Synthesis and characterization of star-comb styrene/butadiene copolymer

<正>A novel star-comb styrene/butadiene copolymer(SC-SBC) was synthesized by anionic polymerization and grafting reaction with epoxidized star liquid polybutadiene(ESPB) as coupling agent.The overall shape of the star-comb macromolecules can be altered by changing the molecular weight and number of the side chain.The molecular parameters and mechanical properties of the SC-SBC resins were investigated.The notched izod impact strength of the SC-SBC resins are excellent and reach as high as to 239 J/m.     

机理转移法合成星形梳状聚丁二烯-g-聚甲基丙烯酸甲酯共聚物的研究

结合活性负离子聚合与原子转移自由基聚合(ATRP),采用机理转移法制备了一系列窄分布且分子量可控的星形梳状聚丁二烯-g-聚甲基丙烯酸甲酯接枝共聚物(SC-(PB-g-PMMA)).首先通过阴离子聚合,制备星形聚丁二烯,后经甲酸-过氧化氢原位环氧化对链中部分双键进行环氧化,再与原位生成2-溴异丁酸发生酯化反应,得到具有链中活性溴的星形大分子引发剂(SPB-Brn).然后,利用该大分子引发剂,采用CuCl/CuCl2/PMDETA催化体系,通过ATRP聚合单体MMA,合成出星形梳状SC-(PB-g-PMMA)聚合物.通过GPC,1H-NMR和FTIR等分析手段对合成的星形大分子引发剂及星形梳状聚合物进结构表征,证实得到目标产物,并同时研究了聚合物的热力学性质与溶液性质.     

Synthesis of low polydispersity polybutadiene and polyethylene stars by convergent living anionic polymerization

Star‐shaped polybutadiene stars were synthesized by a convergent coupling of polybutadienyllithium with 4‐(chlorodimethylsilyl)styrene (CDMSS). CDMSS was added slowly and continuously to the living anionic chains until a stoichiometric equivalent was reached. Gel permeation chromatography‐multi‐angle laser light scattering (GPC‐MALLS) was used to determine the molecular weights and molecular weight distribution of the polybutadiene polymers. The number of arms incorporated into the star depended on the molecular weight of the initial chains and the rate of addition of the CDMSS. Low molecular weight polybutadiene arms (M_n = 640 g/mol) resulted in polybutadiene star polymers with an average of 12.6 arms, while higher molecular weight polybutadiene arms (M_n = 16,000 g/mol) resulted in polybutadiene star polymers with an average of 5.3 arms. The polybutadiene star polymers exhibited high 1,4‐polybutadiene microstructure (88.3–93.1%), and narrow molecular weight distributions (M_w/M_n = 1.11–1.20). Polybutadiene stars were subsequently hydrogenated by two methods, heterogeneous catalysis (catalytic hydrogenation using Pd/CaCO₃) or reaction with p‐toluenesulfonhydrazide (TSH), to transform the polybutadiene stars into polyethylene stars. The hydrogenation of the polybutadiene stars was found to be close to quantitative by ¹H NMR and FTIR spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 828–836, 2006     

Preparation and characterization of spherical polymer packings from polybutadiene for size-exclusion chromatography

Porous polymer spherical particles for column packings in nonaqueous size-exclusion chromatography (SEC) were prepared from 1,2-syndiotactic polybutadiene by suspension and evaporation method. The polymer microbeads obtained were crosslinked by radical reaction between 2-vinyl groups in polybutadiene with ultraviolet radiation, to render them insoluble. These microbeads have wider chromatographic separation width than polystyrene column packings. In addition, the polybutadiene microbeads did not show the excessive retention observed with commercial polystyrene columns for polycyclic aromatic compounds. Therefore, a close correlation between the elution volume and M, for polycyclic aromatic compounds was observed with polybutadiene microbeads columns.     

Etude de copolymères ABS (acrylonitrile–butadiène–styrène): Solvatation préférentielle du polybutadiène par les promoteurs

ABS resins formed by copolymerization of styrene and acrylonitrile (AN) in presence of polybutadiene, consist of a mixture of SAN graft copolymer on polybutadiene (PBut) and of ungrafted SAN copolymer (styrene-co-acrylonitrile). The kinetic study was completed by showing a preferential solvation of polybutadiene by the initiator. This solvation effect was studied as a function of the concentration ratio SAN/PBut and in relation with the type of initiator. The adsorption of initiator appeared to be maximum when its solubility parameter (σ) is close to that of polybutadiene. As a function of the polybutadiene characteristics, this selective adsorption can be given by where I₁ is the quantity of initiator in the polybutadiene medium, I is the total amount of peroxide, [PBut] is the concentration of polybutadiene, and M?_n its molecular weight. It has been shown furthermore that the preferential solvation of polybutadiene by the benzoyl peroxide can be increased by addition of SAN or acrylonitrile. The consequences of this solvation effect on the characteristics of the grafting reaction, more precisely on the molecular weight of grafted and ungrafted SAN and on the rate of polymerization, were examined.     

丁腈橡胶标准物质的1H-NMR表征

应用１Ｈ－ＮＭＲ技术对系列丁腈橡胶（ＢＮＲ）标准物质的结构进行了表征。测定了丁腈橡胶标准物质中聚丁二烯链段中的顺式和反式结构含量、聚丁二烯链段中１,４加成聚合与１,２加成聚合的含量以及丁腈橡胶标准物质中结合丙烯腈的含量,测定的最大相对偏差为８．３％。     

Recycling of ABS and PC from electrical and electronic waste. Effect of miscibility and previous degradation on final performance of industrial blends

The aim of this work, within the framework of polymer recycling, is to upgrade waste from electrical and electronic equipment. Blends of the two major residues were prepared via a melt blending process. These are ABS consisting of a SAN thermoplastic matrix with a dispersed elastomeric (polybutadiene rubber) component and polycarbonate (PC). The effect of partial miscibility and previous degradation levels was investigated. Mechanical characterization of ABS/PC systems was carried out to determine the optimum composition range. Previous degradation levels of the two wastes were investigated by FTIR and little degradation was found on ABS due to the presence of a polybutadiene rubber which is more sensitive to thermo-oxidative processes but no significant degradation was found on PC. Differential scanning calorimetry (DSC) tests demonstrated certain miscibility between the two components by identifying two glass transition temperatures. This partial miscibility, together with the small degradation of the elastomeric component, contributes to a low interaction promoting a decrease on mechanical performance. Scanning electron micrographs (SEM) showed the system morphology and certain lack of adherence along SAN/polybutadiene interface related to degradation of polybutadiene spheres which act as stress concentrators. The use of the equivalent box model (EBM) allowed to quantify the interaction level by determining an interaction/adherence parameter “A”, which turned to be lower than 1 and corroborated the lack of interaction.     

Radical graft polymerization onto composite particles of polydimethylsiloxane and polybutadiene

Submicron-size composite polymer particles consisting of polydimethylsiloxane/core and polybutadiene/shell were synthesized by seeded emulsion polymerization. The morphologies of composite particles were affected by polybutadiene ratio in the composite particles. Highly grafted polymer by poly(styrene-co-acrylonitrile) could be prepared by using the composite particles containing polybutadiene with polymerizable group. The morphologies of the grafted polymer were influenced by the morphologies of composite particles and the kinds of grafting initiators. It was found that surface gloss and lubricity of the graft polymers were influenced by morphologies of composite particles.     

Anionic polymerization. III. Polymerization of butadiene with alkali metal alkoxide-modified alkali metal system

A high molecular weight polybutadiene was prepared in hexane solvent by using alkali metal (Li, Na, K) and metal tert-butoxide (Li, Na, K) as a polymerization initiator. The microstructure of polybutadiene varies, depending on the type of modifiers and polymerization and temperatures. The results and mechanistic implications of this study are discussed.     

Morphology and grafting reactions in core/shell latexes

The particle morphology and percent grafting were investigated as a function of the crosslink density of the seed latex in two systems of core/shell latexes of polybutadiene/polymethyl methacrylate (PB/PMMA) and styrene–butadiene rubber/polymethyl methacrylate (SBR/PMMA) prepared by seeded emulsion polymerization at 50°C. The thin layer chromatography/flame ionization detection (TLC/FID) technique was used to characterize the grafting efficiency of the core/shell latexes. The percent grafting of the shell polymer was found to decrease with increasing the crosslink density of the core material. The particle morphology and precent grafting were also investigated as a function of composition and structure of the core material in four core/shell latex systems: polybutadiene/styrene–acrylonitrile copolymer (PB/SAN), (styrene-butadiene) random copolymer/styrene acrylonitrile copolymer (S:B/SAN), polystyrene : polybutadiene/styrene-acrylonitrile copolymer (PS:PB/SAN) and Kraton/styrene-acrylonitrile copolymer (Kraton/SAN), which were prepared by direct emulsification for the seed followed by emulsion polymerization at 70°C for the shell polymer. Grafting and crosslinking of the core material were found to be competitive reactions depending on the microstructure of the seed latex.     

Hydroxy and Di-Hydroxy End-Capped Polybutadiene as Reactive Steric Stabilizers for the Synthesis of Polyurethane Particles in Organic Dispersant Media

Summary: The synthesis of polyurethane particles by polyaddition of ethylene glycol (EG) and tolylene-2,4-diisocyanate (TDI) in cyclohexane at 60 °C was investigated in the presence of ω-hydroxy and ω,ω′-dihydroxy polybutadiene, used as reactive steric stabilizers. The effect of the functionality and concentration of the reactive polybutadiene, as well as the monomer addition procedure, onto the polyurethane particle formation was studied. Calibrated PUR particles with an average diameter in the range 1–2 µm could be readily obtained.     

聚丁二烯1,2-结构含量和SBS中聚丁二烯段1,2-结构含量的调节

以正丁基锂为引发剂,环己烷为溶剂,研究了四氢呋喃(THF)对聚丁二烯1,2-结构和丁苯嵌段共聚物SBS中聚丁二烯段1,2-结构含量的影响,指出在一定温度下,聚丁二烯1,2-结构含量与体系中THF的浓度有指数关系。控制体系中THF的浓度和聚合反应温度,可调节聚合产物中聚丁二烯1,2-结构含量。     

Cationic polymerization of α-methylstyrene from polydienes. I. Synthesis and characterization of poly(butadiene-g-α-methylstyrene) copolymers

The preparation of poly(butadiene-g-α-methylstyrene) copolymers was investigated with three different alkylaluminum coinitiators. The alkylaluminum compounds in conjunction with polybutadiene which contained a low concentration of labile chlorine atoms initiated the polymerization of α-methylstyrene to produce graft copolymers. Trimethylaluminum gave higher grafting efficiencies than diethylaluminum chloride at comparable monomer conversions. Triethylaluminum produced only very low monomer conversions (<5%), even at long reaction times, and for this reason was not studied extensively. The number of grafts per polybutadiene backbone was determined for a number of copolymers and found to increase slightly as the allylic chlorine concentration in the polybutadiene backbone was increased. In all cases, however, only a low percentage of the available labile chlorine sites along the polybutadiene backbone resulted in grafted α-methylstyrene side chains. The addition of small quantities of water to the polymerization solvent greatly enhanced the grafting rate and ultimate monomer conversion during the synthesis of these poly(butadiene-g-α-methylstyrene) copolymers. The mechanistic role of water during these grafting reactions is unknown at the present time.     

Filler-filler interaction and filler-polymer interaction in carbon black and silica filled ExxproTM polymer

Due to the presence of reactive benzylic bromide, Exxpro has much better interaction with silica in comparison with polybutadiene as demonstrated by the high bound rubber level. The better silica/Exxpro interaction is further substantiated by the low degree of filler network formation in comparison to that observed for silica filled polybutadiene as demonstrated by the much smaller deviation of low strain shear modulus from the Guth-Gold relationship for the silica filled Exxpro. Silane treatement of silica reduces filler network formation in polybutadiene but has only slight effect on silica filled Exxpro indicating that even without silane treatment silica already disperse well in Exxpro due to high degree of filler/polymer interaction. This result in silica filled Exxpro compound exhibiting better processability (lower shear viscosity) as well as dynamic performances for tire applications (higher tan δ at −20 and 0°C, lower tan δ at 60°C). We speculate that nucleophilic substitution reaction takes place between benzylic bromide and surface hydroxide group of silica.     

Sorption and diffusion of ethanol vapor in polybutadiene/acrylonitrile, polybutadiene/styrene and polybutadiene based polyurethanes

The sorption and diffusion behavior of ethanol vapor in series of polyolefine based polyurethanes (PU) made from hydroxyl-terminated polybutadiene/acrylonitrile (HTBN), hydroxyl-terminated polybutadiene/styrene (HTBS) and hydroxyl-terminated polybutadiene (HTPB) were investigated by using the quartz-spring, DSC, FTIR and AFM. The equilibrium absorption reduced with increasing content of hard segments for all the three types of PUs. The values of the maximum absorption were in the order of HTBN > HTBS > HTPB based PU and related to their composition. The non-Fickian diffusion was confirmed and the sorption was discovered mainly in the hard segments. The HTBN based PU revealed different sorption and diffusion behavior from the other two, which was resulted from its hydrogen bonding not only between ethanol and hard segments but also soft segments. The morphologies of PUs before and after ethanol absorption were also compared. The HTBN based PU showed the most evident phase re-congregation after ethanol absorption.     

Telechelic sulfate ionomers. I. Preparation and solution and thermal properties

New telechelic ionomers with zinc and sodium sulfate salt terminal groups on hydrogenated polybutadiene (HPB) backbones ( I ) were prepared from hydroxyl-terminated hydrogenated polybutadiene (HTHPB) of three different molecular weights (1350, 2100, and 3200 g/mol). Quantitative acid-base titration, elemental analysis, and NMR spectroscopy were used to verify the structure, and further characterization included differential scanning calorimetry (DSC) and solution viscometry. The DSC results indicated that the ionomers are free of impurities within the limit of the resolution of the method. Glass transition temperatures determined by DSC indicated that the elevation in glass transition temperature by ionic crosslinking was most strongly dependent on the molecular weight of the backbone of the telechelic ionomer. The solution viscometry results showed that the sulfation reaction did not cause either covalent crosslinking or chain scission. Furthermore, the solubility characteristics of the sulfate-terminated hydrogenated polybutadiene (STHPB) oligomers were shifted towards a preference for polar solvents by the presence of salt groups. The lower molecular weight ionomers of the series showed polyelectrolyte-like extension at very dilute concentrations in polar solvents. The onset of polymer gelation in hexane was observed for the ionomers which had the highest molecular weight backbones.     

Polybutadiene latex particle size distribution analysis utilizing a disk centrifuge

Polybutadiene latexes made in emulsifier-free emulsion polymerization with diameters ranging from 50 to 300 nm of both unimodal and bimodal particles size distributions were analyzed by the line-start (LIST) method in a Brookhaven Disk Centrifuge Photosedimentometer (DCP). A special spin fluid was designed to be able to sediment polybutadiene since the density of the polymer is 0.89 gcm^–3 and is thus less dense than its suspending medium. Density and viscosity gradients were created simply by adding five different mixtures of ethanol, water, and emulsifier in density sequence to the spinning disk. Coagulation problems caused by diluting polybutadiene latices with ethanol were overcome by using nonionic Triton X-100 surfactant. Good agreement in the average particle size and distribution as well as polydispersity between transmission electron microscope and disk centrifuge data was accomplished. The analysis time for polybutadiene latex particle sizing thus was reduced from several days to approximately 1 h.     

Investigation of reactions in carboxyl-terminated polybutadiene and tris-[1-(2-methyl)aziridinyl] phosphine oxide

The functionalities of a series of carboxyl-terminated polybutadiene samples (CTPB) were calculated from an infrared spectroscopic study of the samples reacting to the gel point with tris-[1-(2-methyl)aziridinyl] phosphine oxide (MAPO), Epon X801, and glycerol. Identical functionalities were calculated when Epon X801 and glycerol were used as curing agents. Higher functionalities for CTPB with MAPO were due to additional reactions that MAPO underwent with hydroxyl groups and water, present in carboxyl-terminated polybutadiene, and with itself (homopolymerization). Rate constants were calculated for the homopolymerization of MAPO in Nujol, in nonfunctional polybutadiene, and in CTPB. The homopolymerization resulted in an increase and then a gradual decrease in MAPO functionality, which was in agreement with that predicted from theoretical considerations.     

Synthesis and characterization of amino-terminated telechelic polybutadiene

Butadiene was polymerized with water-soluble 4,4′-azobis(amidinopropane)dihydrochloride initiator in an ethanol-water medium at 60°C. Important variables, such as the initiator concentration, monomer concentration, solvency, and polymerization time and temperature were studied. ¹³C-NMR studies showed that no observable chain transfer to ethanol occurred during the polymerization. The conversion of monomer to polymer was significantly increased while maintaining a relatively narrow molecular weight distribution by intermittent feed of the initiator. The amidino end-groups of the polymer were transformed into amino groups by reduction using lithium aluminum hydride in THF, so that amine-terminated polybutadiene was obtained. The amino functionality of the polybutadiene was determined by titration to be 2.0. © 1995 John Wiley & Sons, Inc.     

用新型茂钛催化剂制备的苯乙烯/丁二烯嵌段共聚物的结构表征

用CpTi(OBz)3/MAO催化体系合成的苯乙烯／丁二烯嵌段共聚合产物经丁酮、甲苯、四氢呋喃、氯仿连续抽提,并用已烷对丁酮的可溶级分进行再抽提;不同级分分别用GPC、^13C -NMR、DSC和WAXD等手段进行分析和表征。发现嵌段共聚物主要存在于氯仿可溶级分中,丁酮可溶级分基本上是无规聚苯乙烯和聚丁二烯组成的混合物（己烷可溶级分为聚丁二烯,不溶级分为无规模聚乙烯）。GPS谱图表明该嵌段共聚反应具有单催化活性中心的聚合特征,^13C-NMR谱图显示该嵌段共聚物分子链由间规聚苯乙链段和聚丁二烯链段组成,WAXD图谱显示嵌段共聚物有较高的结晶度。