Anionic graft polymerization of propylene sulfide on cellulose. I

The anionic graft polymerization of propylene sulfide on cellulose membrane was studied. Alkali cellulosates were used to initiate graft polymerization, and graft polymers of high polypropylene sulfide content were obtained in good yields. The graft polymerization was accompanied by a certain extent of homopolymerization. The effects of reaction solvent, monomer concentration, cellulosate degree of substitution, and type of the alkali metal cellulosate on the graft polymer composition, yield, and on the molecular weight of the grafted side chains were investigated.     

Electroinitiated cationic polymerization of styrene by direct electron transfer

We have studied by cyclic voltammetry the mechanisms of electron transfer and peak potentials of eleven alkenes, propylene oxide, propylene sulfide, and carbon disulfide. We have also studied the cationic polymerization of styrene in acetonitrile solution initiated by controlled potential electrolysis at the anodic peak potential of styrene. The electrolyte used was tetrabutylammonium fluoborate, which was not electroactive at the electrolysis potential, and the reference electrode was a Ag⁰/Ag⁺ electrode. The electrochemical studies show that direct electron transfer from styrene is the initiation steps. Plots of reacted monomer concentrations versus time are sigmoidal curves. The propagation rate constant was found from a kinetic relationship based on an autocatalytic reaction. The activation energy is 15.6 kcal/mole at 20°C. The current behavior and effect of stirring on polymerization rate suggest that the growth of polymer takes place partially on the electrode surface.     

Alternating copolymerization through the complexes of conjugated vinyl monomers–alkylaluminum halides

A vinyl monomer that has the nitrile or carbonyl group conjugated to the C?C double bond, such as acrylonitrile, methyl acrylate, and methyl methacrylate, forms a complex with an alkylaluminum halide, and the complex reacts spontaneously with a hydrocarbon monomer such as styrene, propylene, or ethylene, giving a high molecular weight copolymer. The copolymers always contain the two monomer units in 1:1 ratio. Thus styrene, copolymerized with methyl acrylate or methyl methacrylate in the presence of ethylaluminum sesquichloride in homogeneous toluene solution, gives such an equimolar copolymer regardless of the initial monomer compositions. The NMR spectra of these copolymers are distinctly different from those of the equimolar copolymers obtained with azobisisobutyronitrile as initiator and have simpler and well separated patterns. The copolymers and the corresponding radical copolymers appear to be amorphous, judged by their x-ray diffraction patterns and their differential thermal analyses. Their infrared spectra resemble each other very closely. Hence, the difference in the NMR spectra may be ascribed to the matter of the sequence distribution. The infrared spectrum of ethylene–methyl acrylate copolymer shows no absorption near 720 cm.^?1 due to the methylene sequence arising from ethylene–ethylene linkage. These experimental data lead to the inference that the equimolar copolymers obtained in this work may have an alternating sequence.     

Synthesis, polymerization and Cu complexation studies of a new styrene derivative of 2-hydroxyacetophenone

A new 5-vinyl-2-hydroxyacetophenone monomer was synthesized using Heck reaction. The monomer was obtained by reacting 5-bromo-2-hydroxyacetophenone with ethylene in a palladium catalyzed reaction. Better yield was obtained at low concentration of the catalyst, high temperature and pressure of the ethylene gas. The monomer was homopolymerized and copolymerized with styrene using free radical solution polymerization techniques and investigated for reactivity ratio, retardation effect of the monomer on the polymerization of styrene. Homopolymer with average molecular weight of 40,391 was found to form binuclear complex with Cu²⁺. The complex was evident from shift in n-π^* transition from 332-378 nm in UV region and appearance of strong absorption at 1578 cm⁻¹ in the IR of the precipitated complex.     

RING OPENING POLYMERIZATION OF PROPYLENE SULFIDE BY RARE EARTH COORDINATION CATALYSTS*

Ring opening polymerization of propylene sulfide using rare earth coordination catalysts has been investigated for the first time. It has been found that trinary rare earth coordination catslysts composed of rare earth compounds of phosphonate, naphthenate or acetylacetonate, trialkyl sluminum and water are effective catalysts for the polymerization of propylene sulfide. The polymerization in toluene is a homogeneous reaction. High molecular weight as high as several million poly(propylene sulfide) with high yield can be prepared by these catalysts. Kinetic studies showed that the polymerization rate is of first order with respect to both monomer concentration and catalyst concentration. The activation energy of the polymerization reaction is 61.4 k fJ/mol. The structure of the polymers so obtained has also been characterized by ~(13)C NMR spectroscopy, X-ray diffraction, gel permeation chromatography and differential scanning calorimetry.     

Preparation of thiochromans via thermal cyclization

Formation of the thiochroman ring system is achieved by a two step synthesis that involves heating 3‐thiophenyl‐1‐propanols or 4‐thiophenyl‐2‐butanols in toluene with catalytic amounts of p‐toluenesulfonic acid. The propanols are made by the addition of sulfur stabilized carbanions to styrene oxide, ethylene oxide, propylene oxide, and isobutylene oxide. The carbanions are generated by treatment of either benzyl phenyl sulfide or thioanisole with butyllithium. The effect of substitution at the 1 and 3 positions of the propanols on the reaction yields is discussed. The mechanism of the reaction apparently involves intramolecular electrophilic aromatic substitution rather than a Claisen or thio‐Claisen rearrangement.     

Atom transfer radical polymerization of styrene from different poly(ethylene terephthalate) surfaces: Films, fibers and fabrics

Poly(ethylene terephthalate) (PET) is a semi-crystalline thermoplastic polyester used in many fields. For a variety of applications, however, it is necessary to impart desired properties by introducing specific functional groups on the surface. A simple method for growing polymer brushes by atom transfer radical polymerization (ATRP) on PET films, fibers and fabrics was devised. The different PET surfaces were first reacted with 1,2-diaminoethane by aminolysis reaction to incorporate primary amino and alcohol functions on the surface. Then, in a second step, ATRP initiator was grafted by reaction with bromoisobutyryl bromide. The efficiency of these reactions was confirmed by using colorimetric titration and X-ray photoelectron spectroscopy (XPS). Surface-initiated ATRP was performed in bulk using styrene monomer with CuBr/PMDETA catalytic system in the presence of a sacrificial initiator (ethyl 2-bromoisobutyrate). Good control of the polymerization was obtained as attested by comparison of polystyrene molar masses obtained in solution from sacrificial initiator with those obtained from the surface after cleavage. Wetting properties were found to vary systematically depending to the type of functionalization and grafting. Evolution of surface morphology according to reaction steps was investigated using atomic force microscopy (AFM).     

Anionic synthesis of poly[ethylene methylene bis(4-phenyl-carbamate)-g-acrylonitrile]

A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis.     

Admicellar polymerization of styrene on cotton

Thin-film coating on cotton by the admicellar polymerization process was investigated. In this work, styrene was used as the monomer to coat styrene on cotton. The effects of surfactant, styrene, initiator, and electrolyte concentrations on the polymerization process were determined. The polystyrene film formed was characterized by SEM, FTIR, and GPC. The increase in the hydrophobicity of the treated cotton surface was determined by the drop test. Results show that polystyrene thin film was successfully formed on cotton, resulting in cotton that can resist wetting by a water droplet for longer than 30 min.     

单茂钛/MAO体系催化乙烯/丙烯共聚合研究Ⅱ.乙烯/丙烯共聚物的核磁共振分析

用13C NMR测定了由单茂基钛化合物 /mMAO催化体系制备的乙烯 /丙烯共聚物大分子链的立体结构和单体序列分布 ,计算了单体的竞聚率r1=7 91± 0 0 6 ,r2 =0 135± 0 0 3 ,其乘积r1r2 ≈ 1.Fineman Ross计算得到的单体竞聚率与13C NMR测定值相近 ,即r1=7.94,r2 =0 .134,其乘积r1r2 =1 0 4.这表明共聚物是立构无规的 .共聚物经溶剂萃取后 ,乙醚可溶和己烷可溶两个级分中单体的序列分布和竞聚率略有不同 .乙醚可溶级分中丙烯链段稍长 ,而己烷可溶级分中乙烯链段稍长     

Asymmetrically superhydrophobic cotton fabrics fabricated by mist polymerization of lauryl methacrylate

A graft-polymerization process with atomized lauryl methacrylate as monomer is used to fabricate fluorine-less and asymmetrically superhydrophobic cotton fabrics. The polymers synthesized in the process can form nanoscale hierarchical structures on the cotton surface, and the surface morphology can be controlled by choosing a suitable solvent or by varying the feeding quantity of the monomer mist stream. After applying the surface modification to cotton fabrics, an asymmetrically superhydrophobic surface is achieved without any additional nanosized particles, and the solvent damages on the cotton fabrics are controllable at a very low level. Surface characterization reveals that the modified side of the cotton fabric has laundering-durable and mechanically stable superhydrophobicity with a water contact angle of more than 150°, whereas the opposite inherits the hydrophilic property of pristine cotton fabric. The modified cotton fabrics are found to have medium-level water-absorbing ability between pristine cotton and PET fabrics, as well as good vapor transmissibility similar to pristine cotton fabric. These properties are of great significance in textile and medical applications.     

Development of antimicrobial cotton fabric using bionanocomposites

In order to provide antimicrobial activity to cotton, cotton fabrics were treated by montmorillonite (KSF), montmorillonite–dihydroxy ethylene urea (KSF–MDEU), KSF–chitosan (CS) and KSF–CS–MDEU solutions containing 12.5, 25 and 50 ppm silver ion. The effect of modification on the antibacterial activity of cotton fabrics was also evaluated after 10 cycles of washings. MDEU exhibited better antimicrobial activities after washing process. By using 25 ppm silver, KSF and CS modification solution, good performance in terms of antibacterial activity was obtained. The addition of CS and MDEU increased the whiteness index values of cotton fabrics treated with KSF containing different silver concentrations. The characterization of modified cotton samples was done by Fourier transform infrared spectroscopy, X-ray diffraction analysis, inductively coupled plasma-mass spectroscopy, scanning electron microscopy and thermogravimetric analysis.     

载体化Et(Ind)2ZrCl2催化乙烯-苯乙烯共聚

用均相亚乙基二(1-茚基)二氯化锆(Et(Ind)₂ZrCl₂)催化乙烯和苯乙烯共聚时,所得共聚物中苯乙烯链节含量和聚合活性不能同时满足聚乙烯功能化的要求^[1,2].因此我们用SiO₂对Et(Ind)₂ZrCl₂进行载体化.     

Anisotropic Ionic Mobility of Lithium Salts in Lamellar Liquid Crystalline Polymer Networks

New mesogens presenting smectic A (SmA) phases and capable of hosting lithium salts are designed. The mesogens comprise a vinyl‐functionalized spacer to allow further reaction to the polymer backbone, an aromatic core and ethylene oxide chains, able to coordinate lithium ions. Copolymerizing these monomers with a suitable crosslinker yields the first lithium containing liquid crystalline elastomers (LCEs). The SmA structure where the ethylene oxide chains are microphase separated in layers is fixed by the crosslinking and permanent macroscopic orientation is obtained. Diffusion and conductivity measurements of the monomer sample show a large anisotropy of the ion mobility (100 for the cation and 400 for the anion). In the elastomer the anisotropy of the lithium mobility is comparable to that in the monomers.     

Analysis of polymers by pyrolysis/chemical ionization mass spectrometry

Two addition-type polymers, polystyrene and polypropylene, and two condensation-type polymers, poly(ethylene terephthalate) (Mylar) and poly(hexamethylene adipamide) (nylon-6,6), were pyrolyzed directly in the ion source of a mass spectrometer by chemical ionization (CI) to reduce fragmentation. The spectra are relatively easy to interpret because most ion peaks occur at a mass corresponding to the ion formula M±H or M + 3H, where M is the formula of a fragment of the original polymer chain. Oligomer peaks were observed for the addition-type polymers. The intensities of the protonated dimer and monomer were measured as a function of time for styrene (S) and propylene (P). It was found that essentially all the HS⁺2 was produced by the reaction of HS⁺ with S, but at least part of the HP⁺2 was formed by proton transfer to P₂. The absence of the analogous reaction in styrene is presumably a result of the reduced volatility of S₂.     

Free radical generation upon plasma treatment of cotton fibers and their initiation efficiency in surface-graft polymerization

Low-temperature plasma was used to activate mercerized cotton fabrics, to be followed by grafting with various methacrylates. Careful analysis of the experimental electron spin resonance (ESR) lineshapes of cotton samples treated at different RF powers made it possible to recognize and quantify four different species of free radicals still persistent 30 h after irradiation in the samples maintained under inert atmosphere. The decay rate of these species at room temperature was also evaluated with the analysis of the time evolution of the ESR spectra. The nature of the free radical species actually involved in the monomer grafting reaction has been discussed for cotton fabrics prepared under different plasma treatment conditions by analyzing the ESR lineshapes.     

Mechanical and thermo‐mechanical studies of double networks based on thermoplastic elastomers

A new approach to prepare and characterize double network elastomeric systems was investigated. A styrene‐ethylene‐co‐butylene‐styrene (SEBS) triblock copolymer system containing physical crosslinks was used to achieve a double network by additional crosslinking using ultra‐violet (UV) light. An ethylene–propylene–diene monomer (EPDM) terpolymer system containing chemical crosslinks was used to achieve a conventional double network using UV crosslinking. Properties from conventional monotonic tensile tests, dynamic mechanical analysis, and thermomechanical properties were investigated. These double network elastomers show a transition between competitive and collaborative behavior in their mechanical properties and lower coefficients of thermal expansion arising from a competition of the networks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 778–789, 2010     

双金属氧联醇盐催化环硫丙烷的开环聚合

研究了环硫丙烷以铝锌双金属氧联醇盐为催化剂在甲苯中的聚合动力学及分子量分布。结果表明,环硫丙烷的聚合速度对单体浓度是二级关系,对催化剂浓度是半级关系。聚合系统中催化剂存在缔合,认为环硫丙烷以双分子配位增长。测得聚合活化能为12.2±0.5kcal/mol,计算了单体及溶剂的链转移常数。通过淋洗液中加氯化锂的GPC工作研究了分子量及其分布随转化率的变化。     

Unconstrained geometry complexes: Ethylene/α‐olefin copolymerizations with a tetramethyldisilyl‐bridged Cp‐amido titanium complex

A new disilyl‐bridged complex, [(N‐tert‐butylamido)(3‐indenyl)tetramethyldisilyl]titanium dichloride ( 3 ), was synthesized and activated with methylaluminoxane (MAO) for propylene homopolymerization and ethylene/propylene and ethylene/1‐hexene copolymerizations. A polypropylene with a slight isotactic enrichment was obtained. The number of regioerrors present in the polypropylene was somewhat smaller than that found in most polypropylenes made from monosilyl‐bridged [(N‐tert‐butylamido)(3‐indenyl)dimethylsilyl]titanium dichloride. The regioerrors detected in the copolymers obtained from 3 /MAO were on the order of the amounts observed in polymers made with the monosilyl‐bridged constrained geometry catalysts. Ethylene copolymers of propylene and 1‐hexene had random sequence distributions and showed significant comonomer incorporation. Because of the presence of regioerrors, a modified method for determining the monomer composition and sequence distribution was developed from the direct measurement of the monomer content from the number of methylene and methine carbons per polymer chain, regardless of propylene inversion. An estimate of the error in the copolymerization reactivity ratio determination for regioirregular ethylene/α‐olefin copolymers was obtained by the calculation of the reactivity ratios from monomer dyad sequences, with consideration given to the contribution of major regioirregular sequences. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3840–3851, 2005     

Photogenerated hydroperoxides of EPDM rubbers and their characterization

Three different ethylene/propylene/diene (EPDM) rubbers were allowed to react with singlet oxygen. This reaction leads to the production of polymeric pendant hydroperoxides only in one case. Terpolymer ethylene/propylene/5-ethylidene-2-norbornene reacts with singlet oxygen and isolated and associated secondary hydroperoxides are formed. Anthracene was used as a sensitizer for production of singlet oxygen under 365-nm irradiation. The course of hydroperoxide formation was similar in the solid state as well as in the toluene solution. Reactivity of hydroperoxides prepared was tested in their reaction with gaseous dimethyl sulfide (DMS). Both the isolated and associated hydroperoxides react with DMS by dual fast and slow process. Fast process is more significant in the case of the isolated hydroperoxides. © 1995 John Wiley & Sons, Inc.