Amine-containing olefin copolymer with CO2-switchable oil absorption and desorption

Global decrease in crude oil resources and frequent crude oil leaks cause the energy crisis and ecological pollution. The absorption and release of leaked crude oil through absorption materials are a necessary process for environmental protection and recycling. In this article, a CO₂-responsive olefin copolymer was obtained by copolymerization of styrene and an amine-containing olefin monomer. The structure of resultant copolymer was characterized by FTIR; thermal properties and CO₂-responsive morphology changes were determined by DSC/TGA and SEM, respectively. Copolymers had certain absorption capacity for toluene with absorption rate up to 180.0%. The absorbed toluene could be released upon CO₂ stimulation with desorption rate up to 84.6%. The CO₂-responsive copolymer could be regenerated through a simple heating process and showed stable absorption–desorption performance even after being recycled for 4 times. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47439.     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Preparation and polymerization of isopimaric acid derivatives

Isopimaric acid is a typical rosin compound and can account for 30% of the total mass of slash pine rosin. The molecular structure of isopimaric acid derivatives features an unsaturated double bond at the C13 position, opening up the possibility of their industrial polymerization. In this study, isopimaric acid (95.4%), methyl isopimarate (99.5%), and allyl isopimarate (95.1%) were prepared as highly pure monomers. New experimental results are presented and mechanisms based on the investigation of free-radical polymerization under UV irradiation are proposed. New rosin monomers for potential value-added utilization of woody biomass are also identified. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47817.     

Mechanism of smoke suppression by melamine in rigid polyurethane foam

The smoke suppression of rigid polyurethane foam (RPUF) modified by melamine was investigated based on three sections: the condensed phase, the carbon layer, and the gas phase. In the condensed phase, the results of thermogravimetry, X‐ray photoelectron spectroscopy (XPS) N1S spectrum, and Fourier transform infrared spectroscopy indicated that melamine could suppress the degradation of RPUF by reacting with the aromatic hydrocarbons. It also reduced the smoke generation because the volatilizable aromatic hydrocarbons were the principal smoke precursors in a fire. In the carbon layer, the decrease from 38.50% to 24.76% of the inner layer oxygen content identified by XPS full‐spectrum and C1S spectrum indicated that melamine could prevent oxygen from transferring into the inner foam by the formation of an enhanced surface carbon layer, and the enhanced carbon layer could also block the release of smoke precursors. In the gas phase, the content of total aromatic hydrocarbons declined to 59.12% according to pyrolysis gaseous chromatography mass spectroscopy and indicated that melamine could reduce the smoke precursors. The results of smoke density chamber and cone calorimeter tests revealed that the addition of the melamine could decrease the smoke density of burning RPUF. Copyright © 2014 John Wiley & Sons, Ltd.     

不饱和单体熔融接枝PP体系中引发剂的选择

本文选择了过氧化异丙苯、过氧化苯甲酰、二叔丁基过氧化物三种引发剂进行实验。比较了三种引发剂的基本性能。讨论了引发剂种类及用量对接枝反应的影响，并研究了三种引发剂对ＰＰ降解及对接枝物外观颜色的影响。     

液晶基元直接横挂于主链上的液晶共聚物的合成与研究

以含液晶基元的单体２，５－双（４－甲氧基苯甲酰氧基）苯乙与苯乙烯通过自由基共聚合反应，首次合成了一系列含液晶性和非液晶性两种序列结构的共聚物。采用ＤＳＣ、偏光显微镜和Ｘ衍射方法研究了共聚物的液晶行为，发现单体和共聚物（只有ＣＰ－５和ＣＰ－６）有很好的热致液晶性。随共聚物中介晶单体单元含量的增加，共聚物玻璃化转变温度Ｔ和热分解温度Ｔ呈规律变化。     

尼龙6/马来酸酐-苯乙烯多单体接枝聚丙烯反应共混物

用双螺杆挤出机制备了聚丙烯(PP)与尼龙6(PA6)的共混物．先用多组分熔融接枝的方法将马来酸杆（MAH）和苯乙烯（St）共同接枝于聚丙烯（PP）上，制得多单体接枝聚丙烯PP-g-(MAH-St），该接枝物具有较高的MAH接枝率。利用MFR、SEM、TEM和力学性能测试等分析方法，研究了多组分熔融接枝聚丙烯PP-g-(MAH-St)对PA6/PP共混物的形态结构和力学性能等的影响。结果表明，PP-g-(MAH-St)中的酸酐基团与PA6末端的氨基发生化学反应，原位形成的PP-PA6共聚物能有效地改善PA6与PP的相容性，可以使PP均匀地分散在PA6基体中，相区尺寸明显减小，可至0.1μm，并使共混物的力学性能得到均衡的提高，冲击韧性的提高尤其显著，达到了橡胶改性所难以达到的效果。     

In-chain functionalization by alternating anionic copolymerization of styrene and 1-(4-dimethylaminophenyl)-1-phenylethylene

Anionic copolymerizations of styrene (M₁) with excess 1-(4-dimethyl-aminophenyl)-1-phenylethylene (M₂) were conducted in benzene at 25°C for 24h, using sec-butyllithium as initiator. Narrow molecular weight distribution copolymers with M?;_n = 16.1 × 10³ g/mol (M?_w/M?_n = 1.04) and 38.2 × 10³g/mol (M?_w/M?_n = 1.05), and 24 and 38 moles of M₂ per macromolecule, respectively, were characterized by size exclusion chromatography, ¹H NMR spectroscopy and DSC. The monomer reactivity ratio, r₁ = 5.6, was obtained from the copolymer composition at complete consumption of M₁, assuming that the rate constant k₂₂ =0,i.e. r₂ =0. The polymers exhibited T_g values of 128 and 119°C, respectively, which correspond to an estimated T_g = 217°C for the hypothetical homopolymer of M₂.     

Modeling of the bulk free radical polymerization up to high conversion—three stage polymerization model. II. Number-average molecular weight and apparent initiator efficiency

The equations for predicting the number-average molecular weight are derived on the basis of the three stage polymerization model (TSPM) in this paper. By applying the equations, a plotting approach is proposed to determine the apparent initiator efficiency defined as f[(α_td+1)/2] and the constant of chain transfer to monomer, where f is the initiator efficiency and α_td denotes the fraction of the termination rate constants by disproportionation. Using the approach to plot the experimental data in the literature, it is found that the chain transfer to monomer can be neglected for both methylmethacrylate (MMA) and styrene (St) polymerizations, but it can exert a significant effect on ethylmethacrylate (EMA) polymerization. In addition, the apparent initiator efficiency is found to be independent of reaction temperature and initiator concentration at each stage. The values of f[(α_td+1)/2] at gel effect stage are slightly reduced as compared with that at low conversion stage for MMA and EMA polymerizations. However, it decreases significantly at gel effect stage for St polymerization. Using the equations derived and the apparent initiator efficiencies obtained from TSPM plots, the number-average molecular weights at different conversions can be predicted. Comparisons show that the agreement between predictions and experimental data is satisfactory.     

Tannins/melamine–urea–formaldehyde (MUF) resins substitution of chrome in leather and its characterization by thermomechanical analysis

A new sulfonated melamine–urea–formaldehyde (MUF) resin of relatively low melamine content, prepared according to a sequential formulation, has been shown to be highly effective when coupled with different natural vegetable tannins to produce leather with the same good characteristics of leather prepared with chrome salts. In particular, the antishrinkage effectiveness of the leather prepared according to the new approach is comparable to that obtained with chrome tanned leathers. The comparison of the traditional leather shrinkage temperatures test method with a new thermomechanical analysis (TMA) test method in tension yields thermograms presenting three major modulus of elasticity (MOE) peaks. These are closely connected to molecular level phenomena determining the shrinkage temperature of leather. The three determining parameters appear to be as follows: (1) The average value of the temperatures at which the three MOE peaks occur: the higher the value of this average, the lower is the shrinkage of leather. (2) The average of maximum MOE values of the TMA peaks: the higher this average is, the better is the leather in regard to antishrinkage effectiveness. This means the leather maximum MOE at each peak is a measure of the resistance to the contraction force induced by heat. (3) The relative intensity of the first TMA peak in relation to the second: the higher the value of the MOE for the first TMA peak is in relation to the second peak, the lower the leather shrinkage appears to be. However, it has not been possible to better define or quantify this latter effect. This new TMA test method in tension has also yielded a mathematical relationship correlating the thermogram peak temperatures and MOE averages with the traditional shrinkage temperature to a high degree of confidence. A previous TMA test method, in compression, has proven to yield more problematic and finally not very reliable results when one needs to apply it to a wide variety of different cases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1889–1903, 2003