Cyclic poly(lactide)s via the ROPPOC method catalyzed by alkyl‐ or aryltin chlorides

A comparison of tributyltin chloride, dibutyltin dichloride, and butyltin trichloride as catalysts of ring‐opening polymerizations (ROPs) of l‐lactides at 160 °C in bulk reveals increasing reactivity in the above order, but only the least reactive catalysts, Bu₃SnCl, yield a uniform reaction product, namely cyclic poly(L‐lactide)s with weight average molecular weights (M_w's) in the range of 40,000–80,000. A comparison of dimethyltin , dibutyltin , and diphenyltin dichlorides resulted in the following order of reactivity: Me₂SnCl₂ < Bu₂SnCl₂ < <Ph₂SnCl₂. In this series also, the most reactive catalyst yields cyclic polylactides, but the extent of cyclization varies with the molecular weight. The formation of cyclic polylactides is explained by ROP combined with simultaneous polycondensation involving end‐to‐end cyclization (ROPPOC method). ROP of meso‐lactide at 80 or 60 °C yields even‐numbered linear chains as main products, a result supporting the ROPPOC mechanism. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 952–960     

Syntheses of multicyclic poly(ether sulfone)s from 5,5′,6,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethyl spirobisindane and 4,4′‐bis(4‐chlorophenyl) sulfones

5,5′,6,6′‐Tetrahydroxy‐3,3,3′,3′‐tetramethyl spirobisindane (TTSBI) was polycondensed with 4,4′‐dichlorodiphenyl sulfone (DCDPS) or with 4,4′‐bis(4‐chlorophenyl sulfonyl) biphenyl (BCSBP) in DMSO. Concentration and feed ratio were optimized to avoid gelation and to obtain a maximum yield of multicyclic polyethers free of functional groups. Regardless of these reaction conditions, only low fractions of perfect multicycles were obtained from DCDPS apparently due to steric hindrance of ring closure. Under the same conditions high fractions of perfect multicycles were achieved with the longer and more flexible DCSBP. The reaction products were characterized by MALDI‐TOF mass spectrometry, ¹H‐NMR spectroscopy viscosity, and DSC measurements. Relatively low glass transition temperatures (T_gs ≈ 160–175 °C) were found. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3732–3739, 2008     

About formation of cycles in Sn(II) octanoate‐catalyzed polymerizations of lactides

At first, formation of cycles in commercial poly(l ‐lactide)s is discussed and compared with benzyl alcohol‐initiated polymerizations performed in this work. This comparison was extended to polymerizations initiated with 4‐cyanophenol and pentafluorothiophenol which yielded cyclic polylactides via end‐biting. The initiator/catalyst ratio and the acidity of the initiator were found to be decisive for the extent of cyclization. Further polymerizations of l ‐lactide were performed with various diphenols as initiators/co‐catalysts. With most diphenols, cyclic polylactides were the main reaction products. Yet, only catechols yielded even‐numbered cycles as main reaction products, a result which proves that their combination with SnOct₂ catalyzed a ring‐expansion polymerization (REP). The influence of temperature, time, co‐catalyst, and catalyst concentrations was studied. Four different transesterification reactions yielding cycles were identified. For the cyclic poly(l ‐lactide)s weight average molecular weights (M_w's) up to 120,000 were obtained, but ¹H NMR end group analyses indicated that the extent of cyclization was slightly below 100%. The influence of various parameters like structure of initiator and catalyst and temperature on the formation of cyclic poly(l ‐lactide)s has been investigated. Depending on the chosen conditions, the course of the polymerization can be varied from a process yielding exclusively linear polylactides to mainly cyclic polylactides. Three different reaction pathways for cyclization reactions have been identified. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1915–1925     

MALDI‐TOF‐MS analysis of living cationic polymerization of vinyl ethers. III. Polymerization with SnCl4 and TiCl4 in the absence of additives

Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis revealed that the precision control (or the living nature) of the cationic polymerization of vinyl ethers with SnCl₄ or TiCl₄ critically depends on the Lewis acid concentration and temperature. Specifically, at an extremely low Lewis acid concentration, for example, the polymerization with the HCl–vinyl ether adduct (an initiator) is living at ?78 °C in CH₂Cl₂ solvent, whereas side reactions occurred at a higher concentration of SnCl₄ or at a higher temperature, ?15 °C. This was more pronounced with SnCl₄ than with TiCl₄, which was due to a stronger Lewis acidity of SnCl₄ as suggested by NMR analysis of the model reactions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1258–1267, 2001     

MALDI‐TOF‐MS analysis of living cationic polymerization of vinyl ethers. II. Living nature of growing end and side reactions

Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis revealed that the HCl–vinyl ether adduct/SnCl₄/n‐Bu₄NCl initiating system induced living cationic polymerization of isobutyl vinyl ether in CH₂Cl₂ at ?78 °C, that is, the well‐resolved spectra demonstrated that the produced polymers consist of only one series of polymers carrying one initiator fragment at the α end and one methoxy group originated from quenching with methanol at the ω end. The polymer molecular weight as well as the terminal structure were unchanged even when the reaction mixtures were kept unquenched at ?78 °C for an interval of more than five times longer than the reaction period after complete consumption of monomer, which indicates the long lifetime of the living end even under such starved conditions. In contrast, the polymers obtained at a higher temperature, ?15 °C, showed an additional minor series of polymers formed via proton initiation, originating from adventitious water. Under the starved conditions, other side reactions occurred to generate minor series of polymers with an aldehyde ω end or a diisobutyl acetal ω end. Rather surprisingly, however, unsaturated C?C end groups were not detected, which means the absence of β‐proton elimination under these conditions. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1249–1257, 2001     

Synthesis of Conjugated Polymer Nanoparticles in Non‐Aqueous Emulsions

Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.

     

Ring‐expansion polymerization of meso‐lactide catalyzed by dibutyltin derivatives

Meso‐Lactide was polymerized in bulk at 60, 80, and 100 °C by means of three different types of catalysts: dibutyltin sulfides (2,2‐dibutyl‐2‐stanna‐1,3‐dithiolane and 2,2′‐dibutyl‐2‐stanna‐1,3‐dithiane), dibutyltin derivatives of substituted catechols (BuCa, CyCa, and BzCa), and dibutyltin derivatives of 2,2′dihydroxybiphenyl (SnBi) and 2,2′‐dihydroxy‐1,1′‐binaphthyl (SnNa). Only the latter two catalysts were active at 60 °C. The architecture of the resulting polylactides depends very much on the structure of the catalyst and on the temperature. At the lowest temperature (60 °C), SnBi and SnNa mainly yielded even‐numbered linear chains, but SnNa also yielded even‐numbered cycles at 100 °C and short reaction times. In contrast, BuCa, CyCa, and BzCa mainly yielded odd‐numbered cycles, although the same catalysts yielded even‐numbered linear chains when benzylalcohol was added. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 749–759     

Synthesis and ring‐opening polymerization of macrocyclic aryl ketone oligomers

A series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge‐linking electron‐rich aromatic hydrocarbons 3a–d under pseudo‐high dilution conditions in the presence of Lewis base via Friedel–Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI‐TOF‐MS, GPC, and ¹H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring‐opening polymerization in the melt by using potassium 4,4′‐biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring‐opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa · S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring‐opening polymerization. Copyright © 2009 John Wiley & Sons, Ltd.     

Simultaneous Chain‐Growth and Step‐Growth Polymerization—A New Route to Cyclic Polymers

Reinvestigation of numerous ring‐opening polymerizations by means of MALDI‐TOF mass spectrometry has evidenced that cyclic polymers were formed as the only reaction products or, at least, in large fractions. This finding is ascribed to the intermediate formation of difunctional chains having active end groups that can react with each other. Due to the low concentration of these difunctional chains cyclization is favored over chain extension according to the Ruggli–Ziegler dilution principle. A polymerization mechanism which usually favors the formation of cyclic polymers is the zwitterionic polymerization, but an exception from this rule is known. The following classes of monomers were discussed: α‐amino acid, N‐carboxyanhydrides (oxazolidine‐2,5‐diones), dithiolane‐2,4‐diones, 5,5‐dimethyl‐1,3,2‐dioxathiolan‐4‐one‐2‐oxide, salicylic acid O‐carboxyanhydride, L ‐lactide and D ,L ‐lactide, hexamethyl cyclotrisiloxane, and macrocyclic dithiocarbamates.

     

Cationic polymerizations of 2‐alkyloxazolines catalyzed by bismuth salts

Acidic bismuth salts, such as BiCl₃, BiBr₃, BiJ₃, and Bi‐triflate catalyzed the ring‐opening polymerization of 2‐methoxazoline (MOZ) in bulk at 100 °C, whereas less acidic salts such as Bi₂O₃ or Bi(III)acetate did not. Bi‐triflate‐catalyzed polymerizations of 2‐ethyloxazoline (EtOZ) were performed with variation of the monomer–catalyst ratio (M/C). It was found that the molecular weights were independent of the M/C ratio. The formation of cationic chain ends and the absence of cycles was proven by reactions of virgin polymerization products with N,N‐dimethyl‐4‐aminopyridine or triphenylphosphine. The resulting polymers having modified cationic chain ends were characterized by ¹H NMR spectroscopy and MALDI‐TOF mass spectrometry. The polymerization mechanism including chain‐transfer reactions is discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4777–4784, 2008     

New polymer syntheses. CXI. Aliphatic polyesters by the ring‐opening polycondensation of glutaric anhydride with ethylene or trimethylene carbonate

Several polycondensations of ethylene carbonate with succinic anhydride or glutaric anhydride (GA) were conducted in bulk. Low molar mass polyesters were obtained with pyridine‐type catalysts and GA. Analogous polycondensations of trimethylene carbonate (TMC) and GA were successful when quinoline, 4‐(N,N‐dimethylamino)pyridine, or BF₃ · OEt₂ was used as a catalyst. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra revealed the formation of cyclic oligoesters and polyesters by backbiting degradation. Monomer mixtures containing an excess of TMC yielded copoly(ester carbonate)s with number‐average molecular weights up to 16,000 Da. Analogous copoly(ester carbonate)s were obtained from TMC and 3,3′‐tetramethylene glutaric anhydride. Furthermore, combined polycondensation/ring‐opening polymerization reactions of TMC and GA with L ‐lactide or ?‐caprolactone were studied. All copolymers were characterized by viscosity measurements and by IR, ¹H, and ¹³C NMR spectroscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4357–4367, 2002     

Convenient Method of Chain‐Growth Polycondensation for Well‐Defined Aromatic Polyamides

Summary: For the convenient synthesis of well‐defined poly(N‐octyl‐p‐benzamide)s with low polydispersities, the polycondensation of methyl 4‐octylaminobenzoate ( 1 ) was investigated. Methyl ester monomer 1 polymerized with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) in the presence of an initiator in tetrahydrofuran at −10 °C. The highly pure polyamide with a defined molecular weight and a low polydispersity is obtained after simple treatment of the reaction mixture with aqueous NaOH solution, followed by evaporation.

The chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester ( 1 ) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).     

Glycation sites in neoglycoglycoconjugates from the terminal monosaccharide antigen of the O‐PS of Vibrio cholerae O1, serotype Ogawa,and BSA revealed by matrix‐assisted laser desorption–ionization tandem mass spectrometry

We present the MALDI‐TOF/TOF‐MS analyses of various hapten–bovine serum albumin (BSA) neoglycoconjugates obtained by squaric acid chemistry coupling of the spacer‐equipped, terminal monosaccharide of the O‐specific polysaccharide of Vibrio cholerae O1, serotype Ogawa, to BSA. These analyses allowed not only to calculate the molecular masses of the hapten–BSA neoglycoconjugates with different hapten–BSA ratios (4.3, 6.6 and 13.2) but, more importantly, also to localize the covalent linkages (conjugation sites) between the hapten and the carrier protein. Determination of the site of glycation was based on comparison of the MALDI‐TOF/TOF‐MS analysis of the peptides resulting from the digestion of BSA with similar data resulting from the digestion of BSA glycoconjugates, followed by sequencing by MALDI‐TOF/TOF‐MS/MS of the glycated peptides. The product‐ion scans of the protonated molecules were carried out with a MALDI‐TOF/TOF‐MS/MS tandem mass spectrometer equipped with a high‐collision energy cell. The high‐energy collision‐induced dissociation (CID) spectra afforded product ions formed by fragmentation of the carbohydrate hapten and amino acid sequences conjugated with fragments of the carbohydrate hapten. We were able to identify three conjugation sites on lysine residues (Lys235, Lys437 and Lys455). It was shown that these lysine residues are very reactive and bind lysine specific reagents. We presume that these Lys residues belong to those that are considered to be sterically more accessible on the surface of the tridimensional structure. The identification of the y‐series product ions was very useful for the sequencing of various peptides. The series of a‐ and b‐product ions confirmed the sequence of the conjugated peptides. Copyright © 2010 John Wiley & Sons, Ltd.     

Solvent effect on chain‐growth polycondensation for aromatic polyethers

The polycondensation of potassium 5‐cyano‐4‐fluoro‐2‐octylphenolate ( 1b ) was carried out in the presence of 4‐fluoro‐4′‐trifluoromethylbenzophenone ( 2 ) as an initiator for chain‐growth polycondensation in a variety of solvents, and the chain‐growth nature of this polymerization was found to depend on the kind of solvent. In the polycondensation of 1b with 2 in sulfolane at 150 °C, the MALDI‐TOF mass spectra of poly 1b showed only one series of peaks due to poly 1b attached with the initiator 2 unit, and the ¹⁹F NMR spectra indicated that the ratios of the initiator unit to the end group were 1.0. Therefore, chain‐growth polycondensation occured in this condition. On the other hand, the polycondensation in THF, quinoline, DMI, tetraglyme at 150 °C gave poly 1b with broad molecular weight distributions, and the MALDI‐TOF mass spectra showed two series of peaks resulting from both chain‐growth and step‐growth polycondensations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1198–1207, 2004     

Matrix‐assisted laser desorption ionization time of flight mass spectrometry analysis of living cationic polymerization of vinyl ethers. I. Optimization of measurement conditions for poly(isobutyl vinyl ether)

Matrix‐assisted laser desorption ionization time of flight mass spectrometry (MALDI‐TOF‐MS) was utilized for the analysis of polymers obtained by the living cationic polymerization of isobutyl vinyl ether (IBVE) with the HCl‐VE adduct/SnCl₄/n‐Bu₄NCl initiating system in CH₂Cl₂ at −78 °C. Under optimized analysis conditions, well‐resolved spectra were obtained for samples with number‐average molecular weights of ≤10⁴ with the use of 1,8‐dihydroxy‐9(10H)‐anthracenone (dithranol) as a matrix and sodium trifluoroacetate as an added salt. The MS spectra showed only one series of peaks separated exactly by the mass of the IBVE. The observed mass of each peak was in good agreement with the theoretical one, which possesses one initiator fragment at the α end and one methoxy group originated from quenching with methanol at the ω end. Thus, detailed end group analysis is possible for poly(VE). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4023–4031, 2000     

Non‐Catalyst Synthesis of Functionalized Biodegradable Polycarbonate

The thermal ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate (BTMC) in bulk in the absence of any catalyst resulted in high molecular weight poly(BTMC) ( = 80 300) and subsequent catalytic hydrogenolysis resulted in functional poly(5‐hydroxyl‐trimethylene carbonate) (PHTMC). Similar spontaneous polymerization of BTMC in the presence of PEG ( = 2 000) as a macroinitiator can provide amphiphilic block polymers. The results revealed that the thermal non‐catalyst (co)polymerization of BTMC is a highly attractive preparative method because of the lack of usage of toxic initiators or catalysts. Furthermore, an evaluation of the degradation and cytotoxicity of PHTMC demonstrated enhanced degradability compared to poly(trimethylene carbonate) and similar toxicity compared to PLGA, showing PHTMC to be a promising biomaterial.

     

Syntheses of Polyethers from Pentafluorobenzonitrile or Pentafluorobenzophenone and Flexible Diphenols

Cyanopentafluorobenzene (CPFB, pentafluorobenzonitrile) or pentafluoro‐benzophenone (PFBP) were polycondensed with long flexible diphenols at a 1∶1 feed ratio in the presence of K₂CO₃. A rather selective substitution of two C‐F groups was achieved with the formation of cyclic polyethers as the main products. Polycondensations of CPFB with flexible diphenols at 3∶2 feed ratio (a₂/b₃) yielded soluble multi‐cyclic polyethers by highly selective substitution of three C‐F groups. Yet, polycondensation at a feed ratio of 5∶2 gave a complex reaction mixture and substitution of all five C‐F groups was not observed. In all experiments, cyclization played a key role for the avoidance of gelation.     

Fusaricidins from Paenibacillus polymyxa M‐1, a family of lipohexapeptides of unusual complexity—a mass spectrometric study

Paenibacillus polymyxa are rhizobacteria with a high potential to produce natural compounds of biotechnological and medical interest. Main products of P . polymyxa are fusaricidins, a large family of antifungal lipopeptides with a 15‐guanidino‐3‐hydroxypentadecanoic acid (GHPD) as fatty acid side chain. We use the P . polymyxa strain M‐1 as a model organism for the exploration of the biosynthetic potential of these rhizobacteria. Using matrix‐assisted laser‐desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS) about 40 new fusaricidins were detected which were fractionated by reversed‐phase (rp) HPLC. Their structure was determined by MALDI‐LIFT‐TOF/TOF fragment analysis. The dominant fragment in the product ion spectra of fusaricidins appeared at m /z 256.3, 284.3 and 312.4, respectively, indicating variations in their fatty acid part. Two new subfamilies of fusaricidins were introduced which contain guanidino‐3‐hydroxyhepta‐ and nonadecanoic acid as fatty acid constituents. Apparently, the end‐standing guanidine group is not modified as shown by direct infusion nano‐electrospray ionization mass spectrometry (nano‐ESI MS). The results of this study suggest that advanced mass spectrometry is the method of choice for investigating natural compounds of unusual diversity, like fusaricidins. Copyright © 2016 John Wiley & Sons, Ltd.