Effect of the nucleophilicity and solvent on the chemical modification of flexible poly(vinyl chloride) by substitution

The chemical modification might become an alternative to the thermal degradation of waste polyvinylchloride (PVC). Therefore, the nucleophile substitution of chlorine from flexible PVC by hydroxide (OH^?), thiocyanate (SCN^?), azide (N₃^?), and iodide (I^?) was investigated in ethylene glycol (EG) at 190°C. With the exception of I^?, all nucleophiles used resulted in substitution yields of about 20%. However, also high elimination yields were observed. When SCN was used as the nucleophile, the substitution/elimination ratio increased with decreasing temperature. The product at 150°C contained a mixed structure of thiocyanate and isothiocyanate groups, while at 190°C, only the structure of isothiocyanate was present the product, due to the isomerization of the ? S? C?N group under the formation of ? N?C?S at elevated temperatures. The substitution and dehydrochlorination yields increased with an increasing molar SCN/Cl ratio. When EG was replaced by diethylene glycol (DEG) or triethylene glycol (TEG), the dehydrochlorination was found to proceed more rapidly. The use of a solvent with a lower polarity improved the contact between the solvent and the polymer; however, solvents with a lower polarity favor the elimination over the substitution. Therefore, the substitution–elimination ratio increased in the order EG > DEG > TEG. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Dialkyldithiophosphate substituted on poly(vinylchloride): Synthesis and performance

Preparation of sodium salt of di(2-ethylhexyl)dithiophosphoric acid (DTPANa) by reaction of the corresponding DTPA with sodium hydride has been described. Nucleophilic substitution of chlorine on poly(vinylchloride) (PVC) by a di(2-ethylhexyl)dithiophosphate group resulting in modified polymer (MP) was characterized by the second order rate constant equal to 6.6 × 10^?5 M^?1 s^?1. Formation of homogeneous stable gelled phases composed of MP and DTPA, as well as MP, PVC, and DTPA, was demonstrated. The gelled material is capable of selective separation of metal ions under the conditions of extraction chromatography. © 1993 John Wiley & Sons, Inc.     

Chemical modification of rigid poly(vinyl chloride) by the substitution with nucleophiles

The reaction of rigid poly(vinyl chloride) (PVC) with iodide, hydroxide, azide, and thiocyanate as nucleophiles (Nu) in ethylene glycol (EG) resulted in the substitution of Cl by Nu additional to the elimination of HCl, leading to the dehydrochlorination of the rigid PVC. High substitution rates were observed for hydroxide, azide and thiocyanate, while the addition of iodide accelerated predominately the elimination of HCl. The substitution by thiocyanate resulted at 150°C in both thiocyanate and isothiocyanate structures, whereas at 190°C, only isothiocyanate was observed in the polymer. The dehydrochlorination yield increased with an increasing molar SCN/Cl ratio, resulting in a maximum substitution at high molar SCN/Cl ratios. When EG was replaced by diethylene glycol (DEG) as solvent, the dehydrochlorination was found to be accelerated. It was assumed that DEG has a higher compatibility with PVC, making it easier to penetrate the rigid PVC particle. For triethylene glycol (TEG), the rapid dehydrochlorination resulted probably in the coverage of the surface of the PVC particle by methyl methacrylate/butadiene/styrene (MBS), preventing the penetration by the solution. The substitution/dehydrochlorination ratio decreased in the order of EG > DEG > TEG because of the declining polarity of the solvent, stabilizing the activated S_N2 complex. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of poly(vinyl chloride) and polypropylene with styrene in a supercritical CO2 solvent medium: Synthesis and characterization

Graft copolymerization of styrene onto poly(vinyl chloride) (PVC) and polypropylene (PP) was carried out in a supercritical CO₂ medium using AIBN as a free radical initiator. The supercritical CO₂ medium served as a reaction medium in addition to being a solvent for the styrene monomer and the free radical initiator. The reaction temperature and pressure were kept above the critical points of the solvent‐monomer mixture to form a homogeneous single‐phase medium. The resulting graft copolymers were characterized using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and nuclear magnetic resonance (NMR) techniques. The weight percent of grafting was determined using IR absorbance ratio technique. TGA results showed that the thermal stabilily of grafted copolymer of PVC was better than that of PVC, while grafted copolymer of PP had poorer thermal stability than PP. DSC results showed that glass transition temperatures (T_g's) of the grafted copolymers were higher than those of the starting polymers PVC and PP. The presence of polystyrene attached to the backbone polymer was confirmed by ¹H NMR and ¹³C NMR analyses.     

Study on preparation and properties of gel polymer electrolytes based on comb-like copolymer matrix of poly(ethylene glycol) monomethylether grafted carboxylated butadiene-acrylonitrile rubber

A novel kind of gel polymer electrolytes (GPE) based on comb-like copolymers of poly(ethylene glycol) monomethylether (mPEG) grafted carboxylated butadiene-acrylonitrile rubber (XNBR) were prepared by introducing ionic liquids and LiClO₄ into polymer framework. FTIR spectra confirmed the grafting of mPEG to XNBR as side chains, and the content of grafted mPEG were calculated from the integral area of related peaks in ¹ H NMR spectra. Such grafted copolymer based GPE with ionic liquids as solvent showed higher ionic conductivity and reached a maximum ionic conductivity of 1.64?×?10^?3?S/cm (30?°C) in the experimental range, because the copolymers performed better polymer chain flexibility, which could be concluded from the decrease of T _g and crystallinity through DSC analysis. The generated GPE exhibited high electrochemical stability and the unit cell of LiFePO₄/GPE/Li could be cycled at room temperature.     

Effects of Na+ substitution Cs+ on the microstructure and thermal expansion behavior of ceramic derived from geopolymer

As part of a series of studies, effects of Na⁺ substitution on the thermal evolution of cesium‐based geopolymers on heating were studied. A series of sodium‐substituted cesium‐based geopolymers, Cs_(1?x)Na_xGPs (where x=0, 0.1, 0.2, 0.3, and 0.4), were prepared and treated at 1300°C for 2 hours to obtain the corresponding ceramic products. The thermal evolution process was disclosed by virtue of a variety of technical, including TG‐DTA, thermal shrinkage, XRD analysis, SEM, and TEM investigation. The results indicated that unheated Cs_(1?x)Na_xGPs was not completely amorphous after the substitution of Na⁺ and the crystallinity of Cs_(1?x)Na_xGPs gradually increased with the rise of sodium content. Meanwhile, the average particle sizes of Cs_(1?x)Na_xGPs also increased evidently with increases in sodium substitution. The final product after heat treatment mainly consisted of pollucite (CsAlSi₂O₆) and amorphous glass phase. The particle size of pollucite grain gradually decreased as more Cs⁺ were replaced maybe owing to the role of Na⁺ in the nucleation process of pollucite. Two forms of Na⁺ present in the final products: A small portion was present in the pollucite grains due to Na⁺ partial occupied the crystallographic sites of Cs⁺; and the rest were present in the amorphous glass phase among the pollucite grains. The average coefficient of thermal expansion (CTE) of resulting Cs_(1?x)Na_xGPs ceramics increased from 4.80×10^‐6 K^?1 (x=0) to 7.26×10^?6 K^?1 (x=0.4) with increases in sodium substitution, which could be due to the amorphous glass phase had a relatively higher CTE than that of pollucite.     

Polymerisation von Vinylchlorid bei Atmosphärendruck. 2. Chemische und spektroskopische Methoden zur Charakterisierung von U-PVC

PVC, which was polymerized at atmospheric pressure (so called U-PVC) contains relatively high concentrations of defects contrary to normal PVC. The number of chain scissions in U-PVC determined by ozonolytic cleavage resulted in values between 0.026 and 0.058 per 100 monomer units (100 VC). The determination of allylic and tertiary chlorine was done by selective reaction of U-PVC with phenol and NMR-spectroscopic investigations of the phenolized polymers. The average ‘labile chlorine’ content amounts to 0.65/100 VC. Hydroxyl radicals formed during the decomposition of the initiator (K₂S₂O₈) resulted in alcoholic endgroups in U-PVC, which were detectable in the IR-spectrum at 3580 cm^?1. The termination with hydroxyradicals also led to structures at the chain ends changing into ß-chloraldehyde groups accompanied by HCl-elimination. The corresponding signal in the IR-spectrum appeared at 1720 cm^?1. U-PVC raw material contained about two branch points per 100 VC. The CCl₄ extracts of the same polymers revealed the ten-fold content of branching. The olefinic structures ? CH?CH? CHCl? and ? CHCl? CH?CH₂ were determined by NMR-spectroscopy. The concentrations of each ranged from 0.25 to 0.3/100 VC. A typical double bond for U-PVC at the chain ends represented the structure ? CH?CH? CH₂Cl, which was preferably present in the low molecular weight material.     

Sorption von Silber an chlormethyliertem Polystyrol

Silver ions are bound on polystyrene containing ? CH₂Cl groups with a distribution coefficient of about 100 ml/g, but they are not bound on polystyrene itself. This indicates direct interaction between Ag⁺ ions and the chlorine atoms of the ? CH₂Cl groups in the sense of formation of a 1:1 complex. In presence of 0.1 mol/l of ammonium ions somewhat smaller distribution coefficients are found in the range from pH 4 to pH 6. In presence of 10^?3 mol/l of Na₂S₂O₃ the distribution coefficients are only about 6 ml/g. From solutions, however, containing 1 mol/l of NaCl or 0.1 mol/l of Na₂S₂O₃ or 10^?3 mol/l of NaCN, silver is not sorbed in measurable amounts, because complexation in solution predominates.     

Synthesis of borate ester‐grafted carboxylated acrylonitrile butadiene rubber and its use as electron acceptor to dissolve lithium perchlorate

A novel borate ester (BE)‐grafted carboxylated acrylonitrile butadiene rubber (XNBR) was synthesized. From Fourier transform infrared, ¹H NMR and elemental analyses, the borate ester was successfully grafted to XNBR, resulting in a more flexible XNBR chain as revealed by differential scanning calorimetry. The binding energies of boron, oxygen, lithium and chlorine atoms of XNBR‐g‐BE–LiClO₄ are quite different from those of XNBR or LiClO₄. Meanwhile, the wavenumbers of C? O? B? O? C, C?O and C? H vibrations of the benzene ring shift towards lower values and a new shoulder peak for ? CN at about 2260 cm^?1 emerges. By integrating fitting peak areas of ? CN groups and ClO₄^?, the fractions of ? CN group and ClO₄^? bidentate bonding in XNBR‐g‐BE–LiClO₄ are much higher than in NBR–LiClO₄. Based on these experiments, a possible dissociation mechanism is proposed in which the boron atom of XNBR‐g‐BE receives electron pairs from ClO₄^?, releasing partial positive charge of Li⁺ to bind with ? CN group. © 2016 Society of Chemical Industry     

Grafting polythiophene on polyethylene surfaces

Polythiophene (PT) was grafted on PE film using three reaction steps. First, PE films were brominated in the gas phase, yielding PE–Br; second, a substitution reaction of PE–Br with 2‐thiophene thiolate anion gave the thiophene‐functionalized PE; finally PT was grafted on the PE surface using chemical oxidative polymerization to give PE–PT. The polymerization was carried out in a suspension solution of anhydrous FeCl₃ in CHCl₃, yielding a reddish PE–PT film after dedoping with ethanol. ATR‐FTIR shows that the PT was grafted on PE in the 2,5‐position. SEM imaging revealed islands of PT on the PE film. AFM analysis found the thickness of islands to be in the range of 120–145 nm. The conductivity of these thin films was in the range of 10^?6 S cm^?1, a significant increase from the value of ～10^?14 S cm^?1 measured for PE film. © 2003 Society of Chemical Industry     

Properties of fused polysulphides—IV. Cryoscopic studies on solutions of alkali metal polysulphides in potassium thiocyanate

Measurements have been made of the depression of the freezing point of fused KSCN by Na₂S, Na₂S_4.4 and K₂S_5.9. Na₂S gives a freezing point depression corresponding to three region particles. These are believed to be 2Na⁺ and CN^?, the cyanide ion being formed by reaction of S^2? with the solvent. Na₂S_4.4 and K₂S_5.9 give opaque solutions in KSCN which are initially dark blue-green, and which slowly lose sulphur vapour and change colour to blue and finally to pale yellow. The initial freezing point depressions correspond to 4 and 2 foreign particles respectively, but when sulphur evolution is complete the final depressions correspond to 2 and 0 foreign particles. The following schemes are consistent with the observations

     

Synthesis and characterization of fullerene functionalized poly(vinyl chloride) (PVC) and dehydrochlorinated PVC using atom Transfer Radical Addition and AIBN based fullerenation

The research presented details chemical modifications of poly(vinyl chloride) (PVC) and its derivative, dehydrochlorinated PVC (DH‐PVC) through the use of two grafting techniques, namely a normal fullerenation, using AIBN (2,2′‐Azoisobutyronitrile), and the atom transfer radical addition (ATRA). The products were characterized and the presence of new FTIR peaks at 528 and 577 cm^?1 along with new ¹H‐NMR signal at 3.9 ppm, suggested that fullerenes has been grafted to the polymer molecules. Percentage of C₆₀ in the fullerene grated products determined by UV/Visible spectroscopy initially increased with the amount of fullerene used to a maximum value (～5.66 % wt) before decreasing again. It was also determined that the C₆₀ content of the fullerene grafted PVC product prepared by using ATRA, was notably greater than that obtained using the normal fullerenation approach, regardless of the amount of C₆₀ used. When the dehydrochlorinated PVC was used as the starting polymer for fullerenation, the fullerene grafted DH‐PVC using ATRA, was markedly insoluble in many common solvents (THF and dichlorobenzene). This was not the cases for the fullerene grafted DHPVC prepared via an AIBN based fullerenation. Furthermore, the electrical conductivity values of the modified PVC products determined by using a four‐point probe method were found to increase linearly with the amount of C₆₀ present. Overall our data suggest that the suitable and efficient techniques for grafting C₆₀ onto PVC and DHPVC chains are ATRA and AIBN‐based fullerenation, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2410–2421, 2013     

Synthesis of montmorillonite-modified acrylic impact modifiers and toughening of poly(vinyl chloride)

A series of Na-montmorillonite (Na⁺-MMT) modified acrylic impact modifiers (mAIM) were prepared by seeded emulsion polymerization. These mAIM modifiers were characterized by XRD. A 0.24?nm of increased interlayer distance of Na⁺-MMT was an indication of polymer chains intercalation within interlayer spacing. The notched Izod impact tests proved that the impact strength of the PVC/AIM composites prepared by melt blending was 43?J/m, markedly higher than the impact strength of pure PVC. Furthermore, with increasing content of AIM, the composites exhibited changes from brittle fracture to ductile fracture, with the impact strength increasing from 200 to about 1,000?J/m. The impact strength of PVC/mAIM also showed the same trend, although there were drops in some values. The impact strength of PVC/mAIM composites decreased with the increases in Na⁺-MMT content, but the yield strength and modulus of the composites increased with higher Na⁺-MMT content. The result also showed that the tensile strength of mAIM with 2 wt?% Na⁺-MMT is lower than that of mAIM with 0.8 and 1 wt?% contents, but still sufficiently large in comparison to the tensile strength of mAIM with 0 wt?% Na⁺-MMT. The dynamic mechanical analysis (DMA) result showed that the glass transition temperature (T _g) of mAIM did not show obvious changes and the elasticity of mAIM was reduced with the additional Na⁺-MMT content.     

A novel solid solution (K1-xNax)2Mo2O7 (0.0 ≤ x ≤ 0.3) ceramics with ultra-low sintering temperatures

The (K_1-xNa_x)₂Mo₂O₇ (0.0?≤?x?≤?0.3) ceramics with ultra-low sintering temperatures were prepared by a modified solid-state reaction method. Polyvinyl ethanol (PVA) binder was replaced by ethanol and isostatic pressing technology was used, which improved the density of the ceramics effectively and avoided the side effect of the residual PVA. When x?≤?0.3, the (K_1-xNa_x)₂Mo₂O₇ ceramics are with a triclinic phase and all components can be sintered well at 450?°C. The substitution of Na⁺ at the K-site modified the dielectric properties of K₂Mo₂O₇ ceramic and in particular increased the Q?×?f value. Among all the components, the (K_0.8Na_0.2)₂Mo₂O₇ ceramic exhibited the best microwave dielectric properties with a permittivity of 8.7, a Q?×?f value of 50 300?GHz and a temperature coefficient of ?64?ppm/°C. The (K_1-xNa_x)₂Mo₂O₇ (0.0?≤?x?≤?0.3) ceramics are very potential candidates for ultra-LTCC devices and the modified solid-state reaction method is an excellent substitution for the conventional solid-state method.     

A low temperature NaS battery incorporating A soluble S cathode

A NaS battery having the configuration

is described. This cell, operating just above the melting point of Na, utilizes sodium polysulfides (Na₂S_n) dissolved in an organic solvent as the cathode. Use of this cathode system allows operation at a lower temperature than in the Na/molten Na polysulfide battery. In order to find a suitable solvent for the cathode, solubility and stability data for Na₂S and Na₂S₄ were obtained in 26 organic solvents at 150°C. The solvent meeting the optimum requirements of high boiling point, polysulfide solubility, thermal stability and chemical compatibility with Na₂S_n is N,N-dmethylacetamide (DMAC). Charge—discharge data for cells incorporating an Na₂S₄/DMAC cathode are presented. Discharge to at least S^?2₂ appears possible. On recharge, a long chain, soluble Na polysulfide is formed rather than elemental S. This avoids possible problems due to separation of two phases as in the high temperature NaS battery.     

Effect of PBMA on PVC‐based polymer blend electrolytes

Poly(vinyl chloride) (PVC)—poly(butyl methacrylate) (PBMA) blended polymer electrolytes with lithium perchlorate (LiClO₄) as the complexing salts are prepared by solution casting technique. The addition of PBMA into PVC matrix is found to induce considerable changes in physical and electrical properties of the polymer electrolytes. Addition of PBMA into PVC matrix is found to increase the conductivity by two orders of magnitude (1.108 × 10^?5 S cm^?1) when compared with that of the pristine PVC polymer electrolyte (10^?7 S cm^?1). Structural, thermal, mechanical, morphological, and polymer–salt interactions are ascertained from X‐ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), mechanical analysis, scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) respectively. A thermal stability upto 250 °C is asserted from the TG/DTA analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44939.     

Chitosan-<Emphasis Type="Italic">g</Emphasis>-poly(4-acrylamidobenzenesulfonamide) copolymers: synthesis,characterization, and bioactivity

The monomer, 4-acrylamidobenzenesulfonamide (ABS), was synthesized via reaction of acryloyl chloride with 4-aminobenzenesulfonamide in acetone at 0 °C. This monomer was then grafted onto chitosan using solution containing 2% acetic acid and mixture of K₂S₂O₈ and Na₂SO₃ as the redox promoter. An optimal G% of 150% was obtained when the process is conducted at 60 °C for 3 h employing 3.0 × 10^?3 M K₂S₂O₈ and 1.5 × 10^?3 M Na₂SO₃. The graft copolymers, chitosan-g-poly(4-acrylamidobenzenesulfonamide), were characterized by using FTIR, XRD, and SEM. The results were shown that the crystallinity of chitosan is enhanced by increasing the monomer content through the grafting process. Potential Antimicrobial activities of the permethyl ammonium salt forms of chitosan and its grafted copolymers against selected microorganisms were evaluated. The results show that the graft copolymers display better inhibitory effects on the growth of bacteria and some fungi than does chitosan.     

Reaction rate and MWD changes in crosslinking of PVC,with dithioltriazine

The reaction rate of crosslinking of PVC with dithioltriazine has been studied by following gel formation and changes in the molecular weight distribution (MWD). Compounding was performed on a roll mill at 145°C and crosslinking by heat treatment at 180 or 90°C. In this system crosslinking is executed by the thiolate anion, formed in situ by reaction with MgO. We have studied the catalyzing effect of several polyols in order to achieve a more efficient reaction. Most likely, these catalysts work by chelating the Mg²⁺ ions, thus increasing the nucleophilic character of the thiolate. With the most efficient ones, ditrimethylolpropane and HO(CH₂CH₂)_6-7H, complete crosslinking can be obtained in 3 min at 180°C, i.e., at processing temperatures. We also followed the changes in the MWD before gelation at a considerably lower temperature, 145°C, and found an extensive molecular enlargement even after 5-10 min. Most surprisingly, μM_n increased up to 100% without formation of insoluble material. By ¹H-NMR measurements on low molecular weight extracts, we have shown this to be due to a fast and selective reaction with allylic chlorine in the unsaturated end groups, ～ CH₂? CH?CH? CH₂Cl, formed in the mechanism of chain transfer to monomer. Due to this reaction, formulations with too high reactivity may crosslink during processing, which calls for a careful balancing of the reactivity for each processing case.     

Emulsion polymerization of butadiene and subsequent grafting of methylmethacrylate. High impact properties of blends from this grafted polymer and polyvinylchloride

The paper illustrates the graft emulsion polymerization of methylmethacrylate onto polybutadiene in two steps. In the first butadiene is polymerized using two radical initiators (AIBN and (NH₄)₂S₂O₈), whose ratio does not influence the relative amount of 1,2-, 1,4-trans and 1,4-cis structures. The second step uses AIBN only: the grafting yield is very high. Grafting mechanism is discussed. The grafted polymer has good mechanical properties and its blends with PVC present very high impact strength. The mechanical properties are discussed. A statistical copolymer of butadiene and methylmethacrylate was prepared and compared with the grafted polymer. The copolymer is also a very good additive for PVC to elevate its impact strength.     

Chemical recycling of poly(vinyl chloride): Application of partially dehydrochlorinated poly(vinyl chloride) for producing a chemically modified polymer

Poly(vinyl chloride) (PVC) pipes were chemically modified to produce a sulfonated polymer with dehydrochlorinated PVC samples as intermediates. Two intermediates were formed: (1) partially dehydrochlorinated PVC with long sequences of conjugated double bonds and (2) the product of the partial dehydrochlorination of PVC and the nucleophilic substitution of chlorine by hydroxyl groups. The IR spectra showed that the dehydrochlorinated samples were heterogeneous materials, showing different proportions of elimination products, hydroxyl substitution, and partial oxidation. Samples dehydrochlorinated with poly(ethylene glycol) with a molecular weight of 400 g/mol for 24 h and 15 min showed the highest sulfonation yield, which was related to the sulfonation mechanism occurring predominantly because of the presence of hydroxyl groups in a mixture of vinyl alcohol and vinyl chloride units. The sulfonation was confirmed by the presence of a medium‐intensity band at 1180 cm^?1, assigned to sulfonic groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010