Reaction of thiol to diene polymer in the presence of various catalysts

The addition reaction of benzylmercaptan to diene polymer (natural rubber, and cis-1,4-polyisoprene) by various optically active catalysts such as d-camphorsulphonic acid, d-percamphoric acid, and active-amylalcoholate (sodium and barium) were carried out in benzene or anisole at room temperature to 100°C. The optically active adduct polymer was only obtained from the reaction of benzylmercaptan to natural rubber and cis-1,4-polyisoprene by active-amylalcoholate (barium), but was not obtained by the other catalysts. The [α]²⁵ value of optically active adduct polymer was ?0·1°C～?0·6°C (in benzene), and the optical rotatory dispersion curves were found to fit the simple Drude equation. The reaction of benzylmercaptan to cis-1,4-polybutadiene, various styrene-butadiene copolymers, and alternating butadiene-acrylonitrile copolymer were carried out, but the optically active adduct polymers were not obtained by these catalysts.     

DSC study of thermal decomposition of partially ozonized diene rubbers

The thermal decompositions of partially ozonized 1,4-cis-polybutadiene (E-BR), 1,4-cis-polyisoprene (E-IR), 1,4-trans-polyisoprene (Z-IR), 1,4-trans-polychloroprene (Z-PCh), and of polybutadiene elastomer (BR) (microstructure: 1,4-cis, 47%; 1,4-trans, 42%; 1,2, 11%) were studied. The respective thermograms were described by the presence of an intense and relatively broad exothermic peak in the 60–200°C range, which is the result of thermolysis of functional groups of the peroxide type. The measured values of the enthalpy of the reaction, normalized with respect to the amount of reacted ozone (kJ/mol O₃), were as follows: 337 (E-BR), 260, (BR), 197 (E-IR), 180 (Z-IR), and 239 (Z-PCh). Values of the activation energy and reaction order were also determined: 122.6, 118.5, 108, 113, 101.5 and 1.0, 0.96, 1.04, 1.08, and 1.25, respectively. The enthalpy values, obtained by means of differential scanning calorimetry, should be used for quantitative determination of ozonides from polydienes and polyisoprenes. © 1996 John Wiley & Sons, Inc.     

Acetylene–butadiene copolymer for polymer coatings

Low molecular weight, M?_n 1800–2400, and soluble copolymers of acetylene and butadiene were prepared by nickel naphthenate–diethylaluminum chloride catalyst. These copolymers possess high cure tendency to give insoluble and highly crosslinked films. The curing ability can be controlled by the amount of acetylene content in the copolymer and is in the following order: acetylene–butadiene copolymer > tung oil > cis-1,4-polybutadiene ? linseed oil, 1,2-polybutadiene, butadiene–isobutylene copolymer. Chemical modifications of the copolymer such as maleic reaction, metallation by lithium or sodium, graft polymerization by methyl methacrylate, 4-vinylpyridine or vinyl acetate, and epoxidation were also examined. The divinyl methylene in the copolymer gives a high cure tendency and high chemical reactivity.     

Liquid chlorine as chlorinating agent for preparation of chlorinated natural and synthetic rubbers

In order to overcome the use of solvents like carbon tetrachloride (during the industrial preparation of chlorinated natural rubber or chlorowaxes) which are suspected of damaging the layer of atmospheric ozone, I proposed the use of liquid Cl₂ as both chlorinating agent and solvent. It is shown that natural rubber or synthetic cis-1,4-polyisoprene can be swelled by liquid chlorine at ?40°C. By equilibrating to room temperature, the rubber is chlorinated by the expansion of the chlorine trapped in the rubber granules in a process resembling popcorn formation. Chlorine uptake was found to be 56.5% and the chlorinated rubber obtained was studied by FT-IR spectroscopy. Cis-1,4-polybutadiene, when chlorinated with liquid chlorine, gives a hard insoluble product with chlorine content of 36%. © 1995 John Wiley & Sons, Inc.     

Molecular dynamics simulation of cis-1,4-polybutadiene. 2. Chain motion and origin of the fast process

Molecular dynamics (MD) simulations of cis-1,4-polybutadiene in bulk amorphous state were performed to elucidate the origin of a fast relaxation process observed by quasielastic neutron scattering (QENS) measurements. The details of the torsional motion for each dihedral angle were investigated with the torsional auto- and cross-correlation functions for several temperatures in this study. Temperature dependence of the correlation between the torsional autocorrelation and cross-correlation functions is also evaluated. The origin of the fast process of cis-1,4-polybutadiene is found to be mainly the cooperative conformational transitions of two dihedral angles located at both sides of the CH₂-CH₂ bond when the bond is in the trans conformation. The cooperative conformational transitions exhibit even below the glass transition temperature of cis-1,4-polybutadiene. The cooperative motion appears at about 50 K below the glass transition temperature, corresponding to the Vogel-Fulcher temperature.     

Effects of nuclear radiations on structure and molecular motions in some crystalline stereoregular polymers

Young's modulus and the mechanical damping factor have been determined between ?180 and +280°C. (at a frequency of several kilocycles), in samples of isotactic polypropylene, isotactic polystyrene, and trans-1,4-polybutadiene, subjected to pile irradiation (γ-rays and neutrons) at γ-doses from 90 to 4000 Mrad. In isotactic polypropylene no important structural changes are produced by the irradiation, except for a partial destruction of crystallinity. The samples receiving high radiation doses exhibit a low temperature loss region, which is attributed to the formation of a certain number of branches. Isotactic polystyrene shows very slight modifications of the dynamic mechanical properties at room temperature. At low temperature an increase of intensity of the δ relaxation phenomenon (probably due to oscillations of phenyl rings) with increasing radiation dose is observed. Important structural modifications produced by the radiation, destruction of crystallinity accompanied by crosslinking, which transform the material into a crosslinked rubber, are observed in trans-1,4-polybutadiene. Unlike conventional (sulfur) vulcanization, crosslinking by radiation does not cause a marked shift of the glass transition point. A secondary low-temperature relaxation effect, not existing in the unirradiated material, appears in the mechanical loss curves of the irradiated samples; it is attributed to the formation of ? CH₂? sequences in the main chains through saturation of C?C bonds. The mechanical spectrum of irradiated polybutadiene is very similar to those shown by crosslinked ethylene–butadiene copolymers.     

Characterization of sulfur-cured styrene–butadiene copolymer rubbers and their polybutadiene blends

Dissolution of sulfur-cured, carbon black-loaded copolymers and their blends with cis-1,4-polybutadiene (PBD) are brought about by boiling with o-dichlorobenzene which contains a small amount of 2,2′-dibenzamidodiphenyl disulfide. The resulting slurries are subjected to a sequence of separations which include high-speed centrifugation to remove solids, and solvent precipitation followed by filtration to isolate the precipitates. The precipitates are washed with solvent to remove soluble organic materials followed by carbon disulfide washing to dissolve the polymers. Cast films of the polymers are obtained by evaporating the carbon disulfide washings onto sodium chloride discs. The infrared spectra of the cast films of these preparations are very similar to those of their respective polymers prior to loading and curing. Calculations for relative concentrations of bound styrene and PBD microstructures permit nominal identification of the kinds of styrene–butadiene rubber and the amounts of cis-1,4-PBD used in a cured rubber formulation. Absorption bands used are near 3.35 μ for cis-1,4-PBD, 6.65μ for bound styrene, 10.35 μ for trans-1,4-PBD; and 11.0 μ for vinyl-1,2-PBD. Efforts are being made to improve the data by using a grafting infrared instrument and also to extend the calibrations to include other rubber blends.     

Synthesis and characterization of symmetrical triblock copolymers containing crystallizable high-trans-1,4-polybutadiene

A series of symmetrical triblock copolymers containing crystallizable high-trans-1,4-polybutadiene (HTPB) were synthesized by sequential anionic polymerization of 1,3-butadiene (Bd) with isoprene (Ip) (or styrene (St)) using barium salt of di(ethylene glycol) ethyl ether/triisobutylaluminium/dilithium (BaDEGEE/TIBA/DLi) as initiation system. The microstructures of the symmetrical triblock copolymers were determined by IR, ¹H NMR, and ¹³C NMR. The results indicated that polyisoprene-block-high-trans-1,4-polybutadiene-block-polyisoprene (IBI) contained HTPB segments and medium 3,4-polyisoprene (PI) segments, and polystyrene-block-HTPB-block-polystrene (SBS) contained HTPB and atatic-polystyrene (PS) segments. The DSC analysis revealed that SBS tended to phase separate but IBI did not. The cold crystallization was observed in IBI but not in SBS.     

Synthesis of spherical trans-1,4-polyisoprene/trans-1,4-poly(butadiene-co-isoprene) rubber alloys within reactor

Trans-polydiene rubber family as high-performance tire stock possessed excellent dynamic properties, including excellent anti fatigue, low rolling resistance, low heat buildup, good green strength, and low abrasion loss. Here, Reactor Granule Technology (RGT) was introduced into the field of synthetic rubber for the first time to produce trans-1.4-polyisoprene/trans-1,4-poly(butadiene-co-isoprene) rubber alloy, which showed significant improvement in rubber synthetic technologies and great development in abundance of trans-rubber family. A series of trans-polyisoprene alloys with excellent spherical morphology were successfully synthesized by using sequential multistage polymerization. The alloy was fractionated into four fractions by temperature-gradient fractionation, and the fractionation was analyzed by ¹H NMR, ¹³C NMR, DSC and WAXD.     

Diimide reduction of cis-1,4-polyisoprene with p-toluenesulphonylhydrazide

The hydrogenation of cis-1,4-polyisoprene with diimide generated in situ from p-toluenesulphonylhydrazide (TSH), was investigated under various conditions. In aromatic solvents at 100–140°C, the rate of hydrogenation was increased with increase in concentration of polyisoprene and of TSH. Part of the polymer was depolymerized and cyclized during the reaction. Increasing the hydrogenation tended to decrease the rate of sulphur vulcanization, of the compounded rubber and the physical properties of vulcanizates were poor. The reaction of polyisoprene rubber with TSH, was also carried out in a solid state at 140°C for 20–60 min. It was found that by using a large amount of TSH hydrogenation and cyclization of rubber occurred. The quantity of TSH used as a blowing agent, for rubber in the manufacture of sponge rubber, i.e. 5–10 phr, did not cause hydrogenation.     

Synthesis and characterization of stereotriblock polybutadiene containing crystallizable high trans-1,4-polybutadiene block by barium salt of di(ethylene glycol) ethylether/triisobutylaluminium/dilithium

A series of high trans-1,4-low-cis-1,4-high trans-1,4-stereotriblock polybutadienes (HTPB-b-LCPB-b-HTPBs) were synthesized through a sequential anionic polymerization of butadiene (Bd) initiated by barium salt of di(ethylene glycol) ethylether/triisobutylaluminium/dilithium (BaDEGEE/TIBA/DLi). The polymers consisted of elastic low-cis-1,4-polybutadiene (LCPB) chemically bonded with crystallizable high trans-1,4-polybutadiene (HTPB). The block ratios (HTPB:LCPB:HTPB) were designed at 25:50:25 (molar ratio) and finally determined by SEC. The microstructures and sequences of the specimens were investigated by FTIR and NMR. The resultant HTPB-b-LCPB-b-HTPBs consisted of LCPB block with 52.5% trans-1,4 content and HTPB block with 55.9–85.8% trans-1,4 content. According to differential scanning calorimetry (DSC), HTPB-b-LCPB-b-HTPB showed a significant cold crystallization which was discussed in terms of entanglement concept. The cold crystallization temperature (T_cc) decreased whereas the melting temperature (T_m) increased with the increasing trans-1,4 content of HTPB block.     

Kinetics of graft polymerization of styrene on cis-1,4-polybutadiene

By measurements of polymerization rate, grafting efficiency and number-average molecular weight of free and grafted polystyrene, the α-dicumyl peroxide initiated polymerization of styrene on cis-1,4-polybutadiene at 100°C and at low extents of reaction was studied. The polymerization rate and the polystyrene molecular weights decreased with the rubber content of the solution. The grafting efficiency was found to be substantially independent of the peroxide concentration, but to increase with rubber content. A rigorous mathematical model of the reaction was developed, from which it has been possible to confirm the proposed mechanism and to establish the value of many kinetic constants.     

Structural characterization of vulcanizates. Part VIII. The N-cyclohexylbenzothiazole-2-sulfenamide-accelerated sulfur vulcanization of natural rubber at 140–180°C. and of synthetic cis-1,4-polyisoprene at 140°C

Vulcanization of natural rubber at 140°C. with a CBS-accelerated sulfur system of conventional type gives rise to a structurally complex network in which the number of sulfur atoms combined per chemical crosslink present increases from 12 to 21 with increasing reaction time. The complexity of the network increases with increasing temperature of vulcanization. Crosslinking of a purified synthetic cis-1,4-polyisoprene proceeds more slowly and yields a slightly more complex network. Despite this overall similarity the natural rubber vulcanizates exhibit considerably higher tensile strengths.     

Reclamation of vulcanized rubbers by chemical degradation. VIII. Absorption of oxygen and degradation of cis-1,4-polyisoprene by phenylhydrazine–iron(II) chloride system

Absorption of oxygen and degradation of cis-1,4-polyisoprene by the phenylhydrazine–iron(II) chloride system was investigated at 30°C in connection with the mechanism of reclamation of vulcanized rubbers by the system. In the presence of iron(II) chloride, phenylhydrazine rapidly absorbed an equimolar amount of oxygen and evolved an equimolar amount of nitrogen. Gas-chromatographic analysis of the reaction mixture showed the presence of benzene, phenol, and biphenyl in 37%, 35–60%, and 4–8% yields, respectively, based on phenylhydrazine. When cis-1,4-polyisoprene was added to the reaction mixture, additional absorption of oxygen was observed. Molecular weight of the polymer decreased during the oxygen absorption, and the scission efficiency (i.e., number of mole scissions/mole oxygen) was 0.14–0.26.     

Crystalline structures and thermal properties of poly(ethylene-co-α,ω-nonconjugated diene)s prepared by zirconocene catalysts

Crystalline structures and thermal properties of poly(ethylene-co-α,ω-nonconjugated diene)s, [diene=1,5-hexadiene (HD), 1,7-octadiene (OD), and 1,9-decadiene (DD)] have been investigated in relation to insertion mode of the dienes. In the case of poly(ethylene-co-HD), the copolymer containing high cis-1,3-cyclopentane units shows lower melting point depression with increasing the comonomer content than the copolymers containing high trans-1,3-cyclopentane units. In the case of poly(ethylene-co-OD) and poly(ethylene-co-DD), the copolymers containing pendant vinyl groups show higher ΔH_m than that of the copolymers with cyclic units or branching structures. Thermal degradation of the copolymers has been investigated under nitrogen atmosphere and the degradation of the copolymers containing the cyclic structures begins at lower temperature than the copolymers containing pendant vinyl groups.     

Differential thermal analysis using high frequency dielectric heating II. Curing kinetics studies

A previous paper described the theory and equipment of Differential Thermal Analysis using High Frequency Dielectric Heating, DTA/HF. Curing studies using DTA/HF on cis-1,4-polyisoprene rubber filled with 50 phr of CaCO₃ and containing from 1.5 to 4.5 phr of dicumyl peroxide (DCP) curative indicated that below about 185°C, the curing reaction was first order with respect to DCP; the mean activation energy was 32.6 kcal/mole; and the heat of reaction ranged from 60 to 80 kcal/mole DCP. These results are in agreement with published results. Above 185°C both thermodynamic and kinetic evidence implied that the reaction mechanism changed; the first order peroxide decomposition no longer controlled the overall rate of reaction. The curing of both stereo styrene-butadiene rubber (SBR) and cis-1,4-polybutadiene rubber (BR) containing 50 phr of CaCO₃ and 0.5 phr of DCP was found to follow first order kinetics as expected. The magnitude of the heat of curing was used to determine the frequency of a vinyl propagation-type cross-linking reaction. Eight to 36 crosslinks per molecule of DCP were obtained. This reaction became more extensive at high temperature, in agreement with published results.     

Synthesis and characterization of bioactive molecules grafted on poly(?-caprolactone) by “click” chemistry

A facile and efficient strategy to graft bioactive molecules (nicotinic acid, p-aminobenzoic acid, and phthaloyltryptophan) onto poly(?-caprolactone) (P(?CL)) was achieved by copper-catalyzed Huisgen’s 1,3-dipolar cycloaddition known as click reaction. P(αCl?CL), with 10, 20, and 30% of α-chloro-?-caprolactone (αCl?CL) units were copolymerized by ring opening polymerization using ?CL and αCl?CL as starting materials in the presence of 1,4-butanediol and Sn(Oct)₂. Subsequently, the chloride pendent was converted to azide followed by cycloaddition with terminal alkyne derivatives of the aforementioned bioactive molecules. The complete addition was accomplished at all ratios. The characteristic molecular features of these copolymers were evaluated by FTIR, NMR, and GPC. Thermal analysis data indicated that the grafted compounds led to polymorphic alteration and different pattern of thermal degradation depending on the molecular structure and the size of the grafted compounds. They are the basis for further development of grafted copolymer as drug delivery carriers.     

Head-to-head polymers: 19. Chlorination of cis-1,4-polybutadiene

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH₂CHCICHCICH₂units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.     

Strain-induced crystallization of cis-1,4-polybutadiene containing dispersed 1,2-polybutadiene crystalline particles

Some grades of cis-1,4-polybutadiene contain dispersed crystalline particles made up of a block copolymer having amorphous cis-1,4- and crystalline 1,2 blocks. The particles are known to enhance the strain-induced crystallization of cis-1,4 matrix rubber. The deformational behavior was examined by dynamic shear measurements at small deformation and tensile stress–strain measurements at large deformation. In the shear measurements (linear behavior), the temperature dependence of the shift factor in the time-temperature superposition has been evaluated. The higher temperature dependence was observed for the lower crystalline particle content and higher degree of branching of the matrix rubber. The presence of the crystalline particles resulted in the viscosity enhancement like that expected from the dispersed particles. In the tensile measurements (non-linear behavior), the rubbers showed strain softening. The higher degree of strain softening was observed for the higher amount of the crystalline particles and lower degree of branching. The strain softening is a result of the crystalline particles facilitating the elongation. Because these particles posses the branches which are cis-1,4 chains of the block copolymer, the branches are lubricating the system during the stretching. The length of the branches must be short enough so as to produce no significant entanglement constraint. This observation is in accord with the previous one that a relatively long branch gives strain hardening, whereas a relatively short branch gives strain softening. The strain softening was found to enhance the strain-induced crystallization. This conclusion is opposite to what one might expect from the entanglement constraints by the long branches, forcing the orientation of the chains, and thus enhancing the strain-induced crystallization. © 1996 John Wiley & Sons, Inc.     

Green Process for Natural Rubber Latex Hydrogenation via Metathesis

Natural rubber (NR) is an important renewable polymeric material which contains cis-1,4-polyisoprene as a major component. A new approach for a green hydrogenation process has been developed in this research work. This metathesis/hydrogenation method has less detrimental environmental impact and provides improved thermal stability of NR.