Glycoconjugated polymer: Synthesis and characterization of poly(vinyl saccharide)‐block‐polystyrene‐block‐poly(vinyl saccharide) as an amphiphilic ABA triblock copolymer

Styrene (St) was polymerized with α,α′‐bis(2′,2′,6′,6′‐tetramethyl‐1′‐piperidinyloxy)‐1,4‐diethylbenzene ( 1 ) as an initiator (bulk, [St]/] 1 ] = 570) at 120 °C for 5.0 h to obtain polystyrene having 2,2,6,6‐tetramethylpiperidiloxy moieties on both sides of the chain ends ( 2 ) with a number‐average molecular weight (M_n) of 14,300 and a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.14. 4‐Vinylbenzyl glucoside peracetate ( 3a ) was polymerized with 2 as a macromolecular initiator and dicumyl peroxide (DCP) as an accelerator in chlorobenzene at 120 °C. The polymerization with the [ 3a ]/[ 2 ]/[DCP] ratio of 30/1/1.2 for 5 h afforded a product in a yield of 73%; it was followed by purification with preparative size exclusion chromatography to provide the ABA triblock copolymer containing the pendant acetyl glucose on both sides of the chain ends ( 4a ; M_n = 21,000, M_w/M_n = 1.16). Similarly, the polymerization of 4‐vinylbenzyl maltohexaoside peracetate produced the ABA triblock copolymer containing the pendant acetyl maltohexaose on both side of the chain end ( 4b ; M_n = 31,800, M_w/M_n = 1.11). Polymers 4a and 4b were modified by deacetylation into amphiphilic ABA triblock copolymers containing the pendant glucose and maltohexaose as hydrophilic segment, 5a and 5b , respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3978–3985, 2006     

Novel neodymium (III) isopropoxide‐methylaluminoxane catalyst for isoprene polymerization

A novel catalyst composed of neodymium (III) isopropoxide [Nd(OiPr)₃] and methylaluminoxane (MAO) was examined in isoprene polymerization. The Nd(OiPr)₃‐MAO catalyst proved to be highly effective in heptane even at low [Al]/[Nd] ratios (ca. 30) to give polyisoprene that possessed high cis‐1,4 stereoregularity (> ca. 90%), a high number‐average molecular weight (M_n ～10⁵), and relatively narrow molecular weight distributions (M_w/M_n = 1.9–2.8). The catalyst activity increased with an increasing [Al]/[Nd] ratio from 10 to 80 as well as temperature of aging and polymerization from 0 to 60 °C. The polymerization proceeded in the first order with respect to the monomer concentration. Aliphatic solvents (heptane and cyclohexane) achieved a higher yield and M_n of polymer than toluene as a solvent. The M_w/M_n ratio remained around 2.0, and the gel permeation chromatographic curve was always unimodal, indicating that this system is homogeneous and involves a single active site. The microstructure of polyisoprene was determined by IR, ¹H NMR, and ¹³C NMR. The cis‐1,4 contents of the final polymers stayed in the range of 90–92%, regardless of reaction conditions, indicating the high stability of stereospecificity of the catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1838–1844, 2002     

Intramolecular cyclization in the polymerization of ABx monomers: Approaches to the control of molecular weight and polydispersity in hyperbranched poly(siloxysilane)

Different approaches to control the molecular weight of hyperbranched poly(siloxysilane) have been explored. Because the intramolecular hydrosilylation competitively consumes the vinyl groups of the monomer and other oligomeric intermediates, the conventional single-batch bulk process generally affords polymer with a relatively low molecular weight (M_w = 5000) in ca. 60% yield. We have developed a progressive slow addition process that effectively increases the molecular weight of the final polymers and improves preparation yield by reducing the occurrence of cyclization. Using this gradual growth method, polymers with molecular weights in the range of 6–86,000 (M_w) and polydispersities in the range 2–15 were easily obtained in yields of ca. 70–80%. More importantly, both the molecular weight and the polydispersity could be controlled by changing the rate of addition or the amount of monomer fed. The slower the addition, or the larger the amount of monomer added, the higher the molecular weight and polydispersity of the resulting polymer. In seeded polymerizations, a similar trend was observed with a maximum M_w near 84,000 and a yield of 80%, values that are very significantly higher than those obtained by the single batch process described earlier. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3193–3201, 1999     

Macrocycles IV. Macrocyclic polylactones as bifunctional monomers for polycondensations

Tin containing macrocyclic polylactones were prepared by di-n-butyl-2-stanna-1,3-dioxepane-initiated polymerizations of ε-caprolactone in bulk. The average ring size was varied from 10 to 100 monomer units via the monomer/initiator (M/I) ratio. Addition of terephthaloyl or sebacoyl chloride to the in situ prepared macrocycles yielded polycondensates under elimination of di-n-butyl tin dichloride. The molecular weights increased with the reaction temperature (e.g., 80–140°C) and with the size of the macrocycles. Number-average molecular weights (M_ns) up to 90,000 and polydispersities between 1.65 and 2.0 were obtained. Further polycondensations were conducted with isophthaloyl chloride, 4,4′-biphenyldicarbonylchloride and 4,4′-phenylenebisacryloylchloride. Several polycondensations were performed with macrocyclic poly (δ-valerolactone) and poly (β-D ,L -butyrolactone). In those cases the increase of the molecular weight was lower. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1373–1378, 1998     

Molecular weight dependence of mechanical properties of poly(p,p′-oxydiphenylene pyromellitimide) films

The mechanical properties, i.e., Young's modulus, elongation, and tensile stress, were determined as functions of the molecular weight for films of poly(oxydi-p-phenylene pyromellitimide) prepared by thermal cyclization of the precursor poly(amic acid). The molecular weights of the samples were controlled by the monomer stoichiometry employed for the solution condensation of pyromellitic dianhydride and p,p′-oxydianiline. Weight-average molecular weights were determined by light scattering of the precursor poly(amic acid) as well as the fully cyclized polyimide. The elongation-at-break is most sensitive to the molecular weight, undergoing a rapid increase at M _w ? 8000 and reaching a limiting value of about 60% for M _w > 20,000.     

Randomly branched bisphenol A polycarbonates. I. Molecular weight distribution modeling,interfacial synthesis,and characterization

Randomly branched bisphenol A polycarbonates (PCs) were prepared by interfacial polymerization methods to explore the limits of gel‐free compositions available by the adjustment of various composition and process variables. A molecular weight distribution (MWD) model was devised to predict the MWD, G, and weight‐average molecular weight per arm (M_w /arm) values based on the composition variables. The amounts of the monomer, branching agent, and chain terminator must be adjusted such that the weight‐average functionality of the phenolic monomers (F_OH ) was less than 2 to preclude gel formation in both the long‐ and short‐chain branched (SCB) PCs. Several series of SCB and long‐chain branched PCs were prepared, and those lacking gels showed molecular weights measured by gel permeation chromatography–UV and gel permeation chromatography–LS consistent with model calculations. In SCB PCs, the minimum M_w /arm that could be realized without gel formation depended on both composition (molecular weight, terminator type) and process (terminator addition point, coupling catalyst) variables. The minimum M_w /arm achieved in the low molecular weight series studied ranged from ∼3300 to ∼1000. The use of long chain alkyl phenol terminators gave branched PCs with lower glass‐transition temperatures but a higher gel‐free minimum M_w /arm. SCB PCs where M_w /arm was less than ∼M_c spontaneously cracked after compression molding, a result attributed to their lack of polymer chain entanglements. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 560–570, 2000     

Living carbocationic polymerization. IV. Living polymerization of isobutylene

Truly living polymerization of isobutylene (IB) has been achieved for the first time by the use of new initiating systems comprising organic acetate-BCl₃ complexes under conventional laboratory conditions in various solvents from ?10 to ?50°C. The overall rates of polymerization are very high, which necessitated the development of the incremental monomer addition (IMA) technique to demonstrate living systems. The living nature of the polymerizations was demonstrated by linear M _n versus grams polyisobutylene (PIB) formed plots starting at the origin and horizontal number of polymer molecules formed versus amount of polymer formed plots. DP _n obeys [IB]/[CH₃COOR^t · BCl₃]. Molecular weight distributions (MWD) are very narrow in homogeneous systems (M _w/M _n = 1.2–1.3) whereas somewhat broader values are obtained when the polymer precipitates out of solution (M _w/M _n = 1.4–3.0). The MWDs tend to narrow with increasing molecular weights, i.e., with the accumulation of precipitated polymer in the reactor. Traces of moisture do not affect the outcome of living polymerizations. In the presence of monomer both first and second order chain transfer to monomer are avoided even at ?10°C. The diagnosis of first and second order chain transfer has been accomplished, and the first order process seems to dominate. Forced termination can be effected either by thermally decomposing the propagating complexes or by nucleophiles. In either case the end groups will be tertiary chlorides. The living polymerization of isobutylene initiated by ester. BCl₃ complexes most likely proceeds by a two-component group transfer polymerization.     

SYNTHESIS AND CHARACTERIZATION OF POLY(L-GLUTAMIC ACID-co-L-ASPARTIC ACID)

Poly(amino acid)has been widely utilized in drug delivery,tissue engineering and biomedical materials.The biomaterials based on poly(glutamic acid)are usually modified via copolymerization with other monomers such as L-aspartic acid to improve the uncontrolled degradation rate.The ring-opening homo- and co-polymerization ofγ-benzyl-L-glutamate N-carboxyanhydride(BLG-NCA)andβ-benzyl-L-aspartate N-carboxyanhydride(BLA-NCA)were carried out in solution by using triethylamine(TEA)as initiator.The BLG-NCA homo...     

Titanium complexes of dialkanolamine ligands as initiators for living ring‐opening polymerization of ε‐caprolactone

The titanium complexes with one ( 1a , 1b , 1c ) and two ( 2a , 2b ) dialkanolamine ligands were used as initiators in the ring‐opening polymerization (ROP) of ε‐caprolactone. Titanocanes 1a and 1b initiated living ROP of ε‐caprolactone affording polymers whose number‐average molecular weights (M_n) increased in direct proportion to monomer conversion (M_n ≤ 30,000 g mol^?1) in agreement with calculated values, and were inversely proportional to initiator concentration, while the molecular weight distribution stayed narrow throughout the polymerization (M_w/M_n ≤ 1.2 up to 80% monomer conversion). ¹H‐NMR and MALDI‐TOF‐MS studies of the obtained poly(ε‐caprolactone)s revealed the presence of an isopropoxy group originated from the initiator at the polymer termini, indicating that the polymerization takes place exclusively at the Ti–OⁱPr bond of the catalyst. The higher molecular weight polymers (M_n ≤ 70,000 g mol^?1) with reasonable MWD (M_w/M_n ≤ 1.6) were synthesized by living ROP of ε‐caprolactone using spirobititanocanes ( 2a , 2b ) and titanocane 1c as initiators. The latter catalysts, according MALDI‐TOF‐MS data, afford poly(ε‐caprolactone)s with almost equal content of α,ω‐dihydroxyl‐ and α‐hydroxyl‐ω(carboxylic acid)‐terminated chains arising due to monomer insertion into “Ti–O” bond of dialkanolamine ligand and from initiation via traces of water, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1230–1240, 2010     

Atom transfer radical copolymerization of n‐hexylmaleimide and styrene in an ionic liquid

Dendritic polyarylether 2‐bromoisobutyrates of different generations (Gn‐Br, n = 1–3) as macroinitiators for the atom transfer radical copolymerization of N‐hexylmaleimide and styrene in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, were investigated. The copolymerization carried out in the ionic liquid with CuBr/pentamethyldiethylenetriamine as a catalyst at room temperature afforded polymers with well‐defined molecular weights and low polydispersities (1.18 < M_w/M_n < 1.36, where M_w is the weight‐average molecular weight and M_n is the number‐average molecular weight), and the resultant copolymers possessed an alternating structure over a wide range of monomer feeds (f₁ = 0.3–0.8). Meanwhile, the copolymerization was also conducted in anisole at 110 °C under similar conditions so that the effect of the reaction media on the polymerization could be evaluated. The monomer reactivity ratios showed that the tendency to form alternating copolymers for the two monomers was stronger in ionic liquids than in anisole. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3360–3366, 2002     

Block copolymerization of allene derivatives with 1,3-butadiene by living coordination polymerization with π-allylnickel catalyst

The block copolymerization of allene derivatives (3A–3D) with 1,3-butadiene (2) by [(allyl)NiOCOCF₃]₂ (1) is described. For instance, the living coordination polymerization of phenylallene (3A, 50 equiv) starting from the living poly(2), which was prepared by the polymerization of 2 (160 equiv) by 1, successfully gave a block copolymer of 2 and 3A in high yield. The molecular weight of the block copolymer (4A) in gel permeation chromatography shifted clearly to the higher molecular weight region and kept a unimodal distribution (M_n = 17,400, M_w/M_n = 1.23) in comparison with that of the starting living poly(2) (M_n = 5,600, M_w/M_n = 1.67). The ratio of each segment and the molecular weight of the resulting copolymers could be controlled by the feed ratio of each monomer. The block copolymerization also proceeded successfully by the inverse order of the monomer feeding (i.e., the polymerization of 3A followed by that of 2) to obtain the corresponding block copolymers in high yields. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3916–3921, 1999     

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     

Living ring-opening polymerization of cyclic thiocarbonate

This work deals with the cationic ring-opening polymerization of a cyclic thiocarbonate, 5,5-dimethyl-1,3-dioxane-2-thione (1). The polymerization was carried out with 2 mol% of trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, boron trifluoride etherate, or triethyloxonium tetrafluoroborate as an initiator to afford the polythiocarbonate with the narrow molecular weight distribution (M_n = 11200-31000, M_w/M_n = 1.04-1.15). The molecular weight of the obtained polymer could be controlled by the feed ratio of the monomer to the initiator and increased when the second monomer was added to the polymerization mixture after quantitative consumption of 1 in the first stage, supporting that the cationic ring-opening polymerization of 1 proceeded via a living process.     

Chain‐growth condensation polymerization approach to synthesis of well‐defined polybenzoxazole: Importance of higher reactivity of 3‐amino‐4‐hydroxybenzoic acid ester compared to 4‐amino‐3‐hydroxybenzoic acid ester

Application of chain‐growth condensation polymerization (CGCP) to obtain well‐defined polybenzoxazole (PBO) was examined. CGCP of both phenyl 3‐{(2‐methoxyethoxy)methoxy (MEM‐oxy)}‐4‐(octylamino)benzoate ( 1b ) (para‐substituted monomer) and phenyl 4‐MEM‐oxy‐3‐(octylamino)benzoate ( 3b ) (meta‐substituted monomer) was examined in the presence of metal disilazide base and phenyl 4‐nitro‐ or methylbenzoate 2 as an initiator. Polymerization of the latter monomer, but not the former, afforded polymer with controlled molecular weight based on the feed ratio of monomer to initiator and with a narrow molecular weight distribution. Accordingly, monomer 3c , in which the octyl group on the amino nitrogen of 3b was replaced with a 4‐(octyloxy)benzyl (OOB) group, was polymerized in the presence of lithium 1,1,1,3,3,3‐hexamethyldisilazide (LiHMDS), phenyl 4‐methylbenzoate ( 2b ), and LiCl in THF at 0 °C to yield poly 3c with well‐defined molecular weight (M_n = 4520–9080) and low polydispersity (M_w/M_n ≤ 1.11). Treatment of poly 3c with trifluoroacetic acid simultaneously removed the MEM and OOB groups, affording poly(o‐hydroxyamide) (poly 4 ) without scission of the amide linkages. Cyclodehydration of poly 4 proceeded at 350 °C to yield PBO (poly 5 ), which was insoluble in organic solvents and acids. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1730–1736     

RAFT Polymerization of Styrene in the Presence of 2‐Nonyl‐benzoimidazole‐1‐carbodithioic Acid Benzyl Ester

A novel dithiocarbamate, 2‐nonyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1a ), was synthesized and successfully used in RAFT polymerization of styrene in bulk with thermal initiation. The effect of molar ratio of styrene to RAFT agent on the polymerization was investigated. The linear relationship between ln([M]₀/[M]) and polymerization time indicated that the polymerization was first‐order with respect to monomer concentration. The molecular weights increased linearly with monomer conversion and were close to corresponding theoretical values. The molecular weight distributions (M _w /M _n ) kept very narrow (M _w /M _n <1.1) at a wide range of conversions of 14.2% to 73.3%. The obtained polymer had a strong ultraviolet absorption at 329 nm, which indicated that the 1a moiety remained at the end of polymer chain.     

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.     

6,6′-Bisfunctionalized 2,2′-bipyridines as metallo-supramolecular initiators for the living polymerization of oxazolines

[Cu(I) {6,6′-bis(bromomethyl)-2,2′-bipyridine}₂](PF₆) complexes were used as metallo-supramolecular initiators for the polymerization of 2-oxazolines resulting in defined polymers with a central 6,6′-disubstituted 2,2′-bipyridine unit. The living character of the polymerization was demonstrated with the linear relationship between the weight-average molecular weight M̄_w and the [monomer]/[initiator] ratio as well as in the synthesis of block copolymers. The metal ions could be removed resulting in uncomplexed polymers with a free central metal binding unit.     

Living radical graft polymerization of methyl methacrylate to polyethylene film with typical and reverse atom transfer radical polymerization

Nickel‐mediated atom transfer radical polymerization (ATRP) and iron‐mediated reverse ATRP were applied to the living radical graft polymerization of methyl methacrylate onto solid high‐density polyethylene (HDPE) films modified with 2,2,2‐tribromoethanol and benzophenone, respectively. The number‐average molecular weight (M_n) of the free poly(methyl methacrylate) (PMMA) produced simultaneously during grafting grew with the monomer conversion. The weight‐average molecular weight/number‐average molecular weight ratio (M_w/M_n) was small (<1.4), indicating a controlled polymerization. The grafting ratio showed a linear relation with M_n of the free PMMA for both reaction systems. With the same characteristics assumed for both free and graft PMMA, the grafting was controlled, and the increase in grafting ratio was ascribed to the growing chain length of the graft PMMA. In fact, M_n and M_w/M_n of the grafted PMMA chains cleaved from the polyethylene substrate were only slightly larger than those of the free PMMA chains, and this was confirmed in the system of nickel‐mediated ATRP. An appropriate period of UV preirradiation controlled the amount of initiation groups introduced to the HDPE film modified with benzophenone. The grafting ratio increased linearly with the preirradiation time. The graft polymerizations for both reaction systems proceeded in a controlled fashion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3350–3359, 2002     

Living cationic polymerization of ethyl 2-(vinyloxy)ethoxyacetate: A vinyl ether with an ether and an ester function in the pendant

Ethyl 2-(vinyloxy)ethoxyacetate ( 4 ; CH₂?CH? OCH₂CH₂OCH₂? COOC₂H₅), a vinyl ether having both carboxylic acid ester and oxyethylene unit in its pendant, afforded well-defined living polymers when polymerized by the hydrogen iodide/iodine (HI/I₂) initiating system in toluene at ?40°C. The polymers possessed a narrow molecular weight distribution (M _w/M _n ≤ 1.15), and their molecular weight (M _n) increased proportionally to monomer conversion or the molar ratio of the monomer to hydrogen iodide. The polymer molecular weight also increased upon addition of a fresh feed of the monomer to a completely polymerized reaction mixture. Polymers of high molecular weights (M _n > 5 × 10⁵) and broad molecular weight distributions were obtained by BF₃OEt₂ in toluene at ?40°C. Polymerization rate of 4 with HI/I₂ is ca. 100 times greater than that of the corresponding alkyl vinyl ether, and thus 4 was found to be one of the most reactive vinyl ethers thus far studied. Alkaline hydrolysis of the pendant ester groups of the polymers gave a vinyl ether-based polymeric carboxylic acid 6 with a narrow molecular weight distribution.     

Preparation of monodisperse hydrophilic polyamide by anionic polymerization of bicyclic oxalactam

The preparation of a monodisperse hydrophilic polyamide was achieved in the anionic polymerization of a bicyclic oxalactam, 8-oxa-6-azabicyclo[3.2.1]octan-7-one (abbreviated BOL) with the use of N-benzoyl BOL and potassium pyrrolidonate (2 and 0.5 mol % to BOL, respectively) in dimethyl sulfoxide at 25°C. The number-average molecular weight of the polyamide increased in direct proportion to the monomer conversion, and was consistent with the value calculated from the amounts of the consumed monomer and activator. The molecular weight distribution (MWD) of the polyamide obtained until the middle stage of polymerization (polymerization time, < 10 min; monomer conversion, < 60%) was found to be narrow (M_w/M_n = 1.1). The MWD was gradually broadened in the later stage of the polymerization, which may result from the redistribution of molecular weight of the resulting polyamide not only by the polymerization–depolymerization equilibrium, but also by transamidation between polymer chains.