A Novel Process for Ultrasound‐Induced Radical Polymerization in CO2‐Expanded Fluids

Summary: A strong viscosity increase upon polymerization hinders cavitation and subsequent radical formation during an ultrasound‐induced bulk polymerization. In this work, ultrasound‐induced radical polymerizations of methyl methacrylate (MMA) have been performed in CO₂‐expanded MMA in order to reduce the viscosity of the reaction mixture. For this purpose, the phase behavior of CO₂/MMA systems has been determined. With temperature oscillation calorimetry, the influence of CO₂ on the viscosity and on the reaction kinetics of ultrasound‐induced polymerizations of MMA has been studied. In contrast to polymerizations in bulk, this technique shows that a low viscosity is maintained during polymerization reactions in CO₂‐expanded MMA. As a consequence, a constant or even increasing polymerization rate is observed when pressurized CO₂ is applied. Moreover, the ultrasound‐induced polymer scission in CO₂‐expanded MMA is demonstrated, which appears to be a highly controlled process. Finally, a preliminary sustainable process design is presented for the production of 10 kg/h pure PMMA (specialty product) in CO₂‐expanded MMA by ultrasound‐induced initiation.

Process flow diagram of the ultrasound‐induced polymerization of MMA in CO₂‐expanded MMA.     

Preparation of Nano‐Polyethylene Fibers and Floccules by Extrusion Polymerization Under Atmospheric Pressure Using the SBA‐15‐Supported Cp2ZrCl2 Catalytic System

Summary: Nano‐polyethylene fibers and floccules were prepared under atmospheric pressure via ethylene extrusion polymerization in suit, using the SBA‐15‐supported Cp₂ZrCl₂ catalytic system. The major morphology units in the samples were fibers and floccules. The diameter of the single nano‐fibers was 120–200 nm. The single nano‐fibers could aggregate to form fiber aggregates and bundles. The number of PE floccules increased with extension of polymerization time, while the melting point of PE with nano‐fibers was little higher than that of common polyethylene.

SEM micrograph of the nano‐polyethylene fibers produced at a polymerization time of 60 min: micro‐fibers and floccule surface morphologies.     

Inhomogeneity Effects in Vapor Phase Polymerized PEDOT: A Tool to Influence Conductivity

Low‐MW urethanes were investigated to control domain formation as well as inhibiting cleavage reactions during vapor phase polymerization of PEDOT. A diurethanediol (DUDO) was identified as a highly efficient mediator for the process, resulting in PEDOT films exceeding conductivities of 1 000 S · cm^?1. All the urethanes investigated had the desired inhibiting effect on the polymerization, but all apart from DUDO also introduced unwanted domain formation on the micrometer scale. The addition of PEG generally improved conductivity by suppressing the domain formation and, with an optimized combination of DUDO and PEG, conductivities over 1 200 S · cm^?1 were achieved.

     

Kinetic and Thermodynamic Studies of Emulsion Polymerization of a Sugar Monomer by Calorimetry with Compensation Heating and Differential Cooling

The kinetic and thermodynamic features of free‐radical batch emulsion polymerization of a sugar monomer (3‐MDG) and butyl acrylate (BA) were investigated in a power compensation calorimeter. The homopolymerizations as well as the copolymerization have been studied. The overall activation energy of 3‐MDG homopolymerization was 140 ± 3.8 kJ · mol^?1, the polymerization enthalpy was ΔH_MDG = ?51.6 ± 1.9 kJ · mol^?1 and the calculated adiabatic temperature rise was ΔT_ad = 78.5 K. The effects of the initiator and the emulsifier concentrations on the 3‐MDG/BA batch copolymerization kinetics and on the colloidal properties of the final sugar latexes were studied at 60 °C. At higher emulsifier and initiator concentration, respectively, the polymerization rate increases and the particle size decreases, but the trends do not conform to the Smith‐Ewart theory. Polydisperse sugar latex particles with a mean diameter in the range of 50–67 nm were obtained.

Relationship between the activation energy and the conversion for BA (open symbols) and 3‐MDG (solid symbols).     

Long‐Aliphatic‐Segment Polyamides: Salt Preparation and Subsequent Anhydrous Polymerization

Long‐aliphatic‐segment polyamides were prepared based on hexamethylenediamine and α,ω‐(CH₂)_x biosynthetic diacids (x = 10, 11, 12). The pertinent monomers (salts) were isolated as solids, thoroughly characterized for the first time, and then submitted to an anhydrous melt prepolymerization technique. The obtained prepolymers exhibited in the range of 5 100–11 800 g · mol^?1, and the molecular weight was further increased by up to 55% through solid‐state finishing. The suggested overall polyamidation cycle was conducted at short melt‐reaction times, so as to avoid any thermal degradation, and was proved efficient, indicating similar reactants polymerizability independently of the methylene content.

     

Co(acac)2‐Mediated Radical Polymerization of Acrylonitrile: Control Over Molecular Weights and Copolymerization With Methyl Methacrylate

The cobalt‐mediated radical polymerization of acrylonitrile in DMSO using cobalt (II) acetylacetonate [Co(acac)₂] as mediator is studied. Both the evolution of molecular weight and conversion over time under various conditions are monitored. Molecular weights increase sharply at the beginning of the reaction and subsequently grow linearly with conversion. No branching of the polymer is observed by ¹³C NMR. By a careful design of the reaction parameters, number‐average molecular weights >1.2 · 10⁵ g · mol^?1 with a PDI around 2.4 together with conversions of up to 90% within 24 h are achieved. The copolymerization parameters of acrylonitrile with methyl methacrylate in DMSO at 30 °C are determined using the Kelen‐Tüdõs approach giving r_AN = 0.33, r_MMA = 0.71.

     

Comparison of Olefin Polymerization Processes with Metallocene Catalysts

Summary: Solution and gas phase processes of the polymerization of ethene are compared using new types of pentalenyl bridged ansa‐metallocenes such as [Me₃Pen(Flu)]ZrCl₂. As of the bridge, the catalyst system is remarkable thermostable up to 105 °C and a deactivation of the metallocene on the silica support can be suppressed. Compared to the non‐supported catalyst in a solution process, the application of the heterogenized system in a gas phase process leads to a decrease in activities while molar masses of the polyethenes are similar. Due to a higher degree of short chain branches of 20–30 per 1 000 carbon atoms instead of 10–17, the melting temperatures are 10 °C lower than those for polymers obtained in the solution process.

Basic structure of the here used pentalenyl bridged ansa‐metallocenes.     

Comparison of Gas and Liquid Propylene Polymerization Technique – Hydrogen Effect on Thermal,Rheological, and Morphological Properties of PP

Summary: A comparison of PP qualities, which are produced with two different polymerization techniques–gas phase(GP) and liquid pool (LP)–under precise control of the polymerization temperature (70 °C) and pressure (GP = 25 bar, LP < 60 bar) using identical Ziegler‐Natta catalyst (TiCl₄/phthalate/MgCl₂ + TEA/silane), is presented. A series of homopolymer PP in a wide MW range from 100 000 to 1 600 000 g · mol^?1 was polymerized. During polymerization all samples were characterized exactly by their Rp‐profil. The effect of hydrogen on the initial reaction rate and on MW and MWD was analyzed on the basis of this so‐called kinetic fingerprint. The results showed that the polymerization rate reached a maximum for LP, of about 150 kg · g_cat^?1 · h^?1, in contrast to GP with a maximum of R_p,₀ = 45 kg · g_cat^?1 · h^?1. Analysis was carried out by means of GPC, SEM, DSC, platte‐platte rheometer, and WAXS. The results first showed that the MWD of LP PP is narrower (PD ～ 6.8) than for the GP PP (PD ～ 8), polymerized in two steps. An SEM study of the powder particle shows the typical dent surface morphology of polymers using Ziegler‐Natta catalysts for polymerization. WAXS and DSC analysis demonstrated that almost only the α‐modification of crystalline structure exists and that the crystallinity becomes considerably higher after solidification from melt. Furthermore, it was found that the crystallite size distribution depends on the polymerization technique. Rheological studies indicate that GP PP behaves more elastically. To summarize, it is shown that PP produced with the LP polymerization technique is more homogenous and of high quality.

Particle geometry of gas phase and liquid pool polymerized PP powder observed by SEM (PP‐L0).     

Metallocene‐Catalyzed Solution Polymerization of Ethene at Elevated Pressure

The kinetic of ethene polymerization catalyzed by (ⁿBuCp)₂ZrCl₂/AlⁱBu₃/[Me₂PhNH]⁺[B(C₆F₅)₄]^? has been investigated at 100 and 140 °C at pressures from 2 to 7 MPa. The initial polymerization rate R_p0 increases linearly with increasing catalyst concentration, whereas a second‐order dependence of R_p0 on the ethene concentration is found the number‐average molecular weight M _n increases with increasing ethene pressure (ethene concentration). The relation between M _n and ethene concentration can be explained by an equation based on a kinetic model involving a single center, two‐state catalyst system.

Influence of the Zr concentration on the initial polymerization rate R_p0. p_Ethene = 7 MPa, solvent (toluene/ethene) = 275 mL.     

Artificial Opals as Effect Pigments in Clear‐Coatings

Summary: In this paper, we describe the use of artificial opals from polymer beads as effect pigments in transparent industrial and automotive coatings. For this purpose, we synthesized monodisperse colloids from fluorinated methacrylates by surfactant‐free emulsion polymerization. The fluorinated monomers, in combination with crosslinking, lead to a refractive index contrast, thermal stability, and solvent resistivity necessary for use as effect pigments. After crystallization of the monodisperse polymer beads, crystal flakes with iridescent colors can be obtained. The crystal flakes can act as effect pigments in various transparent industrial and automotive coatings. Due to photonic crystal behavior of effect pigments, color flops up to 100 nm are observed.

Crystal flakes of CS ‐7 as effect pigments in a transparent coating. The diameter of the tube is 5 mm.     

The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Effect of Cyclic Deformations on the Dynamic‐Mechanical Properties of Silica‐Filled Butyl Rubber

The effect of the chemical modification of the silica surface by the silane coupling agent (Si69) on both the real and the imaginary parts of the shear compliance (J′, J″) on silica‐filled butyl rubber vulcanizates was investigated in a wide temperature and frequency range, ?70 to 120 °C and 10^?4 to 10 Hz, respectively. In addition, the stress‐strain measurements, DSC, and TEM were carried out. Moreover the effect of stress‐strain cyclic deformation up to ten times with maximum deformation 80% of the elongation at break on J′, J″ is also studied. It was found that the filler network recovers after cyclic stress‐strain in a time scale of one year at room temperature.

Transmission electron photographs of the butyl rubber [IIR] vulcanizates: (a) IIR, unfilled, (b) IIR, filled with 20 phr SiO₂, (c) IIR,filled with 20 phr SiO₂ + 1.6 phr Si69.     

Fire Retardance in Poly(butylene terephthalate). The Effects of Red Phosphorus and Radiation‐Induced Cross‐Links

Summary: The combustion performance of poly(butylene terephthalate) (PBT) can be improved by the addition of red phosphorus provided it is intermolecularly cross‐linked upon irradiation with ⁶⁰Co γ‐rays in the presence of triallyl cyanurate (TAC). At a content of 3 or 4 wt.‐% the latter significantly promotes cross‐linking in the presence of air. From combustion tests with samples containing red phosphorus (P_red) and having been γ‐irradiated in the presence of TAC it turned out that an improved fire resistance of PBT is achieved if the red phosphorus content is at least 12.5 wt.‐%. In this case test samples were self‐extinguishing and the UL 94 rating corresponded to V‐1. Product analysis and thermal gravimetric analysis revealed that P_red stimulates aromatization and charring. These processes involve the reaction of P_red with the polymer. ³¹P NMR spectroscopy revealed that the residue contained chemically bonded phosphorus.

Decomposition of anhydride groups resulting in phenyl radicals.     

PTFE Micropowder Functionalized with Carboxylic Acid Groups

PTFE powder irradiated in air at room temperature was studied by infrared spectroscopy, potentiometric titration with sodium hydroxide, and polyelectrolyte titration with poly(diallyl dimethylammonium chloride). Through the radiation‐induced degradation ? COF groups are formed in the material, which can be hydrolyzed to ? COOH groups. About 10–20% of the ? COOH groups are located at the surface of the PTFE particle. The ? COOH groups start to decompose under oxidizing conditions at temperatures above 200 °C. The decarboxylation results in the formation of ? CF?CF₂ groups, which are oxidized to ? COF groups in the presence of air.

     

Polymerization of Cyclic Monomers, 12

Summary: The radical polymerization of different substituted methyl 2‐(bicyclo[3.1.0]hex‐1‐yl) acrylates, 1a – f , was initiated by 2,2′‐azoisobutyronitrile (AIBN) at 65 °C in chlorobenzene. The radical homopolymerization of 1a – f occurred through the opening of the cyclopropane ring, and lead to polymers with number‐average molecular weights of 13 000 to 434 400 g · mol^?1 and glass transition temperatures between 77 and 121 °C. The monomers 1a – f showed a similar reactivity to MMA (in the copolymerization with MMA). Selected monomers were determined to be diluent monomers for dental filling composites and enable the preparation of composites that show a significantly reduced polymerization shrinkage, compared to composites based on dimethacrylate diluents.

     

Intercalated Polycarbonate/Clay Nanocomposites: Nanostructure Control and Foam Processing

Intercalated polycarbonate (PC)/clay nanocomposites (PCCN)s have been prepared successfully through the melt intercalation method in the presence of a compatibilizer. The internal structure and morphology of the PCCNs has been established by using wide‐angle X‐ray diffraction (WAXD) analyses and transmission electron microscopic (TEM) observations. The morphology of these nanocomposites and degradation of the PC matrix after nanocomposites preparation can be controlled by varying surfactants used for the modification of clay and compatibilizer. The intercalated PCCNs exhibited remarkable improvements of mechanical properties when compared with PC without clay. We also discuss foam processing of one representative PCCN using supercritical CO₂ as a foaming agent.

TEM bright field image of intercalated polycarbonate/synthetic fluorohectorite nanocomposite.     

The Solid State Postcondensation of PET, 4

Summary: A new method of polymerising PET in the solid state is proposed in either a gas phase reactor, or in hydrocarbon dispersion. It is shown that the reaction can be carried out efficiently at temperatures on the order of 200–240 °C directly from a prepolymer without the need for a melt phase step. It is shown that the crystal structure of the prepolymer plays a determining role in the kinetics of the SSP reaction.

Schema of the reactor used for gas phase SSP.     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

Simulation of Nylon 6 Polymerization in an Industrial Two‐Step VK Tubular Reactor

A commonly used nylon 6 two‐step VK tubular reactor is simulated in this work. To verify the reliability of the model, careful comparison with results obtained on different continuous plants is made. The effect of various conditions and parameters, e.g. feed composition, temperature, pressure, etc. on the product properties such as caprolactam conversion, degree of polymerization (DP), dimer, integral heat and their distribution index is studied. It is observed that the caprolactam conversion and DP of the product may be affected by various conditions in the first stage and the temperature profile at the top of the second stage, but they finally reach the equilibrium values if the residence time is long enough. The most effective way to increase DP of the product is to increase the vacuum at the top of the second stage.

CPL conversion and DP profile for pressure of tube 2: 0.032, 0.037, 0.042 mPa; other parameters as given for example A of Table 5 .     

Polymerization Catalysis in Liquid Propylene: High Activities and Molecular Weights in Propylene/CO Copolymerization Reactions

Summary: The dicationic [(dppp)Pd(NCCH₃)₂](BF₄)₂ catalyst (dppp = 1,3‐bis(diphenylphosphino)propane) was applied in a liquid monomer, two phase process for the CO/propene copolymerization reaction. For the first time it was possible to synthesize propene/CO copolymers with an activity up to 7 500 g/(mol · h) and molecular weights of 500 000 g/mol. Activities up to 40 000 g/(mol · h) could be obtained with the use of the unsymmetric catalyst [(CF₃‐dppp)Pd(NCCH₃)](BF₄)₂ (CF₃‐dppp = 1‐diphenylphosphino‐3‐bis[3,5‐di(trifluormethyl)phenyl]phosphinopropane) in homogeneous liquid propene solution.

Granules found after copolymerization.