Atom transfer radical polymerization of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene

Atom transfer radical polymerization (ATRP) of (R)‐2‐methacryloyloxy‐2′‐methoxy‐1,1′‐binaphthalene ((R)‐MAMBN) mediated by different amine ligands, copper(I) chloride and ethyl 2‐bromopropionate in different solvents, and reverse ATRP of (R)‐MAMBN were studied. It was shown that optically active polymers were obtained, with poor control of the molecular weights, and low polydispersities. Specific rotation of the polymers increased with increasing molecular weights. By comparison with (R)‐MAMBN, poly((R)‐MAMBN)s exhibits higher specific rotation and a positive Cotton effect. Copyright © 2003 Society of Chemical Industry     

Microwave‐promoted rapid synthesis of new optically active poly(amide imide)s derived from N,N′‐(pyromellitoyl)‐bis‐L‐isoleucine diacid chloride and aromatic diamines

A pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) was reacted with L ‐isoleucine in acetic acid, and the resulting imide acid [N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine] (4) was obtained in a high yield. 4 was converted into N,N′‐(pyromellitoyl)‐bis‐L ‐isoleucine diacid chloride by a reaction with thionyl chloride. The polycondensation reaction of this diacid chloride with several aromatic diamines, including 1,4‐phenylenediamine, 4,4′‐diaminodiphenyl methane, 4,4′‐diaminodiphenylsulfone (4,4′‐sulfonyldianiline), 4,4′‐diaminodiphenylether, 2,4‐diaminotoluene, and 1,3‐phenylenediamine, was developed with two methods. The first method was polymerization under microwave irradiation, and the second method was low‐temperature solution polymerization, with trimethylsilyl chloride used as an activating agent for the diamines. The polymerization reactions proceeded quickly and produced a series of optically active poly(amide imide)s with good yields and moderate inherent viscosities of 0.17–0.25 dL/g. All of the aforementioned polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 951–959, 2004     

Microwave‐assisted polycondensation of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L‐leucine) diacid chloride with aromatic diols

A new facile and rapid polycondensation reaction of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine) diacid chloride (1) with several aromatic diols such as phenol phthalein (2a), bis phenol‐A (2b), 4,4′‐hydroquinone (2c), 1,4‐dihydroxyanthraquinone (2d), 1,8‐dihydroxyanthraquinone (2e), 1,5‐dihydroxy naphthalene (2f), dihydroxy biphenyl (2g), and 2,4‐dihydroxyacetophenone (2h) was performed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions proceeded rapidly, compared with the conventional solution polycondensation, and was completed within 10 min, producing a series of optically active poly(ester‐imide)s with quantitative yield and high inherent viscosity of 0.50–1.12 dL/g. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of this optically active poly(ester‐imide)s are reported. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3003–3009, 2000     

Microwave‐assisted and conventional polycondensation reaction of optically active N,N′‐(4,4′‐sulphonediphthaloyl)‐bis‐L‐leucine diacid chloride with aromatic diamines

3,3′,4,4′‐Diphenylsulfonetetracarboxylic dianhydride ( 1 ) was reacted with L‐leucine ( 2 ) in acetic acid and the resulting imide‐acid ( 3 ) was obtained in high yield. The diacid chloride ( 4 ) was prepared from diacid derivative ( 3 ) by reaction with thionyl chloride. The polycondensation reaction of diacid chloride ( 4 ) with several aromatic diamines such as 4,4′‐sulfonyldianiline ( 5a ), 4,4′‐diaminodiphenyl methane ( 5b ), 4,4′‐diaminodiphenylether ( 5c ), p‐phenylenediamine ( 5d ), m‐phenylenediamine ( 5e ), 2,4‐diaminotoluene ( 5f ), and 1,5‐diaminonaphthalene ( 5g ) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions were also performed under two conventional methods: low temperature solution polycondensation in the presence of trimethylsilyl chloride, and a short period reflux conditions. A series of optically active poly(amide‐imide)s with inherent viscosity of 0.25–0.42 dL/g were obtained with high yield. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation techniques. Some structural characterizations and physical properties of these optically active poly (amide‐imide) s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2992–3000, 2004     

Microwave‐assisted and classical heating polycondensation reaction of bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine with diisocyanates as a new method for preparation of optically active poly(amide imide)s

A new class of optically active poly(amide imide)s were synthesized via direct polycondensation reaction of diisocyanates with a chiral diacid monomer. The step‐growth polymerization reactions of monomer bis(p‐amido benzoic acid)‐N‐trimellitylimido‐L‐leucine (BPABTL) (5) as a diacid monomer with 4,4′‐methylene bis(4‐phenylisocyanate) (MDI) (6) was performed under microwave irradiation, solution polymerization under gradual heating and reflux condition in the presence of pyridine (Py), dibuthyltin dilurate (DBTDL), and triethylamine (TEA) as a catalyst and without a catalyst, respectively. The optimized polymerization conditions according to solvent and catalyst for each method were performed with tolylene‐2,4‐diisocyanate (TDI) (7), hexamethylene diisocyanate (HDI) (8), and isophorone diisocyanate (IPDI) (9) to produce optically active poly(amide imide)s by the diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.09–1.10 dL/g. These polymers are optically active, thermally stable, and soluble in amide type solvents. All of the above polymers were fully characterized by IR spectroscopy, ¹H NMR spectroscopy, elemental analyses, specific rotation, and thermal analyses methods. Some structural characterization and physical properties of this new optically active poly(amide imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1647–1659, 2004     

Preparation and characterization of new optically active poly(amide‐imide)s derived from N,N‐(4,4′‐Oxydiphthaloyl)‐bis‐(s)‐(+)‐valine diacid chloride and aromatic diamines

4,4′‐Oxydiphthalic anhydride (1) was reacted with (s)‐(+)‐valine (2) in acetic acid and the resulting imide‐acid 3 was obtained in high yield. This compound 3 was converted to diacid chloride 4 by reaction with excess amount of thionyl chloride. The polycondensation reaction of diacid chloride 4 with several aromatic diamines such as 4,4′‐sulfonyldianiline (5a), 4,4′‐diaminodiphenyl methane (5b), 4,4′‐diaminodiphenylether (5c), p‐phenylenediamine (5d), m‐phenylenediamine (5e), and 4,4′‐diaminobiphenyl (5f) was performed by two conventional methods: low temperature solution polycondensation and a short period reflux conditions. To compare conventional solution polycondensation reaction methods with microwave‐assisted polycondensation, the reactions were also carried out under microwave conditions in the presence of small amount of o‐cresol that acts as a primary microwave absorber. The reaction mixture was irradiated for 4 min with 100% of radiation power. Several new optically active poly(amide‐imide)s with inherent viscosity ranging from 0.26–0.44 dL/g were obtained with high yield. All of the above polymers were fully characterized by ¹H‐NMR, FTIR, elemental analyses, and specific rotation techniques. Some structural characterizations and physical properties of these new optically active poly (amide‐imide)s are reported. POLYM. ENG. SCI. 46:558–565, 2006. © 2006 Society of Plastics Engineers     

Microwave‐assisted synthesis of new optically active poly(ester‐imide)s containing N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine moieties

Pyromellitic dianhydride (benzene‐1,2,4,5‐tetracarboxylic dianhydride) (1) was reacted with L‐phenylalanine (2) in a mixture of acetic acid and pyridine (3 : 2) and the resulting imide‐acid [N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid] (4) was obtained in quantitative yield. The compound (4) was converted to the N,N′‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid chloride (5) by reaction with thionyl chloride. A new facile and rapid polycondensation reaction of this diacid chloride (5) with several aromatic diols such as phenol phthalein (6a), bisphenol‐A (6b), 4,4′‐hydroquinone (6c), 1,8‐dihydroxyanthraquinone (6d), 4,4‐dihydroxy biphenyl (6e), and 2,4‐dihydroxyacetophenone (6f) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as o‐cresol. The polymerization reactions proceeded rapidly and are completed within 20 min, producing a series of optically active poly(ester‐imide)s with good yield and moderate inherent viscosity of 0.10–0.26 dL/g. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐imide)s are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2211–2216, 2002     

Synthesis and characterization of new optically active poly(amide‐imide‐urethane) thermoplastic elastomers,derived from 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L‐leucine‐p‐aminobenzoic acid) and PEG‐MDI

A new class of optically active poly(amide‐imide‐urethane) was synthesized via two‐step reactions. In the first step, 4,4′‐methylene‐bis(4‐phenylisocyanate) (MDI) reacts with several poly(ethylene glycols) (PEGs) such as PEG‐400, PEG‐600, PEG‐2000, PEG‐4000, and PEG‐6000 to produce the soft segment parts. On the other hand, 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine‐p‐amidobenzoic acid) (2) was prepared from the reaction of 4,4′‐(hexafluoroisopropylidene)‐N,N′‐bis(phthaloyl‐L ‐leucine) diacid chloride with p‐aminobenzoic acid to produce hard segment part. The chain extension of the above soft segment with the amide‐imide 2 is the second step to give a homologue series of poly(amide‐imide‐urethanes). The resulting polymers with moderate inherent viscosity of 0.29–1.38 dL/g are optically active and thermally stable. All of the above polymers were fully characterized by IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of this new optically active poly(amide‐imide‐urethanes) are reported. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2288–2294, 2004     

Optically active helical vinyl polymers via radical polymerization of (S)‐3‐vinyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl

(S)‐3‐Vinyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl ( 3 ) was synthesized via the Wittig reaction. Radical polymerization of all the monomers can take place smoothly in the temperature region tested. These polymers (poly‐ 3 ) showed very large specific optical rotations which were four times as large as those of the corresponding monomers 3 . Poly‐ 3 displayed optical rotations and Cotton effects in the UV?visible absorption region of side groups which were different from the corresponding monomers 3 and the model compounds (S)‐3‐ethyl‐2,2′‐bisalkoxy‐1,1′‐binaphthyl ( 4 ). These facts imply the formation of helicity of the main chain and the helical conformations were quite stable demonstrated by the unchanged pattern of temperature variable circular dichroism spectra. © 2015 Society of Chemical Industry     

Synthesis and characterization of novel optically active poly(amide‐imide)s

4,4′‐(Hexafluoroisopropylidene)‐bis‐(phthalic anhydride) (1) was reacted with L ‐leucine (2) in toluene solution at refluxing temperature in the presence of triethylamine and the resulting imide‐acid (4) was obtained in quantitative yield. The compound (4) was converted to the diacid chloride (5) by reaction with thionyl chloride. The polymerization reaction of the imide‐acid chloride (5) with 1,6‐hexamethylenediamine (6a) , benzidine (6b) , 4,4′‐diaminodiphenylmethane (6c) , 1,5‐diaminoanthraquinone (6d) , 4,4′‐sulfonyldianiline (6e) , 3,3′‐diaminobenzophenone (6f) , p‐phenylenediamine (6g) and 2,6‐diaminopyridine (6h) was carried out in chloroform/DMAc solution. The resulting poly(amide‐imide)s were obtained in high yield and are optically active and thermally stable. All of the above compounds were fully characterized by IR, elemental analyses and specific rotation. Some structural characterization and physical properties of those optically active poly(amide‐imide)s are reported. © 1999 Society of Chemical Industry     

Synthesis and characterization of novel optically active poly(imide–urethane)s derived from N,N′‐(pyromellitoyl)‐bis‐(L‐leucine) diisocyanate and aromatic diols

N,N′‐(Pyromellitoyl)‐bis‐(L ‐leucine) diacid was reacted with ethyl chloroformate in the presence of triethylamine followed by reaction with activated sodium azide and gave N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diacylazide in high yield. This diacylazide was heated in dry benzene and gave the unstable N,N′‐(pyromellitoyl)‐bis‐(L ‐leucine) diisocyanate ( 5 ) in quantitative yield. Thus, diisocyanate 5 was generated in situ and polycondensation reaction of this monomer with several aromatic diols, such as 4,4′‐dihydroxybiphenyl, 1,4‐hydroquinone, bisphenol A, phenolphthalein and 1,4‐dihydroxyanthraquinone, was performed in dry toluene under refluxing in the presence of 1,4‐diazabicyclo[2.2.2]octane (triethylenediamine) as a catalyst. The polymerization reactions proceeded within 48 h, producing a series of optically active poly(imide–urethane)s with good yield and moderate inherent viscosity in the range 0.18–0.28 dl g^?1. All of the above polymers were fully characterized by infrared spectra, elemental analyses and specific rotation. Some structural characterization and physical properties of these optically active poly(imide–urethane)s are reported Copyright © 2003 Society of Chemical Industry     

Synthesis of new optically active poly(amide‐imide)s containing EPICLON and L‐phenylalanine in the main chain by microwave irradiation and classical heating

EPICLON [3a,4,5,7a‐Tetrahydro‐7‐methyl‐5‐(tetrahydro‐2,5‐dioxo‐3‐furanyl)‐1,3‐isobenzofurandione] or [5‐(2,5‐dioxotetrahydrofurfuryl)‐3‐methyl‐3‐cyclohexyl‐1,2‐dicarboxylic acid anhydride] ( 1 ) was reacted with L ‐phenylalanine ( 2 ) in acetic acid, and the resulting amic acid was refluxed under a Dean‐Stark system with benzene, which produced diacid ( 3 ) in high yield. Compound ( 3 ) was converted to the diacid chloride ( 4 ) by reaction with oxalyl chloride in dry carbon tetrachloride. The polycondensation reaction of this diacid chloride ( 4 ) with several aromatic diamines such as 4,4′‐sulfonyldianiline ( 5a ), 4,4′‐diaminodiphenylmethane ( 5b ), 4,4′‐diaminodiphenylether ( 5c ), 1,4‐phenylenediamine ( 5d ), 1,3‐phenylenediamine ( 5e ), 2,4‐diaminotoluene ( 5f ), and 1,5‐diaminonaphthalene ( 5g ) was developed by using a domestic microwave oven in the presence of a small amount of a polar organic medium such as N‐methylpyrrolidone ( NMP ). The polymerization reactions were also performed under two different classical heating methods: low temperature solution polycondensation in the presence of trimethylsilyl chloride, and high temperature polymerization. A series of optically active poly(amide‐imide)s with moderate yield and inherent viscosity of 0.14–0.22 dL/g were obtained. All of the above polymers were fully characterized by IR, elemental analyses, and specific rotation. Some structural characterization and physical properties of this optically active poly(amide‐imide)s are reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3281–3291, 2004     

Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Preparation and characterization of novel optically active polyurethanes containing 1,1′‐binaphthol

Novel optically active polyurethanes (BPUs) based on chiral 1,1′‐binaphthol were synthesized via direct hydrogen transfer addition polymerization. The polymers were analyzed by FTIR, ¹H NMR, DSC‐TGA, CD spectra.The results showed that the specific rotation [α]²⁵_D were ?78.0° and +54.6° for the S‐BPU and R‐BPU respectively, and these polymers showed better thermal stability. The circular dichroism spectra of the chiral polymers were almost identical except that they gave opposite signals at each wavelength, and the infrared emissivity values of the S‐BPU and R‐BPU were 0.618 and 0.682, they displayed low infrared emissivity. Meantime the polymers implanted with PEG group exhibit better solubility, however thermal stability reduced to some extent. Some properties of the new optically active polyurethanes were reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Star poly(2‐ethyl‐2‐oxazoline)s—synthesis and thermosensitivity

A series of star‐shaped poly(2‐ethyl‐2‐oxazoline)s was prepared by cationic polymerization. The polymerization was initiated by dipentaerythrityl hexakis(4‐nitrobenzene sulfonate) and a tosylated hyperbranched polymer of glycidol. The polymerization proceeded in a controlled manner. The star structure of the products was determined by nuclear magnetic resonance. The molar mass distributions that were measured by gel permeation chromatography with multiangle laser light scattering were narrow, and the experimental values of the molar masses were close to those predicted. The very compact structure of the polymers obtained (compared with the linear counterparts) confirmed the star formation. The star poly(2‐ethyl‐2‐oxazoline)s show a phase transition temperature in the range 62–75 °C. Comparison of this phase transition temperature with that of the linear poly(2‐ethyl‐2‐oxazoline)s with the same molar masses indicates the influence of molar mass and topological structure of the macromolecule on temperature behavior. The prepared copolymers are spherical, which might be useful for the controlled transport and release of active compounds. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of novel poly(amide imide)s based on bis(p‐amidobenzoic acid)‐n‐trimellitylimido‐L‐leucine

N‐Trimellitylimido‐L ‐leucine was reacted with thionyl chloride, and N‐trimellitylimido‐L ‐leucine diacid chloride was obtained in a quantitative yield. The reaction of this diacid chloride with p‐aminobenzoic acid was performed in dry tetrahydrofuran, and bis(p‐amidobenzoic acid)‐N‐trimellitylimido‐L ‐leucine (5) was obtained as a novel optically active aromatic imide–amide diacid monomer in a high yield. The direct polycondensation reaction of the monomer imide–amide diacid 5 with 4,4′‐diaminodiphenylsulfone, 4,4′‐diaminodiphenylether, 1,4‐phenylenediamine, 1,3‐phenylenediamine, 2,4‐diaminotoluene, and benzidine (4,4′‐diaminobiphenyl) was carried out in a medium consisting of triphenyl phosphite, N‐methyl‐2‐pyrolidone, pyridine, and calcium chloride. The resulting novel poly(amide imide)s (PAIs), with inherent viscosities of 0.22–0.52 dL g^?1, were obtained in high yields, were optically active, and had moderate thermal stability. All of the compounds were fully characterized with IR spectroscopy, elemental analyses, and specific rotation. Some structural characterization and physical properties of these new optically active PAIs are reported. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 35–43, 2002; DOI 10.1002/app.10181     

Synthesis and characterization of novel aromatic poly(amide‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl or 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic diamines

New aromatic diimide‐dicarboxylic acids having kinked and cranked structures, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b), were synthesized by the reaction of trimellitic anhydride with 2,2′‐bis(4‐aminophenoxy)biphenyl (1a) and 2,2′‐bis(4‐aminophenoxy)‐1,1′‐binaphthyl (1b), respectively. Compounds 2a and 2b were characterized by FT‐IR and NMR spectroscopy and elemental analyses. Then, a series of novel aromatic poly(amide‐imide)s were prepared by the phosphorylation polycondensation of the synthesized monomers with various aromatic diamines. Owing to structural similarity, and a comparison of the characterization data, a model compound was synthesized by the reaction of 2b with aniline. The resulting polymers with inherent viscosities of 0.58–0.97 dl g^?1 were obtained in high yield. The polymers were fully characterized by FT‐IR and NMR spectroscopy. The ultraviolet λ_max values of the poly(amide‐imide)s were also determined. The polymers were readily soluble in polar aprotic solvents. They exhibited excellent thermal stabilities and had 10% weight loss at temperatures above 500 °C under a nitrogen atmosphere. Copyright © 2003 Society of Chemical Industry     

Synthesis and properties of new photosensitive and chiral poly(amide‐imide)s based on bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic diimide and dibenzalacetone moieties in the main chain

Aromatic poly(amide‐imide)s (PAIs) are high‐performance materials with a good compromise between thermal stability and processability when compared with polyamides or polyimides of analogous structures. In addition, the incorporation of photosensitive functional groups and chiral segments into the polymer backbone can lead to interesting polymers for various applications. In this work, six new photosensitive and chiral PAIs were synthesized from the direct polycondensation reaction of novel N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L ‐amino acids with 2,5‐bis(4‐aminobenzylidene)cyclopentanone as dibenzalacetone moiety using two different methods. The polymerization reactions produced a series of photosensitive and optically active PAIs in high yields and with good inherent viscosities. The resulting polymers were characterized using Fourier transform infrared and ¹H NMR spectroscopy, elemental analysis, inherent viscosity, specific rotation, solubility tests and UV‐visible spectroscopy. The thermal properties of the PAIs were investigated using thermogravimetric analysis. Due to the presence of the dibenzalacetone moiety in the polymer chain, the PAIs have photosensitive properties. Also, these PAIs are optically active and soluble in various organic solvents. These resulting new polymers have the potential to be used in column chromatography for the separation of enantiomeric mixtures. Copyright © 2009 Society of Chemical Industry     

Preparation of polystyrene/poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] fluorescent microspheres by miniemulsion polymerization

Fluorescent microspheres have great potential for use as probes in biological diagnostics. In this context, poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV), a conjugated polymer which has high quantum yield, controllable emitting wavelength and facile processing in manufacture, was used as a fluorescent material for the preparation of polystyrene (PS)/MEH‐PPV fluorescent microspheres via miniemulsion polymerization. We demonstrate that the emitting wavelength of the PS/MEH‐PPV fluorescent microspheres can be regulated by changing the amount of azobisisobutyronitrile initiator in the polymerization process. Using acrylic acid comonomer, poly[styrene‐co‐(acrylic acid)]/MEH‐PPV fluorescent microspheres with functional carboxyl groups were also prepared. All the microspheres were characterized using transmission electron microscopy, scanning electron microscopy, fluorescence microscopy and fluorescence spectrophotometry. The functional carboxyl groups were characterized using Fourier transform infrared spectroscopy. This work provides a novel platform for the preparation of conjugated polymer fluorescent microspheres for biological applications. © 2012 Society of Chemical Industry     

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

The quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (M_n) and narrow molecular weight distribution (M_w/M_n) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry