Toward an understanding of the role of water‐soluble oligomers in the emulsion polymerization of styrene–butadiene–acrylic acid. Function of carboxylic acid

In a further effort to understand the role of water‐soluble oligomers formed during the emulsion terpolymerization of styrene/butadiene/acrylic acid (St/Bu/AA), the reaction temperature, initiator concentration, and ionic strength were varied and the kinetics and resulting oligomers were characterized as a function of reaction time. The rate of polymerization (R_p) was observed to increase with increasing temperature and initiator concentration; the reasons for this vary. The increase in R_p with increasing initiator concentration is mainly attributed to the increase in the number of oligomeric radicals formed and, subsequently, the resulting number of particles (N_p). Increasing the temperature increases the water solubility of both monomers and polymers, which results in changes in the composition and molecular weight of the oligomeric radicals being formed. The primary reaction locus in the St/Bu/AA system was noted to shift to the aqueous phase after most of the styrene and butadiene had reacted, based on the unreacted AA profile. The role of water‐soluble oligomers (both oligomeric radicals and dead oligomers) during the emulsion polymerization of St/Bu with acrylic acid can be described by three periods: (1) particle generation and (2) before and (3) after the critical surface saturation concentration (CSSC) is reached during the particle growth period. The incorporation of AA monomer into the oligomer chains after the CSSC may cause destabilization of the latexes through a bridging flocculation mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1988–1999, 2003     

Properties of syndiotactic-rich poly(vinyl alcohol) thin film in water. V. Effect of initial temperature of heating on elongation

The effect of the initial temperature of heating on the elongation of syndiotactic-rich poly(vinyl alcohol) thin films was investigated in water under a load. The elongation ratios E_i after 4 h at fixed temperatures increased roughly with an increase in the initial temperature T_i and a decrease in the annealing temperature. E_i after 4 h was the smallest at T_i = 45°C for the films annealed at temperatures below 100°C. E_i was 6.8 at T_i = 60°C for the unannealed film and 1.12 at T_i = 70°C for the film annealed at 200°C. The elongation at break decreased and the temperature at break increased with an increase in annealing temperature, but those at the annealing temperature of 100°C were the smallest. The films annealed at 200°C did not break even at 98°C (boiling temperature) in water and the elongation ratio was 1.42–1.97 in the initial temperature range of 10–70°C. From these results, the relation between the elongation in water and the state of polymer chains in film was discussed.     

Remarkable improvement of thermal stability of main‐chain benzoxazine oligomer by incorporating o‐norbornene as terminal functionality

A new main‐chain benzoxazine oligomer with o‐norbornene functionality as end groups has been designed and synthesized. As compared to traditional main‐chain type benzoxazine polymers, this benzoxazine oligomer with o‐norbornene terminal functionality can undergo further crosslinking polymerization after general ring‐opening polymerization of oxazine rings. Another main‐chain benzoxazine oligomer has also been designed based on the reaction of bisphenol‐A, 4,4′‐diaminodiphenylmethane, paraformaldehyde, and phenol for comparison. The structure of the synthesized oligomers is confirmed by ¹H nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FTIR). The molecular weight has been determined by using gel permeation chromatography (GPC). The benzoxazine oligomer containing o‐norbornene functionality can polymerize with multiple polymerization mechanisms rather than the single mechanism common to traditional 1,3‐benzoxazine resins. The polymerization mechanisms are monitored by in situ FTIR and differential scanning calorimetry (DSC). Moreover, the thermoset derived from the benzoxazine oligomer containing o‐norbornene functionality exhibits high thermal stability with the transition temperature of 360 °C and a high T_d5 of 404 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45408.     

Study of siloxane-modified epoxy resin using thermally stimulated current(II)

Thermally stimulated current (TSC) and relaxation map analysis (RMA) was used to characterize the low temperature relaxation of epoxy resin modified with siloxane oligomers. In aminopropyl-terminated siloxane oligomer (ATSO) the β-relaxation of epoxy resin and the glass transition temperature of siloxane oligomer were folded regardless of the concentration of diphenyl. The β-relaxation of epoxy resin and the glass transition temperature of oxiranylmethoxy-terminated siloxane oligomer (OTSO) were folded and shifted to higher temperature as the concentration of diphenyl in siloxane oligomer increased. In the systems containing of diphenyl in siloxane oligomer a new relaxation peak due to the space charge was observed in the range of − 80 °C to − 50 °C and − 30 °C to 5 °C. As the concentration of diphenyl increased the compensation temperature (T_c) and the degree-of-disorder (DOD) were increased while the compensation time, τ _c was decreased. Received: 26 May 1997/Accepted: 27 June 1997     

Gas transport properties in (6FDA‐RTIL)‐(6FDA‐MDA) block copolyimides

This article reports synthesis and structure property studies of block copolyimides synthesized using diamino room temperature ionic liquids (RTIL) as diamine monomers. Specifically, polyimide oligomers of different lengths were synthesized using 2,2‐bis (3,4‐carboxylphenyl) hexafluoropropane dianhydride (6FDA) and diamino RTIL (1,3‐di(3‐aminopropyl) imidazolium bis[(trifluoromethyl) sulfonyl] imide). These oligomers were copolymerized with 6FDA and m‐phenylenediamine (MDA) using in situ polymerization to form (6FDA‐RTIL)‐(6FDA‐MDA) block copolyimides. The impact of the length and relative concentration of 6FDA‐RTIL oligomer in the copolymer on the resulting thermal, physical, and gas transport properties was monitored. As the concentration of the 6FDA‐RTIL segments increased, the backbone of the block copolyimides became more flexible resulting in a decrease in the glass transition temperature (T_g) and an increase in the density. The permeabilities of the RTIL containing copolyimides were consistently lower than those of the base polyimide, 6FDA‐MDA, with some increase in selectivities. Interestingly, the permeabilities of films produced with the low molecular weight oligomers were very different than those produced with same composition of the high molecular weight oligomers. This may be indicative of very different morphologies within these copolyimides. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43077.     

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane initiated by potassium isopropoxide

Kinetics of the anionic ring‐opening polymerization of octamethylcyclotetrasiloxane (D₄) in bulk initiated by potassium isopropoxide was studied. Several promoters including N‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and diglyme were used. It is indicated that the reactions are first‐order in D₄ during the initial stage of polymerization. The polymerization rate of D₄ is influenced by a number of factors, such as the nature of promoters, the molar ratio of promoter to initiator (C_p/C_i ratio), and the reaction temperatures. With the use of NMP as promoter, the polymerization rate constant at 30°C is 10.482 h^?1 with the C_p/C_i ratio equal to 3.0. As the C_p/C_i ratio increases, the polymerization rate constant increases sharply and the cyclic oligomers content in polymer decreases evidently. The back‐biting reaction that leads to the formation of decamethylcyclopentasiloxane (D₅) occurred in the polymerization of D₄. The rate of the D₅ formation relatively to the rate of D₄ conversion increases with the conversion of D₄. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3510–3516, 2006     

Peculiarities of establishment of steady-state frontal polymerization of vinyl monomers

Frontal radical polymerization of vinyl monomers in non-stationary mode is investigated theoretically. It is shown that the formation and the time of establishment of steady-state polymerization heat autowaves considerably depend on the initial temperature, T_i. When T_i is less than the adiabatic heating temperature (T_a), the excess heat and relatively high conversion foster front formation before the non-stationary one. Whereas, for T_i > T_a, steady-state frontal polymerization regime is established, when the heat flow from the outer source is considerably less than the heat evolving due to the chemical reaction.     

Efficient preparation of novel fluoroalkyl end‐capped oligomers/titanium dioxide nanocomposites

Novel fluoroalky end‐capped oligomers/titanium dioxide nanocomposites were prepared by the hydrolysis of titanium isopropoxide in the presence of fluoroalkyl end‐capped N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer [R_F‐(DOBAA)_n‐R_F], fluoroalkyl end‐capped N,N‐dimethylacrylamide oligomer [R_F‐(DMAA)_n‐R_F], and fluoroalkyl end‐capped acrylic acid oligomer [R_F‐(ACA)_n‐R_F] in tetrahydrofuran under mild conditions. In these fluorinated oligomers, R_F‐(ACA)_n‐R_F oligomer is more effective for the preparation of the corresponding oligomers/titanium dioxide nanocomposites, and this oligomer can afford the expected fluorinated titanium dioxide nanocomposites in higher isolated yields. In addition, R_F‐(ACA)_n‐R_F/titanium dioxide composites are nanometer size‐controlled very fine nanoparticles (14–48 nm), and exhibited a good dispersibility not only in water but also in traditional organic solvents. Fluoroalkyl end‐capped oligomers/titanium dioxide nanocomposites were also applied to the surface modification of the common organic polymers such as poly(methyl methacrylate) to exhibit a good oleophobic and hydrophilic characteristics on the surface. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers.     

Modeling of butadiene polymerization using cobalt octoate/DEAC/water catalyst

Two-level fractional factorial designs were employed to study the solution polymerization of butadiene in a batch reactor using cobalt octoate/DEAC/water as catalyst. Conversion and molecular weight data obtained as functions of time were used to develop a kinetic model, and the estimated kinetic parameters were correlated empirically with four operating variables: temperature and concentrations of cobalt octoate, DEAC, and water. The experimental data indicate that at high water concentration a significant amount of oligomers is formed during early stages of polymerization, and the molecular weight of polymer increases with time. Analysis of the data suggests instantaneous initiation, first order propagation with cobalt and monomer, and transfer to monomer. Models which do not take account of the branching are shown to be incapable of fitting data for both M _n and M _w. The catalyst decay seems to follow a first-order mechanism, but the evidence is somewhat inconclusive.     

Two-Component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates. Studies with in situ generated wittig salts

A two-component initiator system based on the in situ generation of Wittig salts (alkytriarylphosphonium bromides) has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers for potential use in composite applications so that the prepolymer can suitably wet the composite material before being converted to high molecular weight polymer. The Wittig salt precursors (an alkyl bromide, such as hexadecyl bromide, and a triarylphosphine, such as triphenylphosphine) did not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. However, when the two mixtures of cyclic BPA carbonate oligomers and initiator component were combined, a high molecular weight polymer (M_w = ∼ 65,000) was produced. The polymerization initiating species is thought to be hexadecyltriphenyl-phosphonium bromide. Consistent with this hypothesis is the observation that authentic Wittig salts did initiate ring-opening polymerization to provide high molecular weight polycarbonate. The effects of structure and concentration of the initiator components, reaction temperature, time, etc. on polymerization were studied; in general, the degree of polymerization ranged from 65 to 85%. © 1996 John Wiley & Sons, Inc.     

Manganese(IV)-initiated graft polymerization of vinyl monomers on polyamide fibers

The feasibility of potassium permanganate to induce graft polymerization of vinyl monomers onto nylon 6 was investigated. The graft yield is greatly enhanced by increasing the monomer concentration, reaction time, and temperature. The addition of metallic ions as promoters to the grafting medium accelerates the graft polymerization. A mechanism for grafting was proposed. The activation energy of initiation E_i for methyl methacrylate was calculated and found to be 5 kcal/mole. The overall rate of graft polymerization R_p depends on the monomer concentration.     

Synthesis and characterization of low‐molecular‐weight poly(2,6‐dimethyl‐1,4‐phenylene oxide) in water

Low‐molecular‐weight poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) with unimodal polydispersity was synthesized by oxidative polymerization of 2,6‐dimethylphenol in the presence of Cu‐ethylene diamine tetraacetic acid catalyst in water. A series of low‐molecular‐weight PPO oligomers with M_n ranged from 360 to 3500 were obtained. It was found that the molecular weight and polydispersity were affected by reaction time, reaction temperature, and catalyst concentration. Based on the detector response‐elution volume curve and the molecular weight from gel permeation chromatography, a possible molecular weight growth mechanism was proposed. The structure and properties of low‐molecular‐weight PPO oligomers were characterized by atomic absorption spectroscopy, differential scanning calorimetry, Ubbelohde viscometer, and nuclear magnetic resonance spectroscopy. Compared to the commercial low‐molecular‐weight PPO, PPO oligomers synthesized in water had a much lower residual copper content. The relationships between T_g and M_n at relatively low‐molecular weight are in good agreement with the equation proposed by Fox and Loshack. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Gelation of poly(vinyl alcohol) solutions at low temperatures (20 to −78°C) and properties of gels

The flow points of atactic poly(vinyl alcohol) (a-PVA) gels with H₂O/dimethyl sulfoxide (DMSO) = 90/10 (v/v) chilled at 20 to ?78°C for 24 h depended on the chilling temperature and were 0–30°C for gels with the initial polymer concentrations (C_i) of 2–5 g/dL, whereas those for H₂O/DMSO = 50/50 chilled at 0 to ?78°C were independent of the chilling temperature and were 70–75°C. Syneresis occurred after eight cycles of freezing (?24°C) and thawing (20°C) for a-PVA hydrogels at concentrations above C_i = 4 g/dL and two such cycles for syndiotacticity-rich PVA (s-PVA) hydrogels at concentrations above C_i = 1 g/dL. The extent of syneresis per one cycle for s-PVA hydrogels was higher than that for a-PVA hydrogels at the initial cycles. In the a-PVA hydrogels with an initial polymer concentration of ca. 30 g/dL, syneresis was expected not to occur even after 20 cycles. If all the free water in the gels is assumed to have transuded by syneresis after 20 cycles, the residual water is bound water and is estimated to be six water molecules per one vinyl alcohol monomer unit. © 1994 John Wiley & Sons, Inc.     

Evaluating The Extent of Bio-Polyester Polymerization in Solid Wood by Thermogravimetric Analysis

In this study, the thermogravimetric analysis (TGA) technique has been applied to determine the extent of in situ polymerization achievable in solid wood on treating with bio-polyester oligomers. Low-molecular-weight oligomers of poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(butylene succinate) (PBS), and poly(butylene adipate) (PBA) were impregnated and then thermally polymerized within solid wood to enhance the physical properties of wood. TGA revealed a similar degree of oligomer polymerization was achieved either with pure oligomers or within the wood structure. The influence of relatively acidic treatments, such as low-molecular-weight PGA oligomers, was observed to lead to degradation of the hemicellulose wood component. Polymerization of PLA and PGA oligomer treatments which penetrate the wood cell wall gave relatively lower wood thermal stability. Treatment and polymerization of lumen filling PBS and PBA oligomers contributed to increased wood thermal stability.     

Polymerization of acrylic bone cement investigated by differential scanning calorimetry: Effects of heating rate and TCP content

The polymerization reaction of a bone cement (standard Surgical Simplex-P Radiopaque) upon heating has been investigated by differential scanning calorimetry (DSC). The effects of the addition of tricalcium phosphate (TCP) on the rate and the heat of polymerization during DSC heating were evaluated. The rate and polymerization heat (ΔH) were characterized by the initial curing temperature (T_i), peak temperature (T_p), completing curing temperature (T_f), the curing range (ΔT = T_f ? T_i) and the area of the DSC exotherm. It was found that T_i, T_p, T_f, ΔT, and ΔH all increase with increasing heating rate. Increasing TCP content also induced increases in T_i, T_p, T_f, ΔT, and ΔH. From the kinetic analysis, the polymerization of acrylic bone cement was found to be a first order reaction. The effects of heating rate and TCP contents on the rate and the heat of polymerization could be explained based on the frequency factor and the activation energy extracted from the kinetic analysis. Increases in both heating rate and TCP content depressed the frequency factor and the activation energy.     

Polymerization of unsaturated dibasic acid derivatives capable of forming micelles. A novel synthetic method for anionic oligomers with high charge densities

A novel synthetic method for producing anionic oligomers with high charge densities was developed by polymerization of surface active monomers in aqueous micellar solutions. Unsaturated dibasic acids, such as itaconic, maleic and fumaric acids, having low or no homopolymerizability in water, were converted to surface active derivatives by introducing a long chain alkyl by ester or amide bonding. Their polymerizabilities were greatly improved to give poly(itaconic acid derivative)s and poly(fumaric acid derivative)s in fairly good yield. However, in the case of sodium salts of maleic acid half ester and N-alkylmaleamic acid, hydrolysis of the monomer as a side reaction during the polymerization occurred to a great extent, reducing the active monomer concentration, and the polymer formation was apparently saturated at a rather early stage of the process. The resulting polymers, with molecular weight in the oligomer region, were hydrolysed to the polyanious.     

High-pressure synthesis and optical limiting property of cyclic diphenylacetylene oligomer

New conjugated oligomers were synthesized by reacting diphenylacetylene under high pressure of 0.13–0.76 GPa at 250 and 300°C for 1–10 h. The number-average molecular weight M _n, and the weight-average molecular weight M _w increased with pressure, but those values were independent of temperature and time (M _n, 320–490; M _w, 350–580). Elementary analysis, field desorption mass spectrometry, Fourier transform infrared, and ¹³C nuclear magnetic resonance experiments revealed that the oligomer above and including pentamer was a new compound having cyclic structure. Toluene solutions of the oligomer (400 M _n) contained within a quartz cell were irradiated with the pulse from a frequency-doubled Nd : Yag laser at 532 nm. The transmittance of the solution decreased with input fluence, and we observed an optical limiting property with saturated output fluence. As the concentration of the oligomer increased, the saturated output fluence decreased. The optical limiting property was analyzed according to the reverse saturable absorption mechanism. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:129–135, 1998     

Free volume and dipole mobility in an epoxide oligomer before crosslinking

The free volume of a bisphenol‐A‐type epoxide oligomer (DGEBA) was studied using Williams–Landel–Ferry parameters and thermal expansion coefficients above and below the glass transition temperature (T_g). The values of the free‐volume fraction at the T_g are around 0.02 for the DGEBA oligomers having weight‐average molecular weights (M _w's) from 1396 to 2640. The dipole mobility, which was obtained from the analysis of the temperature dependence of the dielectric relaxation time, was compared with the segment mobility in terms of the critical volume for the transport of each moving unit. The critical volume for the segment transport increases with increase of the M _w of the oligomer. The critical volume for the dipole movement, on the other hand, is not different between the oligomers studied (1396 ≤ M _w ≤ 2640), which leads to that the dipole mobility in the epoxide oligomer is smaller than is the segment mobility. The low mobility of the dipole is considered to result from the molecular interaction restricting the dipole movement, especially in a smaller M _w oligomer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 207–214, 1999     

Synthesis and properties of waterborne UV‐curable polydimethylsiloxane‐based polyurethane oligomers: UV‐cured film with excellent water resistance and thermostability

Abstract

This paper designed and synthesized a series of waterborne UV-curable polydimethylsiloxane‐based polyurethane oligomers which contain polydimethylsiloxane segment in the end of the main chain, a plurality of double bonds in the side chain and two kinds of hydrophilic groups including nonionic polyethylene glycol with low molecular weight and ionic quaternary ammonium salt groups. The unique structure endowed not only the oligomer with an excellent water solubility, but also the UV-cured film with hydrophobicity, thermostability and mechanical properties. The prepared oligomers could form a stable white emulsion and had excellent photopolymerization capability, and their conversions of double bonds were all over 92%. The UV-cured film containing long chain polydimethylsiloxane exhibited better hydrophobicity, heat resistance and tensile strength. The polydimethylsiloxane segment located in the end of the oligomer molecular chain was more conducive to its enrichment in the surface of the cured films and improving of the hydrophobicity of the cured films. The water absorption, surface water contact angle and the initial decomposition temperature (T_5%) of the obtained UV-cured films were 2.7%, 91 and 301?°C, respectively.     

Concentration dependence on viscosity of oligourethane diols

To obtain viscosity suitable for application, relatively low molecular weight polymers, i.e., oligomers, are used in the formulation of high solids coatings. To support this requirement, the concentration dependence of the viscosity of synthesized oligourethane diols in different solvents was analyzed using Erickson's models. By regression analysis, it was found that the correlation coefficients are fairly good and the plots of the residuals are more random. The weight intrinsic viscosity, [η_o], composed of the oligomer component, O_5[η]o, and the oligomer-solvent interaction component, I_[η]o, was calculated from the intercept of the plot of 1/ln η_r vs. 1/o₀. The parameter I_[η]o, related to the solvent molar volume and the distance between the oligomer and solvent partial cohesion parameter coordinates, indicates the degree of interaction between the oligomer and solvent. The partial cohesion parameters of the oligomers obtained by the group-contribution method were used for calculating the interaction component of oligourethane diols. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1343–1351, 1997