Telechelic diene prepolymers. III. Polymerization temperature study of polybutadienes

A study of the effect of the polymerization temperature on the yield and properties of hydroxyl- and carboxyl-terminated polybutadiene prepolymers has been made. Polymerization reactions were conducted in dioxane with 4,4′-azobis(4-cyano-n-pentanol) and 4,4′-azobis(4-cyanovaleric acid) as the free-radical initiators. The most significant result obtained was the observation that the polymerization temperature exhibited a pronounced effect on the heterogeneity index of the prepolymers.     

Solid state polymerization of poly(lactic acid): Some fundamental parameters

Poly(lactic acid) (PLA) was submitted to solid state polymerization (SSP) in a fixed bed reactor under nitrogen flow, so as to examine technique efficiency for increasing the molecular weight and hence permitting the reduction of the melt polymerization residence times. In order to use a suitable starting material, SSP prepolymers of low and medium molecular weight were first prepared through solid state hydrolysis of commercial PLA grade under acidic and alkaline conditions. During these degradation runs, hydrolysis involved the random scission of ester groups in the polymer backbone, while the relevant kinetics and the resulting thermal properties were also examined. In a subsequent step, the prepolymers obtained were subjected to SSP at three temperatures, approximately 2.5–25.0 °C below their melting point. The process achieved an increase of up to 1.7 times the initial molecular weight, however, with different trends depending on the prepolymer characteristics, reaction temperature and time, as well as the pH of the hydrolysis medium. In addition to molecular weight build up, the effect of the SSP process on end product thermal properties was also investigated.     

Synthesis and properties of poly(sulfone‐arylate) copolymers

Poly(sulfone‐arylate) was synthesized in a reaction between dihydroxy polysulfone prepolymers and either diphenyl terephthalate or terephthaloyl chloride. The dihydroxy polysulfone prepolymers had molecular weights of 2000 and 4000 g/mol. The polymerization with diphenyl terephthalate was carried out at high temperature (280 °C) in the presence of a catalyst, whereas the polymerization with terephthalic chloride was conducted in solution at low temperature in the presence of an acid acceptor. High‐molecular weight copolymers (η_inh ～ 0.60 dL/g) could be obtained through both methods. The copolymers were characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance, DMA, and differential scanning calorimetry measurements and were found to exhibit high T_g values. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3904–3913, 2009     

Telechelic diene prepolymers. I. Hydroxyl-terminated polydienes

Telechelic prepolymers of butadiene, isoprene, and chloroprene with hydroxyl end- groups have been prepared by the solution polymerization of the dienes under free-radical initiation. 4,4′-Azobis(4-cyano-n-pentanol) was employed as the initiator. Liquid prepolymers were obtained with molecular weights of 2000 to 20,000 and with functionalities usually greater than 2. The preparative procedure and prepolymer characterization are described.     

SYNTHESES AND STRUCTURES OF POLYPHENYLSILSESQUIOXANES

Phenyltrichlorosilane was hydrolyzed both ifi. toluene and in ether from which two kinds of prepolymers were obtained with different structures, molecular weights, and molecular weight distributions. Polymers were prepared from the prepolymers in various polymerization conditions. The ladderlike, branched, and crosslinked structures formed under different polymerization conditions were characterized by means of FTIR, ~1H and ~(29)Si-NMR, and elemental analysis. Azeotropic distillation of solvents and H_2O formed during polymerization was found useful in removing H_2O from the system and high molecular weight products with perfect ladderlike structure were obtained.     

Kinetic study of the polymerization of aromatic polyurethane prepolymers by high‐throughput experimentation

In this contribution, high‐throughput screening experiments are reported to study the polymerization of different aromatic polyurethane (PU) prepolymers. The prepared prepolymers were synthesized from toluene diisocyanate (T80) with different molar mass polyether diols and polyether triols, respectively. The reactions were performed in solution using a Chemspeed Accelerator? SLT106 automated parallel synthesizer as well as in bulk to evaluate the high‐throughput approach for this kind of prepolymers. More than 100 samples were prepared and characterized by GPC within 1 week labor time to investigate the reaction kinetics and to compare the resulting trends obtained by high‐throughput experimentation (HTE) or by conventional, bulk prepolymerization. The synthesis of the prepared prepolymers with a linear (T80‐Diol) or a branched (T80‐Triol) structure followed a second‐order kinetic in solution but showed deviation from this phenomenon in bulk under the selected reaction conditions, although the same trends are observed in both cases. The calculation of the rate constants allowed comparing the reactivity of different prepolymer systems, which could have a significant influence on the industrial application and processing of these materials. As a result, the HTE approach was found to represent a powerful tool for the kinetic studies of PU prepolymers. Moreover, in spite of the complexity of the curing process, the results obtained by high‐throughput solution polymerization can be applied for evaluating the bulk polymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 570–580, 2010     

Synthesis and characterization of poly(L‐lactide‐co‐ε‐caprolactone) (B)‐poly(L‐lactide) (A) ABA block copolymers

ABA triblock copolymers of L ‐lactide (LL) and ε‐caprolactone (CL), designated as PLL‐P(LL‐co‐CL)‐PLL, were synthesized via a two‐step ring‐opening polymerization in bulk using diethylene glycol and stannous octoate as the initiating system. In the first‐step reaction, an approximately 50:50 mol% P(LL‐co‐CL) random copolymer (prepolymer) was prepared as the middle (B) block. This was then chain extended in the second‐step reaction by terminal block polymerization with more L ‐lactide. The percentage yields of the triblock copolymers were in excess of 95%. The prepolymers and triblock copolymers were characterized using a combination of dilute‐solution viscometry, gel permeation chromatography (GPC), ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry (DSC). It was found that the molecular weight of the prepolymer was controlled primarily by the diethylene glycol concentration. All of the triblock copolymers had molecular weights higher than their respective prepolymers. ¹³C‐NMR analysis confirmed that the prepolymers contained at least some random character and that the triblock copolymers consisted of additional terminal PLL end (A) blocks. From their DSC curves, the triblock copolymers were seen to be semi‐crystalline in morphology. Their glass transition, solid‐state crystallization, and melting temperature ranges, together with their heats of melting, all increased as the PLL end (A) block length increased. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of well‐defined multigraft copolymers by a two‐step living radical polymerization with nitroxyl‐functionalized poly(methyl methacrylate)

Novel multigraft copolymers of poly(methyl methacrylate‐graft‐polystyrene) (PMMA‐g‐PS) in which the number of graft PS side chains was varied were prepared by a subsequent two‐step living radical copolymerization approach. A polymerizable 4‐vinylbezenyl 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) monomer (STEMPO), which functioned as both a monomer and a radical trapper, was placed in a low‐temperature atom transfer radical polymerization (60°C) process of methyl methacrylate with ethyl 2‐bromopronionate (EPNBr) as an initiator to gain ethyl pronionate‐capped prepolymers with TEMPO moieties, PMMA‐STEMPOs. The number of TEMPO moieties grafted on the PMMA backbone could be designed by varying STEMPO/EPNBr, for example, the ratios of 1/2, 2/3, or 3/4 gained one, two, or three graft TEMPO moieties, respectively. The resulting prepolymers either as a macromolecular initiator or a trapper copolymerized with styrene in the control of stable free‐radical polymerization at an elevated temperature (120 °C), producing the corresponding multigraft copolymers, PMMA‐g‐PSs. The nitroxyl‐functionalized PMMA prepolymers produced a relatively high initiation efficiency (>0.8) as a result of the stereohindrance and slow diffusion of TEMPO moieties connected on the long PMMA backbone. The polymerization kinetics in two processes showed a living radical polymerization characteristic. The molecular structures of these prepolymers and graft copolymers were well characterized by combining Fourier transform infrared spectroscopy, gel permeation chromatography, chemical element analysis, and ¹H NMR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1876–1884, 2002     

A raman LAM study of lamellar thickness of virgin polyethylene powder

The lamellar thickness of polyethylene virgin reactor powder has been successfully measured using the Raman longitudinal acoustic mode (LAM). Relatively high lamellar thicknesses have been found. These values change with polymerization temperature in an unusual way, with lamellar thickness being larger for lower polymerization temperature, i.e., at higher undercooling for crystallization. Agreement within an experimental error of 10% has been obtained between values from LAM and those calculated by the Thompson—Gibbs equation from the melting point measured by differential scanning calorimetry.     

Synthesis and hydrolysis behaviour of poly(ester anhydrides) from polylactone precursors containing alkenyl moieties

Hydroxyl-group functional polylactones were prepared and converted to acid- terminated polyesters in a reaction with a series of alkenylsuccinic anhydrides containing 8, 12, or 18 carbons in their alkenyl chains. These polyester precursors were then linked into higher molecular weight poly(ester anhydrides) containing alkenyl moieties in their polyester blocks. The hydrolysis behaviour of the poly(ester anhydrides) was found to depend on the thermal properties of the polyester precursors. For poly(ester anhydrides) prepared from low molecular weight prepolymers with thermal transitions below 37 degrees C, the presence of hydrophobic alkenyl chains in the polyester precursors slowed the rate of weight loss. Poly(ester anhydrides) prepared from higher molecular weight prepolymers showed the opposite weight-loss behaviour; i.e., the crystallinity and thermal transitions of the alkenyl chain-containing poly(ester anhydrides) were low, and the weight loss was faster than for poly(ester anhydrides) without the alkenyl chains. The differences in length of the alkenyl chain, as such, had little effect on the hydrolysis behaviour and thermal properties of the poly(ester anhydrides).     

Curing process of phenol-urea-formaldehyde-tannin (PUFT) adhesives

Summary Phenol-urea-formaldehyde-tannin (PUFT) adhesives have been prepared by copolymerization at room temperature of pine bark tannins with phenol-urea-formaldehyde (PUF) prepolymers prepared under varying operating conditions. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have been used to analyse the curing of prepolymers and adhesives. DSC curves were obtained at three different heating rates and, by means of the Model Free Kinetics isoconversional method, chemical conversion vs. time at a given temperature was obtained. Mechanical conversion was calculated from DMA storage modulus data for those adhesives which gave the best results for plywood and MDF boards.     

Soluble and curable prepolymers from polyallyl ester monomers containing aromatic imide groups

Five polyallyl ester monomers that contain aromatic imide groups were synthesized as thermally stable laminating resins. From these monomers soluble and low-melting prepolymers were obtained by radical polymerization in aprotic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, or N-methyl -2-pyrrolidone. The prepolymers are oligomeric compounds in which DP = 3–6 and have lower melting points than the corresponding monomers. It is assumed that the reaction of solvent molecule participates in the polymerization. Whereas, the bulk and the solution polymerization in n-butyl acetate or n-propyl alcohol yielded insoluble and infusible polymer. The relatively low-melting prepolymers were curable at 150–180°C without the evolution of volatile by-products. Resulting glass-fiber laminates have no glass transition point below 300°C and thermooxidative stability at 330°C.     

Preparation of a graded‐index polymeric preform by swollen bulk polymerization

A swollen bulk polymerization approach for the preparation of a preform for manufacturing graded‐index plastic optical fibers was examined. The preform prepared by the proposed approach was transparent and bubble‐free and had a parabolic profile of the refractive index, with the highest refractive index at the center of the rod. The influences of the polymerization temperature and the type of dopant on the properties of the prepared preform were discussed. A higher temperature resulted in a steeper parabolic profile of the refractive index for the formed preform, and a lower temperature resulted in a higher refractive index near the core‐cladding region of the preform. The refractive‐index profiles of the preform were affected by the addition of the different types of dopants used. The concentration distribution of the dopant in the preform correlated to the refractive‐index distribution. In a comparison of bromobenzene (BB) and 1,2,4‐trichlorobenzene (TB) as dopants, it was observed that BB distributions along the profile were more uniform than TB distributions, and a dopant with a larger molecular volume was more concentrated in the core center. It was concluded that the refractive‐index distribution of the graded‐index preform could be controlled by the both temperature and the addition of different types of dopants during the swollen bulk polymerization process. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1813–1818, 2003     

高性能自修复微胶囊预聚物组成的研究

为了指导高性能自修复微胶囊的制备研究, 利用偏光显微熔点仪、红外光谱和核磁共振氢谱定量研究了微胶囊预聚物组成随反应条件如反应温度、pH 值和甲醛-尿素物质的量比的变化. 研究结果表明, 升高体系温度和pH 值都会显著促进副反应的发生从而降低产物中二羟甲基脲的产率; 而提高甲醛-尿素的物质的量比, 二羟甲基脲的产率增加,同时三羟甲基脲的产率降低. 此外, 还研究了升温过程中反应体系的温度变化情况. 研究发现: 升温速率一定时, 反应体系的温度变化均匀, 没有温度骤变阶段.     

Polymerization of 1,3,5-trithiane in the solid state initiated by UV-irradiation. I. Polymerization conditions and polymer characterization

The solid-state 1,3,5-trithiane polymerization initiated by UV-irradiation was studied at various irradiation times and various polymerization temperatures. The conversion of monomer to polymer reaches limiting values (at longest) in about 30 min of reaction. The apparent activation energy of this process is somewhat higher than in the chemically initiated polymerization. Generated by UV, active centers, which initiate the polymerization, are stable. On the basis of X-ray diffraction studies it was found that the prepared polythiomethylene has a hexagonal structure and high degree of crystallinity. In the polymer investigated, a new additional crystal phase is formed, which is not stable.     

Poly(urethane‐co‐benzoxazine)s via reaction of phenol terminated urethane prepolymers and benzoxazine monomer and investigation of their properties

In the present work, a new method was developed for the combination of polyurethanes (PUs) and polybenzoxazine (PBz) to obtain novel thermoset poly(urethane‐co‐benzoxazine)s with good thermal, mechanical, and electrical properties as well as low temperature curing profile. Knowing the catalytic effect of compounds possessing free phenolic groups on ring opening polymerization of benzoxazine monomers, preparation of phenol terminated urethane oligomers (PTPU) as the macroinitiator for a benzoxazine monomer (Ba) was considered. Firstly, NCO‐terminated urethane prepolymers were prepared from the reaction of poly(tetramethyleneether glycol), and 2,4‐tolylene diisocyanate, and then end functionalized with bisphenol‐A under proper condition. DSC, DMTA, and gel content measurements were applied to find optimum ring opening polymerization condition (170°C for 1 hr and 200°C for 15 min). Various kinds of thermoset polymers were prepared by the reaction of PTPU at different molecular weights with variable contents of Ba. All of monomeric and polymeric materials were characterized by conventional spectroscopic methods and their thermal, mechanical, viscoelastic, and electrical properties were measured and properties were correlated to their structure. Due to the interesting properties of these new materials, the possibility of using them as electrical insulators with higher service temperature in comparison to common PUs were examined and their potential applicability was confirmed. Copyright © 2010 John Wiley & Sons, Ltd.     

From hydroxyurethane methacrylates to hybrid nonisocyanate polyurethanes

New hybrid polyhydroxyurethane networks were quantitatively synthesized by radical polymerization of new hydroxyurethane methacrylate (HUMA) prepolymers. These HUMAs were synthesized in several steps. First, bis(cyclic carbonate) poly(propylene oxide) was reacted with two different diamines (ethylene diamine and 2,2′‐(ethylenedioxy)diethylamine) in excess. Then, these end‐functionalized hydroxyurethane prepolymers were converted into end‐functionalized hydroxyl prepolymers by ring opening of ethylene carbonate. Finally, a methacrylate function was grafted to the hydroxyl functions. All these steps were performed at room temperature. These prepolymers were thermally either homopolymerized or copolymerized using benzylmethacrylate or poly(ethylene oxide) bisphenol A dimethacrylate as comonomers, leading to new hybrid nonisocyanate polyurethane networks with various properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Polymerization and self‐assembly of thermally responsive in‐chain functionalized double‐hydrophilic macromonomers

Double‐hydrophilic in‐chain functionalized macromonomers consisting of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) were prepared by a multistep procedure including esterification of PNIPAM monoester of maleic acid with α‐methoxy‐ω‐hydroxypolyoxyethylene or its amidation with α‐methoxy‐ω‐aminopolyoxyethylene. The polymerization of the macromonomers was carried out in aqueous solutions. The temperature was the key parameter controlling the polymerization process that was performed in the organized domains formed by the macromonomers below and above the phase transition temperature (T_tr). Polymacromonomers with higher degrees of polymerization were prepared at temperatures just below the T_tr. Static light scattering measurements on dilute aqueous solutions of thermally‐responsive macromonomers and their polymerization products demonstrated that they formed aggregates below the T_tr. Supramolecular structures with low density cores, formed by the polymacromonomers at room temperature, were imaged by SEM. Morphological tuning was achieved by varying both the composition of the copolymer and the concentration of the aqueous solution. The rheological behavior of the polymacromonomers in 25 wt % aqueous solution was compared to that of the respective macromonomers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4720–4732, 2007     

Comparative rheological study of ionic semi-IPN composite hydrogels based on polyacrylamide and dextran sulphate and of polyacrylamide hydrogels

Ionic semi-interpenetrating polymer networks composite hydrogels were synthesized by free-radical polymerization using dextran sulphate (DxS), acrylamide as monomer and N,N′-methylene(bis)acrylamide as cross-linking agent. The viscoelastic properties of these composite hydrogels were investigated by oscillatory shear measurements under small deformation conditions comparative with those of polyacrylamide gels. Changes of the rheological properties of composite hydrogels have been studied in terms of polymerization temperature, cross-linker ratio, initial monomer concentration and molar mass of DxS. The results showed that the stability of the composite hydrogels obtained at room temperature (22?°C) was relatively low because the storage modulus (G′) was only eight times higher than the loss modulus (G″), while for those obtained by cryopolymerization (?18?°C), the stability was improved, the G′ values being about 30 times higher than those of G″. This behaviour indicated that, by conducting the synthesis of hydrogels below the freezing point of the reaction solutions, an enhancement of the hydrogels elasticity was achieved. The network parameters, i.e. the average molecular weight between two cross-links and the cross-link density of the composite hydrogels prepared at ?18?°C, were estimated from rheological data.     

聚合反应条件对渐变型塑料光纤预制棒的折射率分布的影响

用甲基丙烯酸甲酯 (MMA)作为基质 ,采用界面 凝胶聚合技术成功地制备了渐变型塑料光纤预制棒 ,并探讨了掺杂剂浓度及其分子体积以及聚合温度对折射率分布的影响 .观察到聚合温度对折射率分布的影响以及掺杂剂分子的分子体积在极端情况下 (如溴苯与MMA分子的分子体积相似 ,联苯分子体积比MMA则要大的多 )对折射率分布的影响 ,清楚地显示出分子体积在界面 凝胶聚合过程中所起的重要作用 .实验结果表明了高温聚合有利于轴心Δn值的升高 ,可得数值孔径NA较大的预制棒 .低温聚合使得折射率分布趋于平缓化 .