Synthesis and radical polymerization of styrene derivative bearing kojic acid moieties

A styrene derivative ( 1 ) bearing kojic acid moieties was prepared by the base-catalyzed reaction of p-formylstyrene with kojic acid. Hydroxyl groups in 1 were subjected to acetylation. Although 1 did not undergo radical polymerization, the acetylated styrene derivative ( 2 ) showed good radical homo- and copolymerizability. For instance, a polymer having the number average molecular weight (M_n) of 60,000 was obtained in almost quantitative yield (97%) by the polymerization of 2 in chloroform (1.5 M) at 60°C for 36 h using α,α′-azobis(isobutyronitrile) (AIBN, 5 mol %) as an initiator. Under similar conditions, copolymers of 2 with styrene were also obtained in high yield. By partial deacetylation of the copolymer with a triethylamine catalyst, a copolymer containing α-hydroxyketone structures originated from kojic acid moieties was successfully regenerated. The deacetylated copolymer can be crosslinked by complexation with metal salts such as Al³⁺. © 1996 John Wiley & Sons, Inc.     

Utility of malonate‐initiated polymerizations of methyl methacrylate

We have studied the polymerization of methyl methacrylate with cesium and tetramethylammonium salts of diethyl 2‐ethylmalonate carbanion. For polymerizations initiated at room temperature, no effort was made to control the exotherm. The polymerizations proceeded with high conversions and produced polymers characterized by broad polydispersities (M_w/M_n = 2–3). We consistently observed M_n (exptl) < M_n(calcd) for target = 50,000–300,000 g/mol; we observed an apparent upper limit for M_n of 60,000–70,000 g/mol. Chain transfer from impurities in reagents was eliminated as the source of molecular weight lowering. Oligomeric samples were analyzed by mass spectrometry; results were best explained by methoxide initiation of the polymerization. No evidence for malonate end groups was observed in the mass spectra. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 615–620, 1999     

Mobility of a tackifying resin in a pressure-sensitive adhesive

A detailed study of the mobility of a tackifying resin in a pressure-sensitive adhesive (PSA) has been done for the first time. The objective of this work is to relate changes in adhesive performance with tackifier loading to tackifier mobility. Tackifiers are low-molecular weight resins that improve the overall performance of PSAs. They increase the adhesive tack or the ability to form a bond of measurable strength after brief contact under slight applied pressure. In this study the diffusion of n-butyl ester of abietic acid (n-BEAA) in either polyisoprene (PI) (M_w = 195,000 M_w/M_n ∼ 1.05) or poly(ethylene-propylene) (PEP) (M_w = 40,000 M_w/M_n ∼ 2.30) was measured by Pulsed Gradient Spin Echo-Nuclear Magnetic Resonance (PGSE-NMR) as a function of both tackifier concentration and temperature. The concentration dependence of the tackifier's diffusion coefficient was weak for both systems. The weak variation in mobility with composition for the PI/n-BEAA system was consistent with that system's weak variation in tack with composition. On the other hand, blends of PEP/n-BEAA showed only modest variation in mobility, even though these adhesive systems showed appreciable enhancement of tack at intermediate compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 373–381, 1998     

Separation of iron(III) and gold(III) by paper chromatography using mixed solvents containing diisopropyl ether

The separation of iron(III) and gold(III) by partition paper chromatography has been investigated employing a mixture of diisopropyl ether (IPE) and n-alcohol saturated with hydrochloric acid (initial acid concentration 5.0 M) as solvent. Methyl, ethyl, n-propyl, n-butyl, and n-pentyl alcohols were used as components of the solvent. The content of n-alcohol in the initial organic phase was varied. It was found that the R_f values for both of the metals increased with an increase in the carbon-to-oxygen ratio in the alcohol (except in the case or iron(III) and n-pentyl alcohol), and with an increase in the alcohol content in the initial organic phase (except in the case of iron(III) and n-propyl alcohol). The best separation results were obtained by using the systems: hydrochloric acid (5.0 M)-IPE-n-propyl alcohol (50:35:15) gDR_f = 0.56, hydrochloric acid (5.0 M)-IPE-ethyl alcohol (50:15:35) ΔR_f = 0.51, and hydrochloric acid (5.0 M)-IPE-n-pentyl alcohol (50:35:15) ΔR_f = 0.37.     

Syntheses and properties of organosoluble poly(ether imide)s from 1,1‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]cyclohexane dianhydride and aromatic diamines

A bis(ether anhydride) monomer, 1,1‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]cyclohexane dianhydride ( IV‐A ), was synthesized from the nitro displacement of 4‐nitrophthalodinitrile by the phenoxide ion of 1,1‐bis(4‐hydroxyphenyl)cyclohexane ( I‐A ), followed by alkaline hydrolysis of the intermediate bis(ether dinitrile) and dehydration of the resulting bis(ether acid). A novel series of organosoluble poly(ether imide)s ( VI _a–i )(PEIs) bearing cyclohexylidene cardo groups was prepared from the bis(ether anhydride) IV‐A with various aromatic diamines V _a–i via a conventional two‐stage process. The PEIs had inherent viscosities in the range of 0.48–1.02 dL/g and afforded flexible and tough films by solution‐casting because of their good solubilities in organic solvents. Most PEIs showed yield points in the range of 89–102 MPa at stress‐strain curves and had tensile strengths of 78–103 MPa, elongations at breaks of 8–62%, and initial moduli of 1.8–2.2 GPa. The glass‐transition temperatures (T_g's) of these PEIs were recorded between 200–234 °C. Decomposition temperatures of 10% weight loss all occurred above 490 °C in both air and nitrogen atmospheres, and their residues were more than 43% at 800 °C in nitrogen atmosphere. The cyclohexane cardo‐based PEIs exhibited relatively higher T_g's, better solubilities in organic solvents, and better tensile properties as compared with the corresponding Ultem® PEI system. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 788–799, 2001     

Controlled/living polymerization of methacrylamide in aqueous media via the RAFT process

The polymerization of methacrylamide (MAM) was performed in aqueous media via reversible addition fragmentation chain transfer (RAFT) polymerization with the dithiobenzoate chain‐transfer agent (CTA) 4‐cyanopentanoic acid dithiobenzoate (CTP) and 4,4′‐azobis(4‐cyanopentanoic acid) (V‐501) as initiator. The polymerization in unbuffered water at 70 °C with a CTP/V‐501 ratio of 1.5 was controlled for the first 3 h, after which the molecular weight distribution broadened and a substantial deviation of the experimental from the theoretical molecular weight occurred, presumably because of a loss of CTA functionality at longer polymerization times. Conducting the polymerization in an acidic buffer afforded a well‐defined homopolymer (M_n = 23,800 g/mol, M_w/M_n = 1.08). To demonstrate the controlled/living nature of the system, a block copolymer of MAM and acrylamide was successfully prepared (M_n = 33,800 g/mol, M_w/M_n = 1.25) from a polymethacrylamide macro‐CTA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3141–3152, 2005     

The true molecular weight distributions of acrylate polymers formed in propagating fronts

We have analyzed fractionated samples of poly(methacrylic acid) produced in a propagating front for the amount of anhydride that formed and determined that a large percentage of acid groups exist as anhydrides (>20%). By analyzing the samples after cleavage, we found that the molecular weight dropped significantly (from M_n = 1.4 × 10⁵ to M_n = 1.0 × 10⁴). We conclude that the high molecular weights observed previously were the result of intermolecular anhydride formation. Poly(butyl acrylate), which cannot form anhydride bonds, produced in fronts had broad (M_w/M_n = 1.7–2.0) but unimodal molecular weight distributions with M_u < 10⁵. The average molecular weight decreased with increasing initiator concentrations. © 1996 John Wiley & Sons, Inc.     

Living cationic polymerization of vinyl ether with a cyclic acetal group

The living cationic polymerization of 5‐ethyl‐2‐methyl‐5‐(vinyloxymethyl)‐1,3‐dioxane ( 1 ), a vinyl ether with a cyclic acetal unit, was investigated with various initiating systems in toluene or methylene chloride at 0 to ?30 °C. With initiating systems such as hydrogen chloride (HCl)/zinc chloride (ZnCl₂), isobutyl vinyl ether–acetic acid adduct [CH₃CH(OiBu)OCOCH₃]/tin tetrabromide (SnBr₄)/di‐tert‐butylpyridine (DTBP), and CH₃CH(OiBu)OCOCH₃/ethylaluminum sesquichloride (Et_1.5AlCl_1.5)/ethyl acetate (CH₃COOEt), the number‐average molecular weights (M_n's) of the obtained poly( 1 )s increased in direct proportion to the monomer conversion and produced polymers with relatively narrow molecular weight distributions [MWDs; weight‐average molecular weight/number‐average molecular weight (M_w/M_n) = 1.2–1.3]. To investigate the living nature of the polymerization with CH₃CH(OiBu)OCOCH₃/SnBr₄/DTBP, a second monomer feed was added to the almost polymerized reaction mixture. The added monomer was completely consumed, and the M_n values of the polymers showed a direct increase against the conversion of the added monomer, indicating the formation of a long‐lived propagating species. The glass transition temperature and thermal decomposition temperature of poly( 1 ) (e.g., M_n = 13,600, M_w/M_n = 1.30) were 29 and 308 °C, respectively. The cyclic acetal group in the pendants of the polymer of 1 could be converted to the corresponding two hydroxy groups in a 65% yield by an acid‐catalyzed hydrolysis reaction. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4855–4866, 2007     

Cobalt‐mediated radical polymerization routes to poly(vinyl ester) block copolymers

Cobalt‐mediated radical polymerizations (CMRPs) utilizing redox initiation are demonstrated to produce poly(vinyl ester) homopolymers derived from vinyl pivalate (VPv) and vinyl benzoate (VBz), and their block copolymers with vinyl acetate (VAc). Combining anhydrous Co(acac)₂, lauroyl peroxide, citric acid trisodium salt, and VPv at 30 °C results in controlled polymerizations that yield homopolymers with M_n = 2.5–27 kg/mol with M_w/M_n = 1.20–1.30. Homopolymerizations of scrupulously purified VBz proceed with lower levels of control as evidenced by broader polydispersities over a range of molecular weights (M_n = 4–16 kg/mol; M_w/M_n = 1.34–1.65), which may be interpreted in terms of the decreased nucleophilicity of these less electron donating propagating polymer chain ends. Based on these results, we demonstrate that sequential CMRP reactions present a viable route to microphase separated poly(vinyl ester) block copolymers as shown by small‐angle X‐ray scattering analyses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of arborescent styrene homopolymers and copolymers from epoxidized substrates

The synthesis of arborescent styrenic homopolymers and copolymers was achieved by anionic polymerization and grafting. Styrene and p‐(3‐butenyl)styrene were first copolymerized using sec‐butyllithium in toluene, to generate a linear copolymer with a weight‐average molecular weight M_w = 4000 and M_w/M_n = 1.05. The pendant double bonds of the copolymer were then epoxidized with m‐chloroperbenzoic acid. A comb‐branched (or arborescent generation G0) copolymer was obtained by coupling the epoxidized substrate with living styrene‐p‐(3‐butenyl)styrene copolymer chains with M_w ≈ 5000 in a toluene/tetrahydrofuran mixture. Further cycles of epoxidation and coupling reactions while maintaining M_w ≈ 5000 for the side chains yielded arborescent copolymers of generations G1–G3. A series of arborescent styrene homopolymers was also obtained by grafting M_w ≈ 5000 polystyrene side chains onto the linear and G0–G2 copolymer substrates. Size exclusion chromatography measurements showed that the graft polymers have low polydispersity indices (M_w/M_n = 1.02–1.15) and molecular weights increasing geometrically over successive generations. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Rheological Properties of Nansocale Poly(Styrene-Maleic Acid) Encapsulated Organic Pigment Dispersion by Phase Separation Technique

Azo pigment yellow 14 (P.Y.14) was encapsulated into copolymer of styrene and maleic acid (PSMA) via phase separation technique followed by the preparation of composite dispersions. Herein, we mainly investigate its rheological properties. Our results showed that the apparent viscosity (n _a ) of composite dispersion first decreased and then increased with an increase of molar content of maleic acid in PSMA (F _M ), intrinsic viscosity of PSMA ([n]), and the weight ratio of PSMA to P.Y.14 (R _C/P ), respectively. The composite dispersion with low n _a was more close to Newtonian fluid when F _M , [n] and R _C/P were equal to 0.53, 79.65 mL/g, and 12%, respectively. n _a of the composite would increase with increasing the pH value, and first decreased and then increased with a raising of the electrolyte and alcohol concentration, respectively, especially with AlCl₃ and glycerol.     

Synthesis and characterization of novel optically active poly(ester‐imide)s with high Tg and good thermal stability

A series of novel optically active poly(ester‐imide)s (ter‐PEIs) with high glass transition temperature (T_g), good thermal stability, and solubility were successfully designed and synthesized by direct polycondensation reactions, using p‐hydroxybenzoic acid (PHB), 4,4’‐dihydroxybenzophenone, and a chiral diacid, N,N'‐(pyromellitoyl)‐bis‐L‐phenylalanine diacid as monomers. The resulting terpolymers were characterized by¹H‐NMR, FTIR, element analysis, thermogravimetric analysis, different scanning calorimeter and wide‐angle x‐ray diffraction, etc. The ter‐PEIs are amorphous polymers with good heat resistance and high T_gs. They are soluble in many common polar organic solvents and show optically rotation property. The specific rotation values of the ter‐PEIs increase with the molar ratio of the chiral diacid, and the rigid PHB monomer is beneficial to increase the T_gs of the polymers. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and biological evaluation of -n[4-(2-trans-[([2,6-diamino-4(3H)-oxopyrimidin-5-yl]methyl)thio]cyclobutyl)benzoyl] -l-glutamic acid a novel 5-thiapyrimidinone inhibitor of dihydrofolate reductase

The synthesis and biological evaluation of N-[4-(2-trans-[([2,6-diamino-4(3H)-oxopyrimidin-5-yl]methyl)thio]cyclobutyl)benzoyl]-L-glutamic acid (1) is reported. Compound 1 is a potent dihydrofolate reductase (DHFR) inhibitor (K_j = 12 nM) with excellent in vitro cell culture growth inhibition (L1210, IC₅₀ = 29 nM). Protection experiments showed that the cell growth inhibitory activity was due to DHFR inhibition. The key step in the synthesis was the coupling of a cyclobutylmethylthiol with the 5-bromo-2,6-diamino-4-oxopyrimidine ⁸.     

Synthesis of arborescent polystyrene by “click” grafting

A method was developed for the synthesis of arborescent polystyrene by “click” coupling. Acetylene functionalities were introduced on linear polystyrene (M_n = 5300 g/mol, M_w/M_n = 1.05) by acetylation and reaction with potassium hydroxide, 18‐crown‐6 and propargyl bromide in toluene. Polymerization of styrene with 6‐tert‐butyldimethylsiloxyhexyllithium yielded polystyrene (M_n = 5200 g/mol, M_w/M_n = 1.09) with a protected hydroxyl chain end. Deprotection, followed by conversions to tosyl and azide functionalities, provided the side chain material. Coupling with CuBr and N,N,N′,N″,N″‐pentamethyldiethylenetriamine proceeded in up to 94% yield. Repetition of the grafting cycles led to well‐defined (M_w/M_n ≤ 1.1) polymers of generations G1 and G2 in 84% and 60% yield, respectively, with M_n and branching functionalities reaching 2.8 × 10⁶ g/mol and 460, respectively, for the G2 polymer. Coupling longer (M_n = 45,000 g/mol) side chains with acetylene‐functionalized substrates was also examined. For a linear substrate, a G0 polymer with M_n = 4.6 × 10⁵ g/mol and M_w/M_n = 1.10 was obtained in 87% yield; coupling with the G0 (M_n = 52,000 g/mol) substrate produced a G1 polymer (M_n = 1.4×10⁶ g/mol, M_w/M_n = 1.38) in 28% yield. The complementary approach using azide‐functionalized substrates and acetylene‐terminated side chains was also investigated, but proceeded in lower yield. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1730–1740     

Block copolymers by transformation of “living” carbocationic into “living” radical polymerization. II. ABA-type block copolymers comprising rubbery polyisobutene middle segment

A general method for the transformation of “living” carbocationic into “living” radical polymerization, without any modification of chain ends, is reported for the preparation of ABA block copolymers. For example, α,ω-difunctional polyisobutene, capped with several units of styrene, Cl-St-PIB-St-Cl, prepared cationically (M_n = 7800, M_w/M_n = 1.31) was used as an efficient difunctional macroinitiator for homogeneous “living” atom transfer radical polymerization to prepare triblock copolymers with styrene, PSt-PIB-PSt (M_n = 28,800, M_w/M_n = 1.14), methyl acrylate, PMA-PIB-PMA (M_n = 31,810, M_w/M_n = 1.42), isobornyl acrylate, PIBA-PIB-PIBA (M_n = 33,500, M_w/M_n = 1.21), and methyl methacrylate, PMMA-PIB-PMMA (M_n = 33,500, M_w/M_n = 1.47). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3595–3601, 1997     

Power law of nucleation rate of folded-chain single crystals of polyethylene

The number-average molecular weight (M _n) dependence of the primary nucleation rate (I) of polyethylene (PE) folded-chain single crystals was studied in the ordered phase. We observed that the M _n dependence of I is mainly controlled by the diffusion process of polymer chains within the interface between a nucleus and the melt and/or within the nucleus. The results show that I decreases with increasing M _n and follows a power law I∝M _n ^−2.3 for the ordered phase. It is named the power law of the nucleation rate. In a previous article we showed that for the disordered phase I∝M _n ⁻¹. In this article, we concluded that I decreases with increasing M _n and follows a universal power law, I∝M _n ^−H for both ordered and disordered phases. The power H depends on the degree of order of the crystalline phase, which is related to the morphology. Received: 13 September 2000 Accepted: 15 November 2000     

Effect of polycondensation methods on molecular weight distribution of nylon 610

Polycondensation methods greatly influence the molecular weight distribution of poly(hexamethylene sebacamide) (nylon 610) as determined by gel permeation chromatography (GPC). The ratio of weight average molecular weight to number average molecular weight (M_w/M_n) was used as a measure for estimating the molecular weight distribution. The M_w/M_n ratios of nylon 610 obtained from melt, solid phase, and high temperature polycondensation methods were 2 to 3.5, which were expected values for the most probable distribution. However, those for polymers obtained from the direct polycondensation in the presence of triphenylphosphine, interfacial polycondensation and low temperature polycondensation using an acid chloride varied over a wide range from 3.5 to 8.5. The effect of the kind of organic solvents in the interfacial method on the M_w/M_n ratios was especially large, and the molecular weight distribution could be controlled to some extent by selecting an appropriate solvent.     

Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Visible light‐induced RAFT polymerization of methacrylates with benzaldehyde derivatives as organophotoredox catalysts

The benzaldehyde derivatives, such as 2,4‐dimethoxy benzaldehyde (PC1) and p‐anisaldehyde (PC2), were successfully used as photoredox catalysts (PCs) in combination with typical RAFT agent 4‐cyano‐4‐(phenylcarbonothioylthio)pentanoic acid (CTP) for the controlled photoinduced electron transfer RAFT polymerization (PET‐RAFT) of methyl methacrylate (MMA) and benzyl methacrylate (BnMA) at room temperature. The kinetics of the polymerizations showed first order with respect to monomer conversions. Besides, the average number molecular weights (M_n) of the produced polymers increased linearly with the monomer conversions and kept relatively narrow polydispersity (PDI = M_w/M_n). For example, the M_n of PMMA increased from about 3400 to 17,300 g mol⁻¹ with the increasing in monomer conversion from 11% to 85%, and the PDI maintained around 1.36. The living features of polymerizations with the PC1 and PC2 as catalysts have also been further supported by chain extension and synthesis of PMMA‐b‐PBnMA diblock copolymer. As a result, the simplicity and efficiency of benzaldehyde derivatives catalyzed PET‐RAFT polymerization have been demonstrated under mild conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 229–236     

Living ring‐opening polymerization based on neighboring group participation

Cationic ring‐opening polymerization of a five‐membered cyclic dithiocarbonate having benzoxymethyl group; 5‐benzoxymethyl‐1,3‐oxathiolane‐2‐thione, was carried out with TfOH or TfOMe as an initiator in PhCl at rt – 60 °C. The molecular weight distribution (M_w/M_n) of the polymer obtained with TfOMe was very narrow even at 60 °C (M_w/M_n 1.14), and the Mn value of the polymers estimated by GPC was in good agreement with the molecular weight determined from ¹H‐NMR. The living nature of the polymerization was confirmed by the conversion dependence of the Mn (M_w/M_n) and the correlation of the experimental and theoretical M_n (M_w/M_n) values.