ethyl cyanoacetate gives 7-(1-cyano-1-ethoxycarbonyl)methylene-4,7-dihydrothieno[3,2-b]pyridine (82%), stable in this iminodienic tautomeric form.     

New protocol for allylic substitution with aryl and alkenyl copper reagents derived from organolithiums

Substitution of allylic picolinoates with copper reagents derived from sp²-carbon-lithiums and CuBr·Me₂S was established to furnish anti S_N2′ products with almost perfect regioselectivity and chirality transfer. The preparations of organolithiums such as lithium-halogen exchange and ortho lithiation were coupled to the substitution to install various sp²-carbon groups, which include Ph, 2,6-Me₂C₆H₃, 4-Me-2,6-(MOMO)C₆H₂, and cis and trans 1-heptenyl groups.     

Block copolymers of ethylene. I. Butadiene

Block copolymers of ethylene and butadiene have been prepared to study their properties. The method of preparation of polybutadiene, polyethylene, and block copolymers of ethylene and butadiene with n-butyl lithium-tetramethyl ethylene diamine complex is outlined. Kinetic studies have been reported elsewhere and these are assessed to determine that suitability of the system to produce monodispersed “living” chains so that simple correlations between physical properties and molecular weight can be made. The properties were somewhat restricted by the 1,2-microstructure of the butadiene block.     

Gradient graft copolymers derived from PEO‐based macromonomers

Atom transfer radical polymerization (ATRP) of two poly(ethylene oxide) (PEO) macromonomers, with different polymerization degrees (DP_n) and different end groups, was conducted in solution via the grafting through method. Selection of a PEO methacrylate with a methyl end‐group (PEOMeMA, DP_PEO = 23) and a PEO acrylate end‐capped by a phenyl ring (PEOPhA, DP_PEO = 4) for the copolymerization led to a spontaneous gradient of PEO grafts along the copolymer backbone. Such a composition was formed because of significantly different reactivities of the two PEO macromonomers. The resulting copolymer has PEOMeMA at one end of the polymer chain, gradually changing through hetero‐sequences of PEOPhA at the other chain end. An increase in the initial feed ratio of PEO acrylate reduced the rate of change in the shape of the gradient. Amorphous–crystalline structure in the copolymers was demonstrated by DSC and WAXS. The mechanical measurements of copolymers consisting of an amorphous PEOPhA and crystallizable PEOMeMA segments indicated elastomeric properties in the range of a soft rubber (G′ ～ 10⁴ Pa, G′ ? G″). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1347–1356, 2006     

Block copolymers derived from azobiscyanopentanoic acid. X. Synthesis of silicone–vinyl block copolymers via polysiloxane(azobiscyanopentanamide)s

The synthesis of silicone–vinyl block copolymers has been studied by the use of poly(azo-containing siloxaneamide)s (abbreviated as PASAs), i.e., polysiloxane (azobiscyanopentanamide)s as macroazoinitiators. PASAs with number-average molecular weight of 12000–31000 and with siloxane chain lengths of 250–9800 were prepared by the condensation of azobiscyanopentanoyl chloride and α,ω-bis(3-aminopropyldimethyl)polysiloxanes in equimolar feeds. Several kinds of silicone–vinyl block copolymers were synthesized by radical polymerization of vinyl monomers such as methyl methacrylate, styrene, and vinyl acetate, in the presence of PASA in homogeneous media. The block copolymers with siloxane contents up to 30 mol % were then characterized on the basis of infrared absorption, proton NMR spectra, and gel permeation chromatography.     

Carbon-rich organometallic materials derived from 4-ethynylphenylferrocene

Using 4-ethynylphenylferrocene (1) as the building block, a new series of rigid-rod alkynylferrocenyl precursors consisting of fluoren-9-one unit, 2-bromo-7-(4-ferrocenylphenylethynyl)fluoren-9-one (2a), 2,7-bis(4-ferrocenylphenylethynyl)fluoren-9-one (2b), 2-trimethylsilylethynyl-7-(4-ferrocenylphenylethynyl)fluoren-9-one (3) and 2-ethynyl-7-(4-ferrocenylphenylethynyl)fluoren-9-one (4) have been prepared in moderate to good yields. The acetylene complex 4 is a useful precursor for the synthesis of well-defined carbon-rich ferrocenyl heterometallic complexes, trans-[(η⁵-C₅H₅)Fe(η⁵-C₅H₄)C₆H₄CCRCCPt(PEt₃)₂Ph] (5), trans-[(η⁵-C₅H₅)Fe(η⁵-C₅H₄)C₆H₄CCRCCPt(PBu₃)₂CCRC≡CC₆H₄(η⁵-C₅H₄)Fe(η⁵-C₅H₅)] (6), trans-[(η⁵-C₅H₅)Fe(η⁵-C₅H₄)C₆H₄CCRCCM(dppm)₂Cl] (M=Ru (7), Os (8)) (R=fluoren-9-one-2,7-diyl). All new complexes have been characterized by FTIR, NMR and UV-Vis spectroscopies and fast atom bombardment mass spectrometry (FABMS). The molecular structures of 1, 2a, 4, 6 and 8 have been determined by single-crystal X-ray studies where an ironiron through-space distance of nanosized dimension (ca. 42 Å) is observed in the trimetallic molecular rod 6. The electronic absorption, luminescence and electrochemical properties of these carbon-rich molecules were investigated and the data were correlated with the theoretical results obtained by the method of density functional theory.     

Novel polypropene materials derived from vinylidene-terminated oligopropenes

Metallocene-based homogeneous Ziegler–Natta catalysts produce mono-olefin-terminated oligopropenes with narrow molecular weight distributions, controlled stereoregularities, and molecular weights ranging from 100 to 30,000 g/mole in high yield slurry and solution processes. Steric and molecular weight control are influenced by metallocene structures, and by polymerization conditions such as temperature and propene concentration. Predominantly mono-vinylidene-terminated oligopropenes are attractive intermediates, and feedstock for the synthesis of a variety of polypropylene materials, including blends, block and graft copolymers. The key step is the chain end functionalization of the vinylideneterminated oligopropenes via double bond conversion reactions, followed by the controlled synthesis of polypropylene block and graft copolymers. In melt and solution processes the olefinic end groups have been converted into a variety of polar functional groups, e.g. hydroxy, carboxy, succinic anhydride, thiol and acrylic groups. The thiol-terminated oligopropenes are chain transfer agents in radical methylmethacrylate polymerization with chain transfer constant measured to be 0.2. Acrylic monomers and styrene are grown onto the thiol end group via a chain transfer reaction, thus producing a family of block copolymers, e.g. poly(propene-b-methylmethacrylate) and poly(propene-b-styrene). As demonstrated by SEM fracture surface analysis, the poly(propene-b-styrene) block copolymers are efficient dispersing agents for compatibilizing polystyrene/polypropene (70/30) blends. Homo- and copolymerization of acrylic oligopropene macromonomers yield novel classes of graft copolymers with pendant isotactic or atactic oligopropene chains. Hydroxy-terminated oligopropenes are useful initiators in caprolactone polymerization to form poly(propene-b-caprolactone) block copolymers. IR spectroscopic studies demonstrate that succinic anhydride-terminated oligopropenes, obtained by ene-type addition of maleic anhydride to the olefinic oligopropene end group, react with oligomeric diamine-terminated polyamide-6,6 in the melt to yield polypropene-b-polyamide-6,6-b-polypropene triblock copolymers.     

Thermodynamics of plasticized triblock copolymers. I. Theory

The thermodynamic theory of bulk ABA copolymers developed by Leary and Williams is extended to copolymer–solvent systems. Free energy expressions are derived for five hypothetical phase-separated morphologies and evaluated specifically for a polymer with approximately 25% of the A component. The separation temperature, T_s, at which a given morphology will be in equilibrium with a homogeneous mixture, is also evaluated. The major result is the prediction of the T_s(?S) depression, where ?s is the solvent fraction. Depression is maximized when δ_S is equidistant between δ_A and δ_B, but becomes rapidly less when δ_S is outside the δ_A–δ_B range. Morphological favoritism is independent of ?_S and δ_S (model does not apply to preferential precipitation), with a planar microstructure being favored along with microstructures containing domains of B in continuous A for the 25% A polymer.     

Chemistry of a meisenheimer-type σ-adduct derived from a troponoid

The gem-dimethoxy σ-adduct of methoxide addition to 2-methoxy-3-nitro-4,5-benzotropone reacts with either (C₂H₅)₃OBF₄, to change the nitronate into an oxime function, or (CH₃)₃SiCl, to give 2-carbomethoxy-1-nitronaphthalene and the nitronic acid corresponding to the starting adduct.     

Polymerization of complexed monomers. I. Alternating copolymers from cyclopentene and complexed polar monomers

Alternating equimolar copolymers of cyclopentene with acrylonitrile and methyl acrylate were prepared in the presence of ethylaluminum sesquichloride. Varying conditions of monomer ratio, temperature, light, and reaction time were studied. The structures of the polymers and mechanistic implications are discussed.