Solution properties of chlorinated polypropylene and maleic anhydride grafted chlorinated polypropylene

The solution behaviors of the chlorinated polypropylene (CPP) and its grafted polymers (CPP-g-MAH) were systematically studied to characterize their polar change with grafting maleic anhydride (MAH) onto the chain of CPP. The molecular weights of the polymers were determined with light scattering measurements, and the Mark–Houwink equation of CPP in toluene was also obtained. The result showed that the Mark–Houwink equation of CPP was suitable for estimating the molecular weight of the polydisperse samples of CPP and not suitable to CPP-g-MAH because the molecular polarity of the graft polymers had changed with grafting MAH onto CPP. The solubility result of CPP and CPP-g-MAH in various solvents indicated that the polarity of CPP gradually increased with grafting MAH onto its chain, which would cause the solubility of poorly hydrogen bonded solvents for CPP-g-MAH to gradually become poor, whereas that of moderately hydrogen bonded solvents for the polymers becomes better with an increase of the MAH graft content. This is consistent with the results of their dilution ratio and solubility parameter. Stabilities of the 344^# resin–CPP-g-MAH–toluene solutions showed that the miscibility of CPP-g-MAH and 344^# resin was improved with increase of the MAH grafted content.     

Polyaromatic ether–ketones and ether–keto–sulfones having various hydrophilic groups

Polyaromatic ether–ketones and polyaromatic ether–keto–sulfones were sulfonated by suspending the polymer powders in dichloroethane containing liquid sulfur tiroxide and trialkyl phosphate at room temperature. It was found that more than one sulfonic group can be introduced per each repeating unit of the polymers without degradation. The sulfonated polymers were soluble in various organic solvents, and solubility and mechanical properties depended on the initial molecular weight of polymers as well as the degrees of sulfonation. Strong films can be cast from their dimethylformamide solutions.     

Investigation of thermodynamic properties of poly(methyl methacrylate-co-n-butylacrylate-co-cyclopentyl styryl-polyhedral oligomeric silsesquioxane) by inverse gas chromatography

The thermodynamic properties of poly(methyl methacrylate-co-butyl acrylate-co-cyclo -pentylstyryl polyhedral oligomeric silsesquioxane) (poly(MMA-co-BA-co-styryl-POSS)) were investigated by means of inverse gas chromatography (IGC) using 20 different kinds of solvents as the probes. Some thermodynamic parameters, such as molar heats of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between POSS-contained polymers and solvents and the solubility of the polymers in these solvents. It was found that acetates, aromatic hydrocarbons and hydrocarbon halides were good solvents, n-hexane, ethanol, n-propanol, n-butanol and n-pentanol were moderate solvents, while n-heptane, n-octane, n-nonane, n-decane and methanol were poor solvents for all POSS-contained polymers within the experimental temperature range. Incorporation of POSS in polymer increased the solubility of polymers in solvents, and the more the POSS in polymer was, the better the solubility was and stronger the hydrogen bonding interaction was, but the POSS content in polymers seemed to have no obvious influence on the solubility parameter of polymers.     

Investigation of thermodynamic properties of hyperbranched aliphatic polyesters by inverse gas chromatography

Thermodynamic properties of a series of commercial hyperbranched aliphatic polyesters (Boltorn^® H20, H30 and H40) were examined for the first time by inverse gas chromatography (IGC) using 13 different solvents at infinite dilution as probes. Retention data of probes were utilized for an extensive characterization of polymers, which includes the determination of the Flory–Huggins interaction parameter, the weight fraction activity coefficient as well as the total and partial solubility parameters. Analysis of the results indicated that the total and partial solubility parameters decrease with increase of temperature. Furthermore, upon increase of the molecular weight, while the hydrogen bonding component decreases, no influence on the total solubility parameter is noticed within the experimental error margins. Results from the present study while providing new insight to the thermodynamic characteristics of the examined systems, they are also expected to reflect more general aspects of the behavior of hyperbranched polymers bearing similar end-groups.     

Inverse gas chromatographic characterization of triblock copolymer of polystyrene–poly(ethylene oxide)–polystyrene

The thermodynamic properties of triblock copolymer of polystyrene–poly (ethylene oxide)–polystyrene (PS‐b‐PEO‐b‐PS) were investigated by means of inverse gas chromatography (IGC) using 15 different kinds of solvents as the probes. Some thermodynamic parameters, such as specific retention volume, molar heats of sorption, weight fraction activity coefficient, Flory‐Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between PS‐b‐PEO‐b‐PS polymers and solvents and the solubility of the polymers in these solvents. It was found that increasing PEO content in PS‐b‐PEO‐b‐PS resulted in the increase in the solubility of PS‐b‐PEO‐b‐PS in alkanes and acetates solvents, but the solubility in alcohols had no change, and more PEO content in polymer caused a small decrease in the solubility parameter of PS‐b‐PEO‐b‐PS polymer, © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2015–2022, 2007     

Processable heat-resistant polymers. XI. Synthesis and characterization of unsaturated polyamideimides

Polycondensation of the diacid chloride of 2-(3-carboxy vinyl)phenyl-1,3-dioxoisoindoline-5-carboxylic acid with m-phenylenediamine and the diacid chloride of 2-(4-carboxy phenyl)-1,3-dioxoisoindoline-5-carboxylic acid with 1,5-bis(3-aminophenyl)1,4-pentadien-3-one was carried out in polar solvents to produce new unsaturated polyamide–imides. The solution and the thermal, electrical, and a few other properties of the polymers were studies. The polymers were soluble in highly polar solvents. The solubility parameter of the polymers was calculated from the Small's group contribution. The polymers were fairly thermostable and underwent crosslinking creaction when heated, preferably in the presence of a suitable catalyst. The crosslinked polymers were in soluble even in highly polar solvents and possessed higher thermal stability. The swelling behavior of the polymers was studied and the molecular weight between two consecutive crosslinks was determined. X-ray diffraction and the dielectric properties of the polymers and their crosslinked products were also studied.     

Investigation of thermodynamic properties of hyperbranched poly(ester amide) by inverse gas chromatography

Thermodynamic properties of the hyperbranched poly (ester amide) (Hybrane® 1200) were investigated by inverse gas chromatography (IGC) using 19 different solvents as the probes at infinite dilution. Retention data of probes were used for an extensive characterization of the polymer, which includes the determination of the Flory‐Huggins interaction parameter, the weight fraction activity coefficient, the total, partial, and additive solubility parameters. The analysis of the results indicated that the additive value of the solubility parameter is lower than the value obtained from a standard procedure. Furthermore, the solubility parameter decreases with increase of temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2166–2172, 2008     

Poly(MMA-co-MBA-co-MA-POSS)三元共聚物溶液性质的反气相色谱表征

以20种溶剂作为探针分子,采用反气相色谱技术表征了甲基丙烯酸甲酯-甲基丙烯酸丁酯-甲基丙烯酰氧丙基七环戊基倍半硅氧烷三元共聚物[poly(MMA-co-MBA-co-MA-POSS)]的一系列物理化学性质,并分析了溶剂探针分子与共聚物分子间的相互作用以及共聚物在溶剂中的溶解性.结果表明:在实验温度范围内(343～393K),乙酸甲酯、乙酸乙酯、芳烃、二氯甲烷、三氯甲烷是良溶剂,乙酸丙酯、乙酸丁酯、乙酸戊酯、四氯化碳是中等溶剂,烷烃类和醇类是劣溶剂;随着共聚物中POSS含量的增大,溶剂探针分子溶解聚合物的能力增强,但引入POSS对共聚物的溶度参数无明显影响.     

Cohesive energy densities of polymers from turbidimetric titrations

Turbidimetric titrations have been made on polystyrene and poly-o-chlorostyrene in a series of solvents to deduce the solubility parameters of polymers from the Flory-Huggins interaction parameter χ. The assigned solubility parameter for polystyrene agrees well with the reported values obtained from swelling measurements. Brief discussion of the exceptional behavior in the solvent powers of paraffins is given.     

Thermodynamic interactions and characterisation of naphthenic oil by inverse gas chromatography

The thermodynamic properties of naphthenic oil, a plasticiser, were investigated by means of inverse gas chromatography (IGC) using 10 different kinds of solvents as probes. Some thermodynamic parameters, such as specific retention volume, weight fraction activity coefficient, Flory–Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between oil and solvents and the solubility of oil in these solvents. The results indicated that n-heptane, n-hexane, cyclohexane, chloroform, benzene and diethyl ether are good solvents for oil at experimental temperatures. The solubility parameters of oil varied from 13.94 to 13.21?(J?cm^?3)^1/2 at temperature range 323–353?K. The solubility parameter of oil was calculated to be 14.38?(J?cm^?3)^1/2 at room temperature, which is consistent with that obtained using surface tension–solubility parameter relation method.     

The metathetic degradation of polyisoprene and polybutadiene in block copolymers using Grubbs second generation catalyst

A degradation study of polystyrene-polybutadiene-polystyrene and polyisoprene-polystyrene-polyisoprene in both dichloromethane and hexane solvents is presented. Alternative solvents for metathetic degradation provide the potential for greener chemistry, better selectivity, and control over the products. The catalyst concentration and solvent selection both determine the products formed. The degradation of polyisoprene and polybutadiene in a particular solvent was controlled by the solubility of polyisoprene/polybutadiene, and by its solubility relative to polystyrene. A large difference in solubility between the polymers in the selected solvent provides an additional driving force for block separation, encouraging reaction close to the interface between different blocks. Furthermore, solubility of the block copolymer speeds the degradation reaction. This tailoring of the reaction mechanism yields a new control over the products of polymer degradation.     

Convex solubility parameters for polymers

Solubility parameters are certain measurable quantities that are observed to influence the ability of a solvent to fully dissolve a polymer. Current theory partitions the intermolecular forces between dispersion, polar, and hydrogen bonding interactions, thereby generating a three‐dimensional solubility parameter space. The Hansen solubility parameters of a polymer are taken to be the center of a sphere obtained from the best fit of the coordinates of good solvents in the parameter space. Investigations of several polymers (lignin, polyethersulfone, and bitumen) show that the convex hull of all known good solvents in the three‐dimensional parameter space also gives a meaningful interpretation of the solubility region. Several methods for computing the convex solubility parameters of a polymer from the convex solubility region are described. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1089–1097     

The fluorescence of 5-cyano-2-(1-pyrrolyl)-pyridine (CPP) in different solvents and in solid argon: An experimental and theoretical study

The fluorescence spectrum of 5-cyano-2-(1-pyrrolyl)-pyridine (CPP) was measured in several solvents as well as in an argon matrix. Based on comparison with other compounds and on ab initio calculations it is proposed that the fluorescence in the argon matrix and in non-polar solvents is due to two electronic excited states: one is of locally excited nature, the other a charge transfer (CT) state. In polar solvents the spectrum is dominated by the CT emission. The photo-physical behavior of CPP is discussed by comparison with that of other molecules exhibiting dual fluorescence and in view of a recent model developed for the benzene analog.     

Crosslinking of chlorine‐containing polymers by dicyclopentadiene dicarboxylic salts

Alkali‐ and alkali‐earth‐metal salts of dicyclopentadiene dicarboxylic acid (DCPDCA) were prepared and employed as crosslinkers for chlorine‐containing polymers such as polychloromethylstyrene (PCMS), chlorinated polypropylene (CPP), polyepichlorohydrin (PECH), and poly(vinyl chloride) (PVC). Thermally reversible covalent crosslinks (i.e.,  DCPD bridges) between polymer chains were generated through esterification between the chlorine–carbon bonds of the polymer and the carboxylic salt groups of the crosslinker. The crosslinking reactivity decreased in the following sequence: K > Na > LiDCPDCA > alkali‐earth‐metal salts of DCPDCA. In addition, PCMS and CPP had higher gelation rates than PECH and PVC. Good flowability at about 195 °C and solubility in maleimide‐containing dichlorobenzene on heating indicated that the crosslinked PCMS and CPP exhibited thermally reversible crosslinking because of dimer/monomer (cyclopentadiene) conversion of  DCPD moieties via reversible Diels–Alder cycloaddition. Samples of PECH and PVC crosslinked by the alkali salts of DCPDCA were insoluble even when heated in maleimide‐containing dichlorobenzene. However, these crosslinked polymers could be dissolved partially after the same treatment when the crosslinker was an alkali‐earth‐metal salt of DCPDCA. Thermal degradation such as dehydrochlorination of the PECH and PVC might have been responsible for uncontrolled crosslinking because these two polymers are known to be thermally unstable. The unreacted COOK, COONa, or COOLi of the crosslinkers might have initiated base‐induced dehydrochlorination when PECH and PVC were heated at high temperatures. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 818–825, 2000     

Physicochemical Characterization of Transport in Nanosized Membrane Structures

The understanding of polymer–solvent interactions is highly important for the development of tailored membrane manufacturing procedures and for the prediction of membrane performance from transport mechanisms. This study examines the permeation performance of organic solvents through state‐of‐the‐art polyimide membranes (STARMEM, Membrane Extraction Technology Ltd.). Solvents are systematically selected to allow investigation of the effects of key physicochemical transport parameters by keeping constant all other parameters thought to be relevant. The effect of the solubility parameter, polarity (dielectric constant), surface tension, and viscosity are studied in detail. Dead‐end permeation experiments are carried out at 20 bar with STARMEM 122 and STARMEM 240 membranes. Results for the selected solvents show higher permeation rates for ketones over alcohols and aromatics as well as for acids. It is suggested that the viscosity and polarity have a greater influence than the other parameters. The effect of solvent molar volume is also investigated. Transport of solvents with high molar volume, independent of their polarity and compatibility with the membrane material, is slower in all cases than for solvents with smaller molar volume. The solubility parameter does not show any significant effect on transport phenomena.     

The partial solubility parameters: An equation-of-state approach

The division of the well-known solubility parameter into its dispersion, polar, and hydrogen-bonding components has significantly upgraded its capacity and usefulness in the screening and selection of the appropriate solvents in Industry and in Laboratory. This work presents a new statistical thermodynamic approach for the estimation of these partial components over a broad range of temperature and pressure. Key to this approach is the development of explicit expressions for the contribution of dispersion, dipolar, and hydrogen-bonding interactions to the potential energy of the fluid. The approach is applicable to ordinary solvents, to supercritical fluids, as well as to high polymers. Information on various thermodynamic properties of fluids is used in order to estimate the three solubility parameter components. Extensive tables with the key parameters are presented. On the other hand, available information on these separate components is exploited in order to extract information for the thermodynamic behaviour of the fluids over an extended range of external conditions.     

Synthesis and degradation of intelligent hydrogels containing polyacetal segments

Intelligent hydrogels were first obtained by copolymerization of telechelic poly(1,3-dioxolane) (pDXL) with acrylic acid, acrylamide, N-isopropylacrylamide respectively. The synthesis and characterization of the networks were discussed. The swelling behavior of the hydrogel was dependent on the solubility parameter of the solvents and hydrogels. The networks containing polyacetal segments (pDXL) can degrade by acid in different solvents. DXL and few other cycle molecules measured by GC-MS analysis were formed after degradation. According to the degradation products, the polymerization mechanism can be testified.     

Phenoxasilin-containing polyamides and polyesters

Silicon-containing polyamides and polyesters of a new type have been synthesized. They contain phenoxasilin rings with double-stranded structure. The polymers were synthesized by the interfacial polycondensation of 2,8-dichloroformyl-10,10-diphenylphenoxasilin with diamines and bisphenols, and were obtained in nearly quantitative yields. Their reduced viscosities were in the range of 0.53–1.47 dl g^?1 m dimethylformamide (DMF), m-cresol or chloroform. Some of the polyamides were soluble in polar aprotic solvents such as DMF and N-methyl-2-pyrrolidone (NMP) and the polyesters had good solubility in chloroform, phenol-sym tetrachloroethane (60:40 by wt %) and acidic solvents (m-cresol and nitrobenzene). The polymers hardly dissolved in cone. H₂SO₄ and some of them coloured in it. Only the polyester having sulphide bonds was soluble in benzene in addition to the above organic solvents. These polymers hardly degraded below 400° except for the polyamides derived from aliphatic diamines. The polymers from aliphatic diamines melted at 290–325°; the other polyamides and the polyesters decomposed without melting.     

Synthesis and characterization of water-soluble PEGylated lignin-based polymers by macromolecular azo coupling reaction

Water-soluble PEGylated lignin polymers were efficiently synthesized by macromolecular azo coupling reaction between alkali lignin and PEG based macromolecular diazonium salts in alkaline water.     

Extraction of matrine from soil with matrix solid‐phase dispersion by molecularly imprinted polymers derived from lignin‐based Pickering emulsions

Molecularly imprinted polymers prepared by Pickering emulsion method with lignin as stable particle were used as dispersants in matrix solid‐phase dispersion, followed by ultra high performance liquid chromatography with tandem mass spectrometry to research the degradation behavior of matrine in soil. The molecularly imprinted polymers have regular morphology and uniform particles. Moreover, the adsorption experiments and the conditions of matrix solid‐phase dispersion were discussed. With the optimal conditions of matrix solid‐phase dispersion, the recoveries of matrine were 95.4–98.2%, relative standard deviations were 0.6–5.1%, and the detection limit was 5 ng/g. Moreover, the degradation behavior of matrine in soil was researched, it indicated the half‐life of matrine was 2.7–3.2 days, and it was an environmentally friendly botanical pesticide. The method was successfully applied to separate and analyze matrine in soil samples can decrease analysis time, save organic solvents, and improve the selectivity.