The hydrogenation of HO-terminated telechelic polybutadienes in the presence of a homogeneous hydrogenation catalyst based on tris(triphenylphosphine)rhodium chloride

The hydrogenation kinetics of multiple bonds in HO-terminated telechelic polybutadienes was investigated using two types of these prepolymers prepared by the anionic and radical polymerization. The rate of addition of hydrogen to the π-bonds of these polydienes in the presence of tris(triphenylphosphine) rhodium chloride as a homogeneous hydrogenation catalyst was determined by the chemical structures of the starting polydienes, their concentration in the solvent, the partial hydrogen pressure, the concentration of the catalyst, and the temperature. The effect of kinetic parameters given above on the rate of hydrogenation reaction can be interpreted in the sense of Wilkinson's reaction mechanism of the hydrogenation of alkenes in the presence of the Rh(I)-complex. Due to the predominant 1,2-structural units, the anionic prepolymer reacted twice as quickly with hydrogen (k = 0.093 mol^?1 dm³ s^?1) compared with the radical prepolymer (k = 0.045 mol^?1 dm³ s^?1). During the hydrogenation of multiple bonds there is a partial loss of hydroxy groups in modified telechelic prepolymers; the extent of this reaction depends on reaction conditions of the hydrogenation reaction.     

Moisture curing kinetics of isocyanate ended urethane quasi‐prepolymers monitored by IR spectroscopy and DSC

The study of the kinetics of the curing of isocyanate quasi‐prepolymers with water was performed by infrared spectroscopy and differential scanning calorimetry. The influence of the free isocyanate content, polyol functionality, and of the addition of an amine catalyst (2,2′‐dimorpholinediethylether) in the reaction kinetics and morphology of the final poly(urethane urea) was analyzed. A second‐order autocatalyzed model was successfully applied to reproduce the curing process under isothermal curing conditions, until gelation occurred. A kinetic model‐free approach was used to find the dependence of the effective activation energy (E_a) with the extent of cure, when the reaction was performed under nonisothermal conditions. The dependence of E_a with the reaction progress was different depending on the initial composition of the quasi‐prepolymer, which reveals the complexity of the curing process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

The synthesis of lactic-acid-based telechelic prepolymers

We have studied how different catalysts and diols affect the properties of low-molecular-weight (M_w (GPC) < 49800 g/mol) lactic-acid-based telechelic prepolymers. The catalysts and diols were tested separately in our previous studies. In this study, we used the best previously tested diols and catalysts together in order to prepare different types of telechelic prepolymers (for example, crystalline or amorphous). All condensation polymerizations were carried out in the melt, using different diols and different catalysts. The prepolymers were characterized by differential scanning calorimetry, gel permeation chromatography, titrimetric methods, and ¹³C nuclear magnetic resonance (¹³C-NMR). According to NMR, the resulting polymers contained less than 1 mol % of lactic acid monomer and less than 5.1 mol % of lactide. Dibutyltindilaurate, like tin(II)octoate, produced quite good molecular weights, but the resulting prepolymers contained exceptionally high amounts of D-lactic acid structures, and, therefore, these prepolymers were totally amorphous. Antimony(III)oxide produced a high-molecular-weight prepolymer when the diol used was aliphatic. Like DBTL, Sb₂O₃ produced amorphous prepolymers, which contained a lower amount of D-lactic acid structures than DBTL prepolymers. 1,8-dihydroxyanthraquinone produced a different kind of chain structure with Ti(IV)bu and Ti(IV)iso because one prepolymer had high crystallinity, and the other showed only a slight crystallinity. Sulphuric acid produced a very high-molecular-weight prepolymer with aliphatic 2-ethyl-1,3-hexanediol; and with aromatic diols, it produced quite good molecular weights, except with 1,8-dihydroxyanthraquinone. High-molecular-weight prepolymers produced with H₂SO₄ also showed high crystallinity; and, according to ¹³C-NMR, they did not contain lactide and D-lactic acid structures. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 67:1011–1016, 1998     

Unvernetzte epoxid-amin-additionspolymere, 16. HPLC-analyse und 13C-NMR-spektroskopie von telechelen (diglycidylether-bisphenol A)-anilin-prepolymeren

Synthesis and properties of telechelic diglycidyletherbisphenol A (DGEBA)-aniline prepolymers with aminoalcohol endgroups are reported. The composition of the prepolymer mixtures obtained by addition polymerization was analyzed by means of HPLC using a LiChrosorb RP-18 column with water/acetonitrile gradient elution mode. The prepolymers represent a series of homologous oligo(aminodiols) 2 , n = (1), 2, 3, 4 ... which are separated into diastereomers. The average value n? depends on the molar ratio of the monomers and is varied between 1,0 and 14,0 resulting in M?_n (vapor pressure osmometry) 500–6000 g · mol^-1. C, H, N elemental analysis and ¹³C-NMR spectroscopy were used to estimate the chemical structure of the prepolymer mixtures.     

The determination of reactive-group functionality from gel point measurements

The usual method of calculating functionality is to divide the molecular weight by the equivalent weight. Because of the uncertainty of molecular weight determinations in the range 1000–20,000 a more precise method is needed. Several authors have published work concerning the determination of the extent of reaction at the gel point through the functionalities of the reactants. It occurred to us that this method could be reversed. We chose Stockmayer's treatment, with some changes, to calculate the average functionality of carboxyl-terminated polybutadiene (CTPB): (P_AP_B)_gel = (f_E ? 1)^?1 (_gE ? 1)^? where f_E and g_E are the weighted average functionalities of all molecules bearing the reactive groups A and B, and P_A and P_B are the fractions of initially present groups that have reacted. Two systems with an epoxide and glycerol as curing agents were investigated. The influence of dilution was investigated. Nonfunctional polybutadiene did not interfere with the accuracy of the determination of carboxyl functionality. By changing the ratio of epoxide to COOH groups from 0.6 to 1.4 it was shown that the calculated functionality remained constant. Weight-average molecular weights for three CTPB samples were calculated from the functionality and the equivalent weight. They were compared with those obtained from intrinsic-viscosity measurements. The precision of the functionality numbers is believed to be ±1%.     

Syntheses and properties of UV-autocurable prepolymers. Semicrystalline urethane-multiacrylates

A series of UV-autocurable urethane-multiacrylate prepolymers, which were semicrystalline and showed melting points in the region of 40–50°C, was synthesized. Also, the effects of curing temperature and acrylic functionality on the structure and properties of the cured films were investigated. These prepolymers are solids and opaque at room temperature. In general, UV curing reactions of solid prepolymers are less efficient when compared with those of liquid prepolymers. UV curing reactions at curing temperatures below the melting point (T_m) of the prepolymers produced semicrystalline urethane-multiacrylate cured films. On the contrary, UV curing reactions above T_m destroyed the crystalline phase of the prepolymers and improved the transparency of the cured films. The films cured below T_m of the prepolymers had higher both breaking strength and Young's modulus, and a higher glass transition temperature (T_g), but a lower elongation at break than those cured above T_m. Such curing temperature effects were attributed to the retention or disappearance of the crystalline structure of the prepolymers during UV curing reaction. At curing temperatures below T_m, an increase in acrylic functionality of the prepolymer resulted in a fast curing rate and a higher crosslinking density of the cured films. Therefore, an increase in acrylic functionality of the prepolymers gave cured films with higher breaking strength and Young's modulus, but a lower elongation at break.     

Developing toughened aromatic polybenzoxazines using thermoplastic oligomers and telechelics,part 1: Preparation and characterization of the functionalized oligomers

The preparation and characterization of three families of thermoplastic oligomers (M_n = 2918–13263 g mol^?1) based on polyarylsulfone (PSU) differing in both molecular weight and terminal functionality and one series of polyarylethersulfone (PES) of different molecular weights is reported. Infrared and nuclear magnetic resonance spectroscopy data support the formation of both the hydroxyl terminated oligomers and conversion (67–89% depending on molecular weight) to the telechelic PSU oligomer bearing reactive benzoxazine groups. Differential scanning calorimetry reveals that the onset of homopolymerization in the telechelic PSU oligomer occurs at around 100°C (peak maximum 125°C at 10 K/min) and rescans show values of the glass transition (for the homopolymers) ranging from 124 to 167°C depending on molecular weight. The influence on the oligomer backbone and terminal functionality is examined using thermal analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40875.     

Aqueous reactive polyurethane prepolymer with poly(ethylene oxide) monomethyl ether side chains for the hydrophilic finishing of poly(ethylene terephthalate) fabrics

In this study, a series of aqueous polyurethane (PU) prepolymers were synthesized with 4,4‐methylene bis(isocyanatocyclohexane), poly(ethylene glycol) or polycaprolactone diol (PCL), methyl ethyl ketoxime, and dispersing centers produced by isophorone diisocyanate, N‐diethanol amine, and poly(ethylene oxide) monomethyl ether (PEO), containing different hydrophobic groups (? CH₃ and ? C₆H₄C₉H₁₉) at the end. The thermal properties of the prepolymers and the characteristics of poly(ethylene terephthalate) (PET)‐treated fabrics were investigated. The glass‐transition temperature was the highest in the CC prepolymer containing a benzene ring (? C₆H₄C₉H₁₉) and a long PEO side chain, and it was the lowest in the CA prepolymer having a longer PEO side chain. The CB prepolymer containing a shorter PEO side chain did not produce a melting point of PEO, although a heat endothermic peak of the PCL crystal appeared. The melting point and enthalpy from PEO of the CA prepolymer were larger than those of the CC prepolymer. With respect to the hydrophilic finishing effects of aqueous PU prepolymers for PET fabrics, the fabric treated with the CB prepolymer had higher add‐on and washing durability than the fabrics treated with the CA prepolymer, which was followed by the CC prepolymer with the lowest, but the opposite trend was found for the hydrophilic properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Curing reaction and product properties of polysulfones terminated with active functional groups

The curing processes of maleimide-terminated polyether sulfone oligomers (M_n from 1100 to 3000) and ethynyl-terminated polysulfone prepolymers (M_n from 2600 to 12000) were investigated by means of DSC. The initial temperature of cure reaction is increased, and the apparent activation energy E_a of cure reaction is decreased as the M_n of the uncured prepolymer increases. On the basis of the T_g changes during the curing process, the kinetics of cure is proposed to be similar to a stepwise reaction, although the curing reaction is believed to proceed via a free radical chain mechanism. In this proposed reaction some initial reaction products with many branches and one remaining active functional group are formed first. The more these products occur, the more likely they can interreact to form a network. During the curing process the mobility of the active end group is restricted by the rigid polysulfone chain. Therefore, the reaction is mainly controlled by the movement of polymer, i.e., by the kinetics of diffusion. Films of these cured polymers were made by casting from solution. Their β relaxation peaks at low temperatures were examined by dielectric and dynamic mechanical measurements. The films made of the prepolymer with M_n > 3000 are flexible and foldable.     

Synthesis and characterization of natural rubber-based telechelic oligomers via olefin metathesis

Metathesis degradation and functionalization of natural rubber (NR) were conducted with 1-hexene, 1-octene, 1-decene, 1-dodecene, trans-stilbene, and 4,4′-dibromo-trans-stilbene as chain transfer agents (CTAs) in presence of Grubbs 2nd generation catalyst to generate NR-based telechelic oligomers that had been a long-lasting challenge due to the structure and compositions of NR with various impurities. Orthogonal experiments were applied and the effects of the CTA type, CTA concentration, catalyst concentration, reaction time, and reaction temperature on the formation of telechelic oligomers were studied, indicating that the catalyst concentration was the major factor influencing the number average molecular weights (M_n) and polymer dispersity index (PDI) of telechelic oligomers. The structures of the oligomers were characterized using ¹H NMR, ¹³C NMR, and MALDI-TOF-MS, which confirmed the formation of the designed terminal groups. The results showed that well-defined telechelic oligomers with a M_n of a few thousand and a PDI around 1.6 were obtained, with potential applications in binder, lubricant and many other fields.     

Synthesis,characterization and crosslinking of functional star‐shaped poly(ε‐caprolactone)

Star‐shaped low molecular weight poly(ε‐caprolactone)s (PCLs) were synthesized and functionalized with crosslinkable terminal groups for subsequent crosslinking. The ε‐caprolactone (CL) prepolymers were polymerized by ring‐opening in the presence of polyglycerine (PGL) as an initiator (1, 3 and 5 mol%) and Sn(II)2‐ethylhexanoate as a catalyst. Characterization of the prepolymer by ¹³C/¹H nuclear magnetic resonance (NMR) spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) revealed a six‐armed star‐shaped structure for the prepolymer with the molecular weight controlled by the ratio of PGL and CL. Functionalization of the hydroxyl‐terminated prepolymer was carried out with maleic or itaconic anhydride. In both cases, the characterization of the functionalized prepolymer showed that the hydroxyl groups were completely substituted. The functionalized PCLs were successfully crosslinked through the reaction of double bonds. The crosslinking was induced either thermally with organic peroxide or photochemically with a photosensitive initiator. Characterization of the crosslinked PCLs by Soxhlet extraction, DSC and FTIR showed that the itaconic double bond was much more reactive in thermal crosslinking than the maleic double bond. Thus, the crosslinked prepolymers that were functionalized with itaconic double bonds achieved a gel content of about 90%. A gel content of 100% was achieved with several compositions where crosslinking agents were employed. © 2002 Society of Chemical Industry     

Allylic prepolymers from brassylic and azelaic acids

Diallyl brassylate (DAB), a new monomer, and diallyl azelate (DAA) were converted to new prepolymers for comparison with analogous commercial products from diallyl o-and m-phthalate (DAMP). Respective prepolymers from DAB and DAA had M?_n 28,000 and 40,000 and contained approximately 0.8 free allyl moiety per repeating unit. Only the DAB prepolymer exhibited crystallinity at low temperatures as detected by differential scanning calorimetry and x-ray diffraction. Aliphatic prepolymers have greater heat stability than aromatic ones and evolve fewer calories per double bond during curing than reported for DAMP prepolymer. Low shrinkage (<1%) on curing and clear, hard end products indicate the potential of aliphatic prepolymers as thermosetting plastics. Their liquid state at room temperature should be advantageous in many applications.     

Rheological behavior of molten epoxide prepolymers

Flow properties of four molten epoxide prepolymers of number average molecular weight 900(I), 1,500(II), 2,100(III) and 4,000(IV), were measured at temperatures ranging from 361 to 463K, and shear rates from 500 to 10,000 s^?1. Apparent shear viscosities showed that all prepolymers used have Newtonian behavior up to shear rates of 2,000 s^?1. Shear thinning occurs at higher shear rates. Flow activation energies at constant shear rates in the range of 500 to 7,000 s^?1 vary for prepolymer III from 5 to 24 kcal/mol, and for prepolymer IV from 9 to 25 kcal/mol. Flow indices in the same shear rate range vary for prepolymer III from 1.0 to 0.7 and for prepolymer IV from 1.0 to 0.3.     

Cyanuric acid–epichlorohydrin prepolymers

In this study, we investigated the reaction of cyanuric acid and epichlorohydrin (ECH). SnCl₄ was used as a catalyst. Several reaction conditions were tested, and the products were analyzed by means of Fourier transform infrared and ¹H‐NMR spectroscopy, hydroxyl group content, molar mass, elemental and thermal analysis, viscosity, and density. ECH reacted with the amine groups of the cyanuric acid ring to form lateral chains that contained chloroalkyl and hydroxyl end groups. Full substitution of the amine groups was observed in all of the synthesized products. The solvent used in the synthesis was found to be very important for the structure of the final prepolymers. When N,N‐dimethylformamide was used, relatively low‐molar‐mass prepolymers of cyanuric acid and ECH were obtained. When solvents with low dielectric constants were used, no reaction with cyanuric acid was observed. The prepared prepolymers were thermally stable up to 160°C. At this temperature, degradation started via the lateral chains. The viscosity of the products decreased as the ECH–cyanuric acid ratio increased, whereas the density remained basically constant. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3684–3691, 2006     

Effects of functionality and temperature on gel points in random polymerisation

First, the relationship between gel point and average functionality for an RA₂+R′B_f type polymerisation has been investigated by measuring the product of extents of reaction at gelation (α_c) for sebacoyl chloride (SC)/polyoxyproplyene (POP)diol/POP triol mixtures reacting at various initial dilutions in diglyme as solvent at 60°C. Intramolecular reaction always delays gelation and a generalisation of the Ahmad-Stepto gel point expression has been used to interpret the gelation data in terms of the ring-forming parameter λ′_ab. From the variation of λ′_ab with initial dilution, values of b, the effective bond length of the chain forming the smallest ring structure, have been derived. It is found that b decreases with average polyol functionality (f_w). This decrease apparently compensates for the increase in λ′_ab with f_w, so that ring formation is less sensitive to functionality than may have been expected. It is found that the Ahmad-Stepto expression does not predict a consistent relationship between λ′_ab, f_w and the gel dilution of reactive groups. Second, the effect of temperature on the gel point has been studied by measuring α_c for SC/POP triol mixtures reacting at various initial dilutions in diglyme as solvent at 27° C, 40° C and 60° C. At a given temperature, b decreases as triol molar mass increases, indicating that the POP residue of the chain forming the smallest ring structure is more flexible than the SC residue. This result is in keeping with those from previous investigations,^1,2 For a given triol, α_c decreases as temperature increases, indicating an increase in chain stiffness with temperature. Values of d In <r²>/dT are derived and found to be larger than those for linear chains.     

New aspects of unsaturated polyester resin synthesis. Part 2. Reactant sequence distribution and its effect on cure kinetics

The distribution of unsaturations in the prepolymer of a typical unsaturated polyester (UP) resin (maleic anhydride, phthalic anhydride and 1,2‐propylene glycol) has been shown to influence the kinetics of the cure process with styrene monomer. Segments containing double bonds in close proximity appear to lower the reactivity of the resin due to steric hindrance, as indicated by the fact that the rate of cure and the final degree of cure, measured by differential scanning calorimetry (DSC), increase as the average sequence length (SL) of maleic units decreases. This implies that the reactivity of UP resins may be improved by synthesis of prepolymers with certain reactant sequence‐length distributions. The copolymer formed by the melt condensation process of maleic anhydride, phthalic anhydride and 1,2‐propylene glycol in the absence of a transesterification catalyst has a non‐random structure with a tendency towards blockiness. This was established using ¹H NMR analysis in tandem with deterministic and Monte Carlo modelling techniques. Copyright © 2003 Society of Chemical Industry     

The effect of prepolymer crystallinity on solid-state polymerization of poly(bisphenol A carbonate)

The effect of prepolymer crystallinity on the solid-state polymerization (SSP) of poly(bisphenol A carbonate) was examined using nitrogen as a sweep fluid. A low-molecular-weight prepolymer was synthesized by melt transesterification and prepolymers with different crystallinities (11.7%, 23.3%, 33.7%) were prepared with supercritical carbon dioxide treatment. SSP of the three prepolymers was then carried out at reaction temperatures in the range of 150-190 °C, with a prepolymer particle size of 75 μm and a N₂ flow rate of 1600 ml/min. The glass-transition temperature (T_g), absolute weight-average molecular weight (M_n), and percent crystallinity were measured at various times during each SSP. At each reaction temperature, SSP of the lower crystallinity prepolymer (11.7%) always resulted in higher-molecular-weight polymers, compared with the polymers synthesized using the higher crystallinity prepolymer (23.3% and 33.7%). The crystallinity of the polymers synthesized from the high crystallinity prepolymer was significantly higher than for those synthesized from the low crystallinity prepolymer. Higher crystallinity of the prepolymer and the synthesized polymers may lower the reaction rate by reducing chain-end mobility or/and by inhibiting byproduct diffusion.     

Unsaturated polyesters based on terephthalic acid: 3. Characterization of poly(propylene terephthalate) prepolymer by gel permeation chromatography

Oligomers in prepolymers prepared by the polyesterification of terephthalic acid (T) with excess 1,2-propylene glycol (P) have been separated by gel permeation chromatography (g.p.c.). The assignment of chromatogram peaks to oligomers according to the structure P (TP)_n where n is the number of 1,2-propylene terephthalate repeating units has been confirmed by a g.p.c. examination of bis(2-hyroxypropyl) terephthalate and by a ¹H nuclear magnetic resonance (n.m.r.) spectroscopic study of fractions isolated from a preparative separation. The infrared g.p.c. detector response has been interpreted quantitatively in order to deduce the concentration of each oligomer from the area of its chromatogram peak. Mol fraction distributions as a function of n have been determined for the prepolymer samples. Number average molecular weights have been calculated for the terephthalate-based components of the prepolymer and for all components including excess propylene glycol. These g.p.c. molecular weights are in excellent agreement with values previously reported in a study of prepolymers by ¹H n.m.r. spectroscopy. G.p.c. studies on prepolymers after reactions with a carbodiimide and diazomethane suggest a very minor quantity of carboxyl terminated species in the prepolymer samples.     

Exploration of the difference of reaction rates for polyester and polyether urethane prepolymers with 3,3′-dichloro-4,4′-diaminodiphenylmethane

Polyester (PEPA) and polyether (PTMO) prepolymers with NCO end groups were synthesized. The chain extension reaction of these prepolymers with MOCA diamine was studied by FTIR spectrometry and found to be a second-order reaction. Data on chain extension reaction rate constants and activation energy showed that the chain extension reaction rate of the PEPA prepolyme with MOCA was faster than that of PTMO prepolymer with MOCA. Such a difference of chain extension reaction rate for PEPA and PTMO prepolymers with MOCA can be explained by hydrogen bonding interaction and miscibility between hard and soft segments in the cast polyurethane elastomer. The hydrogen bonding interactions of MOCA with PEPA prepolymer and PTMO prepolymer without chain extension reaction convincingly demonstrated the difference of chain extension reaction in the polyurethane-urea systems. © 1995 John Wiley & Sons, Inc.     

Formation of poly(urethane-isocyanurate) networks from poly(oxypropylene)diols and diisocyanate

Summary Reaction conditions leading to the smallest amount of unreacted isocyanate groups for the preparation of poly(urethane-isocyanurate) networks based on 2,4-tolylene diisocyanate and ,-dihydroxypoly(oxypropylene) (M _n = 425–) were found. A tertiary amine, POLYCAT^* 41, was used as a cyclotrimerization catalyst. The networks were prepared by prepolymer two-stage technique. The content of isocyanate groups in the prepolymers and networks was determined by potentiometric titration. Model reactions in 1,4-dioxane were used for the estimation of possible reaction intermediates during poly(urethane-isocyanurate) synthesis.