text:
|Número de publicación
|Tipo de publicación
|Número de solicitud
|Fecha de publicación
|27 Ago 2002
|Fecha de presentación
|10 Abr 2001
|Fecha de prioridad
|14 Oct 1998
|También publicado como
|Número de publicación
|Mats Bäckman, Eeva-Leena Heino, Solveig Johansson, Jussi Laurell, Arja Lehtinen, Jarmo Lindroos, Marja Ora, Elisabeth Ribarits, Teija Sihvonen, Jari {umlaut over (Aa)}rilä
|Cesionario original
|Borealis Technology Oy
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (5), Citada por (44), Clasificaciones (19), Eventos legales (4)
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet
This application is a continuation of international application number PCT/SE99/01679, filed Sep. 24, 1999, pending.
The present invention relates to a multimodal polymer composition for pipes and a pipe prepared thereof.
Nowadays, pipes of polymer material are frequently used for various purposes, such as fluid transport, i.e. transport of liquid or gas, e.g. water or natural gas, during which the fluid can be pressurised. Moreover, the transported fluid may have varying temperatures, usually within the temperature range from about 0° C. to about 50° C. Such pressure pipes are preferably made of polyolefin plastic, usually unimodal ethylene plastic such as medium density polyethylene (MDPE; density: 0.930-0.942 g/cm3) and high density polyethylene (HDPE; density: 0.942-0.965 g/cm3). By the expression "pressure pipe" herein is meant a pipe which, when used, is subjected to a positive pressure, i.e. the pressure inside the pipe is higher than the pressure outside the pipe.
Polymer pipes are generally manufactured by extrusion, or, to a smaller extent, by injection moulding. A conventional plant for extrusion of polymer pipes comprises an extruder, a die-head, a calibrating device, cooling equipment, a pulling device, and a device for cutting or for coiling-up the pipe.
The manufacture of PE materials to be used in pressure pipes is discussed in an article by Scheirs et al [Scheirs, Böhm, Boot and Leevers: PE100 Resins for Pipe Applications, TRIP Vol. 4, No 12 (1996) pp. 408-415]. The authors discuss the production technology and properties of PE100 pipe materials. They point out the importance of proper comonomer distribution and molecular weight distribution to optimize the slow crack growth and rapid crack propagation.
The European patent application EP 739937 A2 discloses a pipe having improved properties. The pipe is made of a bimodal PE resin, and it has a specified stress cracking resistance, impact strength and stiffness. The publication discloses that preferably the material should have an MFRs not higher than 0.35 g/10 min.
The properties of conventional polymer pipes are sufficient for many purposes, although enhanced properties may be desired, for instance in applications requiring high pressure resistance, i.e. pipes that are subjected to an internal fluid pressure for a long and/or short period of time. As examples of properties which it is desirable to improve may be mentioned the processability, the impact strength, the modulus of elasticity, the rapid crack propagation resistance, the slow crack growth resistance, and the design stress rating of the pipe.
A problem when manufacturing large diameter pipes, particularly from multimodal, such as bimodal, polymer material, is that it is difficult to maintain uniform dimensions all over the pipe. This is due to gravity flow of the polymer melt, causing it to flow from the upper part of the pipe to the lower part (often called "sagging"). Thus, the wall thickness at the upper part of the pipe becomes smaller than at the lower part of the pipe. The sagging problem is particularly pronounced for thick-walled large diameter pipes.
The above sagging problem has been discussed in the German patent application DE 19604196 A1. It discloses a process to manufacture a large-bore, thick walled pipe of polyethylene. The pipe is extruded through a ring formed die and cooled on both inner and outer surfaces. This double sided cooling is said to eliminate the deformation of the pipe due to gravity-induced flow of the melt emerging from the die.
The sagging problem has also been discussed in an article by D. N. Githuku and A. J. Giacomin, "Elimination of Sag in Plastic Pipe Extrusion", Intern. Polymer Processing VII (1992) 2, 140-143. The conventional way to reduce sag is by manually adjusting the die eccentricity which typically requires three or four tries at start-up to get an acceptable thickness profile. The article proposes a new way to reduce sag, namely by rotating the pipe during cooling.
A mathematical mode of cooling and solidification, coupled with gravity induced flow during the cooling of extruded plastic pipes is set up and solved by the finite element method in an article by J. F. T. Pittman, G. P. Whitman, S. Beech, and D. Gwynn, "Cooling and Wall Thickness Uniformity in Plastic Pipe Manufacture", Intern. Polymer Processing IX (1994) 2, 130-140. Melt rheology and determination of melt flow properties at the very low stress levels that are relevant at sag is also discussed.
It has now been discovered that the above sagging problem can be overcome by preparing the pipe from a specific, well defined type of multimodal polyethylene. More particularly, the multimodal polyethylene should have a medium to high density, a high viscosity at low shear stress, a carefully selected ratio between its low molecular weight fraction and high molecular weight fraction, and include a comonomer in its high molecular weight fraction only. Preferably, the multimodal polyethylene should have a specific molecular weight and a well defined molecular weight distribution.
Thus, the present invention provides a multimodal polymer composition for pipes, characterised in that it is a multimodal polyethylene with a density of 0.930-0.965 g/cm3, and a viscosity at a constant shear stress of 747 Pa (η747 Pa) of at least 650 kPa.s, said multimodal polyethylene comprising a low molecular weight (LMW) ethylene homopolymer fraction and a high molecular weight (HMW) ethylene copolymer fraction, said HMW fraction having a weight ratio of the LMW fraction to the HMW fraction of (35-55):(65-45)
It is much preferred that the multimodal polyethylene has a viscosity at a shear stress of 2.7 kPa (η2.7 kPa) of 260-450 kPa.s; and a shear thinning index (SHI), defined as the ratio of the viscosities at shear stresses of 2.7 kPa and 210 kPa, respectively, of SHI2.7/210=50-150, and a storage modulus (G′) at a loss modulus (G″) of 5 kPa, of G′5 kPa≧3000 Pa. Preferably densities in the range 0.937-0.942 g/cm3 are used for smaller diameter MD pressure pipes while higher densities of 0.943-0.955 g/cm3 are used for larger diameter HD pressure pipes.
The present invention also provides a pipe comprising said multimodal polymer composition, which pipe withstands a hoop stress of 8.0 MPa gauge during 50 years at 20° C. (MRS8.0)
Preferably, the pipe has a rapid crack propagation (RCP) S4-value, determined according to ISO 13477:1997(E), of −5° C. or lower and a slow crack propagation resistance, determined according to ISO 13479:1997, of at least 500 hrs at 4.6 MPa/80° C.
Other distinguishing features and advantages of the invention will appear from the following specification and the appended claims.
As stated above, the pressure pipe composition of the present invention is made from a specific multimodal polyethylene. This is in contrast to prior art polyethylene pipes which usually are made of unimodal polyethylene or bimodal polyethylene which does not have the specific molecular weight distribution and composition of the multimodal polyethylene of the present invention.
The "modality" of a polymer refers to the form of its molecular weight distribution curve, i.e. the appearance of the graph of the polymer weight fraction as function of its molecular weight. If the polymer is produced in a sequential step process, utilizing reactors coupled in series and using different conditions in each reactor, the different fractions produced in the different reactors will each have their own molecular weight distribution. When the molecular weight distribution curves from these fractions are superimposed into the molecular weight distribution curve for the total resulting polymer product, that curve will show two or more maxima or at least be distinctly broadened in comparison with the curves for the individual fractions. Such a polymer product, produced in two or more serial steps, is called bimodal or multimodal depending on the number of steps. In the following all polymers thus produced in two or more sequential steps are called "multimodal". It is to be noted here that also the chemical compositions of the different fractions may be different. Thus one or more fractions may consist of an ethylene copolymer, while one or more others may consist of ethylene homopolymer.
By properly selecting the different polymer fractions and the proportions thereof in the multimodal polyethylene a pipe with good non-sagging properties together with good processability, good slow crack growth resistance, rapid crack propagation resistance, and a high design stress rating is obtainable.
The pressure pipe composition of the present invention is a multimodal polyethylene, preferably a bimodal polyethylene. The multimodal polyethylene comprises a low molecular weight (LMW) ethylene homopolymer fraction and a high molecular weight (HMW) ethylene copolymer fraction. Depending on whether the multimodal polyethylene is bimodal or has a higher modality the LMW and HMW fractions may comprise only one fraction each or include sub-fractions, i.e. the LMW may comprise two or more LMW sub-fractions and similarly the HMW fraction may comprise two or more HMW sub-fractions. It is a characterising feature of the present invention that the LMW fraction is an ethylene homopolymer and that the HMW fraction is an ethylene copolymer, i.e. it is only the HMW fraction that includes a comonomer. As a matter of definition, the expression "ethylene homopolymer" used herein relates to an ethylene polymer that consists substantially, i.e. to at least 97% by weight, preferably at least 99% by weight, more preferably at least 99.5% by weight, and most preferably at least 99.8% by weight of ethylene and thus is an HD ethylene polymer which preferably only includes ethylene monomer units. Preferably, the lower limit of the molecular weight range of the HMW fraction is 3 500, more preferably 4000, which means that almost all ethylene copolymer molecules in the multimodal polyethylene pipe composition of the invention have a molecular weight of at least 3500, preferably at least 4000. This preferred lower limit of the HMW fraction gives a pressure pipe with enhanced strength.
In the present invention it is further important that the proportions of the LMW and HMW fractions (also known as the "split" between the fractions) are selected properly. More particularly, the weight ratio of the LMW fraction to the HMW fraction should lie in the range (35-55):(65-45), preferably (43-51):(57-49), most preferably (44-50):(56-50). It is important that the split lies within these ranges, because if the proportion of the HMW fraction becomes too great it results in too low strength values and if it is too low it results in an unacceptable formation of gels.
In order to achieve the non-sagging characteristics of the multimodal polyethylene of the present invention it is important that the polymer after being extruded into a pipe and before being cooled does not flow by gravity from the upper part of the pipe down to the lower part of the pipe and thus creates a non-uniform distribution of polymer over the cross-section of the pipe.
The tendency of a polymer to display gravity flow may be determined by means of a conventional melt index apparatus, such as a Göttfert melt index apparatus. Generally, a polymer sample is introduced into the bore (9.550 mm diameter; ISO 1133) of the melt index apparatus, the temperature is set at 230° C., the bottom die is removed, and the polymer loaded with a weight corresponding to the force of gravity that would have acted upon the polymer if it had constituted the upper part of a pipe. One has found that the piston (which weighs 120 g) of the melt index apparatus corresponds to the gravity force on the polymer at the upper part of a 2.2 m diameter pipe, and it is therefore suitable to use the piston without any extra weight as the gravity force acting upon the polymer sample. During the test the polymer flow is determined at intervals for 75 min and the average gravity flow is then determined in mm/10 min. At the present invention the gravity flow of the polymer should be less than 0.1 mm/10 min. A more detailed description of the steps of the gravity flow determination method is given below.
1. Set the temperature to 230° C. and let it stabilise.
2. Weight the piston to an accuracy of 0.1 g.
3. When the temperature is stable insert 6-8 g of the material to be measured.
4. Let the material heat soak for 10 min.
5. After 10 min open the bottom holder for the die and press out the die by pressing the melt pool from above.
6. Take away the die and apply the piston. Press down the piston until the lower marking scratch on the piston is 29 mm above the filling hole.
7. Let the melt pool relax for 10 min as some materials have a more pronounced melt elasticity than others and the induced elasticity from the pressing down of the melt pool may influence the result.
8. Start the measurement by measuring the height of the lower marking scratch above the filling hole with a sliding caliper to an accuracy of 0.1 mm. Start the stop watch.
9. Make a measurement of the height above the filing hole each 20 min and make a final measurement after 75 min.
10. Make notes and present the results of the height each 20 min. Calculate the travelling distance each 20 min in mm as well as the travelling speed expressed as mm/10 min. Finally calculate the average travelling distance and velocity after 75 min (travel. dist/75) and make a report.
11. Clean the equipment in the normal manner.
Although the above method is a simple and easy way of determining the sagging property of a pipe material, the accuracy for very low gravity flow materials is somewhat uncertain. In order to remedy this disadvantage it is preferred to use another method which correlates well with the above described gravity flow method, but gives greater accuracy for materials with very low gravity flow. This preferred method, which is used in connection with the present invention relates to the rheology of the polymer and is based on determination of the viscosity of the polymer at a very low, constant shear stress. A shear stress of 747 Pa has been selected for this method. The viscosity of the polymer at this shear stress is determined at a temperature of 190° C. and has been found to be inversely proportional to the gravity flow of the polymer, i.e. the greater the viscosity the lower the gravity flow. At the present invention the viscosity at 747 Pa and 190° C. should be at least 650 kPa.s. A more detailed description of the steps of the method for determination of the viscosity of the polymer at 747 Pa and 190° C. is given below.
The determination is made by using a rheometer, preferably a Bohlin CS Melt Rheometer. Rheometers and their function have been described in "Encyclopedia of Polymer Science and Engineering", 2nd Ed., Vol. 14, pp. 492-509. The measurements are performed under a constant stress between two 25 mm diameter plates (constant rotation direction). The gap between the plates is 1.8 mm. An 1.8 mm thick polymer sample is inserted between the plates.
The sample is temperature conditioned during 2 min before the measurement is started. The measurement is performed at 190° C. After temperature conditioning the measurement starts by applying the predetermined stress. The stress is maintained during 1800 s to let the system approach steady state conditions. After this time the measurement starts and the viscosity is calculated.
The measurement principle is to apply a certain torque to the plate axis via a precision motor. This torque is then translated into a shear stress in the sample. This shear stress is kept constant. The rotational speed produced by the shear stress is recorded and used for the calculation of the viscosity of the sample.
Rheology measurements according to ASTM D 4440-95a may also be used to characterise other important properties of the polymer, such as the molecular weight and molecular weight distribution (MWD).
The use of rheology is advantageous in those cases where the high molecular weight end of the molecular weight distribution is important. Typically, size exclusion chromatography (gel permeation chromatography), which often is used to measure the molecular weight distribution, is not sensitive enough in this molecular weight range.
The storage modulus (G′) and the loss modulus (G″) together with the absolute value of the complex viscosity (η*) as a function of the frequency (ω) or the absolute value of the complex modulus (G*) are obtained by rheology measurements.
According to Cox-Merz rule the complex viscosity function, η*(ω) is the same as the conventional viscosity function (viscosity as a function of shear rate), if frequency is taken in rad/s. If this empiric equation is valid, the absolute value of the complex modulus corresponds to the shear stress in conventional (that is steady state) viscosity measurements. This means that the function η*(G*) is the same as the viscosity as a function of shear stress.
In the present method the viscosity at a low shear stress or η* at a low G* (which serves as an approximation of the so called zero viscosity) is used as a measure of average molecular weight.
According to the invention, η2.7 kPa (viscosity at 2.7 kPa shear stress) should be between 260-450 kPa.s.
On the other hand, shear thinning, that is the decrease of viscosity with G*, gets more pronounced the broader the molecular weight distribution is. This property can be approximated by defining a so called shear thinning index, SHI, as a ratio of the viscosity at two different shear stresses. In the present invention the shear stresses (or G*) 2.7 kPa and 210 kPa are used for calculating the SHI2.7/210 as a measure of the broadness of the molecular weight distribution.
η*2.7 is the complex viscosity at G*=2.7 kPa and
η*210 is the complex viscosity at G*=210 kPa.
According to the invention, SHI2.7/210 should be between 50-150.
The storage modulus, G′, may also be used as a measure of the molecular weight distribution. As mentioned above, the storage modulus function, G′ (ω) and the loss modulus function G″ (ω), are obtained as primary functions from dynamic measurements. The value of the storage modulus at a specific value of loss modulus increases with broadness of the molecular weight distribution. However this quantity is highly dependent on the shape of the molecular weight distribution of the polymer. Especially it is a measure of the high molecular weight end of the molecular weight distribution. According to the invention, the material should have a G′5 kPa (G′ at G″=5 kPa)≧3000 Pa.
Rheological measurements were made using the dynamic rheometers Bohlin Cs Melt Rheometer like Rheometrics RDA II. The measurements were performed at 190° C. under nitrogen atmosphere using plate & plate test fixture with diameter of 25 mm. The strain amplitude was chosen so that a linear working range was obtained. From the measurements storage modulus (G′) and loss modulus (G″) together with absolute value of complex viscosity (η*) as a function of frequency (ω) or the absolute value of complex modulus (G*) were obtained.
It has been found that when the polymer has been prepared to have the above-mentioned characteristics, the resulting material has low tendency for sagging. It also has a good extrudability and good mechanical properties. All the rheological measurements (except the determination of G′, which was made using a Rheometrics RDA II Dynamic Rheometer) have been made using a Bohlin CS Melt Rheometer and were carried out at 190° C. under nitrogen atmosphere.
The melt flow rate (MFR), which is equivalent to the term "melt index" previously used, is another important property of the multimodal polyethylene for pipes according to the invention. The MFR is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the flowability, and hence the processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer. The MFR is determined at different loadings such as 2.1 kg (MFR2.1; ISO 1133, condition D) or 5 kg (MFR5; ISO 1133, condition T). At the present invention the multimodal polyethylene should have an MFR5 of 0.1-1.0 g/10 min, preferably 0.15-0.8 g/10 min.
Another characterising feature of the present invention is the density of the multimodal polyethylene. For reasons of strength the density lies in the medium to high density range, more particularly in the range 0.930-0.965 g/cm3. Preferably, lower densities of 0.937-0.942 g/cm3 are used for smaller diameter MD pressure pipes, while higher densities of 0.943-0.955 g/cm3 are used for larger diameter HD pressure pipes. The pressure pipes of medium density multimodal polyethylene are somewhat more flexible than pressure pipes of high density multimodal polyethylene and may therefore more easily be coiled into a roll. On the other hand it is possible to obtain pressure pipes of a higher design stress rating with high density multimodal polyethylene than with medium density multimodal polyethylene.
It should be noted that the multimodal polymer composition of the present invention is characterised, not by any single one of the above defined features, but by the combination of all the features defined in claim 1. By this unique combination of features it is possible to obtain pressure pipes of superior performance, particularly with regard to sagging, processability, rapid crack propagation (RCP) resistance, design stress rating, impact strength, and slow crack propagation resistance.
The processability of a pipe (or rather the polymer thereof) may be determined in terms of the number of screw revolutions per minute (rpm) of an extruder for a predetermined output of pipe in kg/h, but also the surface appearance of the pipe is then important.
The rapid crack propagation (RCP) resistance of a pipe may be determined according to a method called the S4 test (Small Scale Steady State), which has been developed at Imperial College, London, and which is described in ISO 13477:1997(E). According to the RCP-S4 test a pipe is tested, which has an axial length not below 7 pipe diameters. The outer diameter of the pipe is about 110 mm or greater and its wall thickness about 10 mm or greater. When determining the RCP properties of a pipe in connection with the present invention, the outer diameter and the wall thickness have been selected to be 110 mm and 10 mm, respectively. While the exterior of the pipe is at ambient pressure (atmospheric pressure), the pipe is pressurised internally, and the internal pressure in the pipe is kept constant at a pressure of 0.5 MPa positive pressure. The pipe and the equipment surrounding it are thermostatted to a predetermined temperature. A number of discs have been mounted on a shaft inside the pipe to prevent decompression during the tests. A knife projectile is shot, with well-defined forms, towards the pipe close to its one end in the so-called initiating zone in order to start a rapidly running axial crack. The initiating zone is provided with an abutment for avoiding unnecessary deformation of the pipe. The test equipment is adjusted in such a manner that crack initiation takes place in the material involved, and a number of tests are effected at varying temperatures. The axial crack length in the measuring zone, having a total length of 4.5 diameters, is measured for each test and is plotted against the set test temperature. If the crack length exceeds 4 diameters, the crack is assessed to propagate. If the pipe passes the test at a given temperature, the temperature is lowered successively until a temperature is reached, at which the pipe no longer passes the test, but the crack propagation exceeds 4 times the pipe diameter. The critical temperature (Tcrit) i.e. the ductile brittle transition temperature as measured according to ISO 13477:1997(E) is the lowest temperature at which the pipe passes the test. The lower the critical temperature the better, since it results in an extension of the applicability of the pipe. It is desirable for the critical temperature to be around −5° C. or lower. A pressure pipe made of the multimodal polymer composition according to the present invention preferably has an RCP-S4 value of −1° C. (minimum requirement for an MD PE80 pipe) or lower, more preferably −4° C. (minimum requirement for an HD PE80 pipe) or lower, and most preferably −7° C. (minimum requirement for an HD PE100 pipe) or lower.
The design stress rating is the circumferential stress a pipe is designed to withstand for 50 years without failure and is determined for different temperatures in terms of the Minimum Required Strength (MRS) according to ISO/TR 9080. Thus, MRS8.0 means that the pipe is a pipe withstanding a hoop stress of 8.0 MPa gauge for 50 years at 20° C., and similarly MRS10.0 means that the pipe withstands a hoop stress of 10 MPa gauge for 50 years at 20° C. A pressure pipe made of the multimodal polymer composition according to the present invention preferably has a design stress rating of at least MRS8.0, and most preferably MRS10.0.
The impact strength is determined as Charpy Impact Strength according to ISO 179. A pressure pipe made of the multimodal polymer composition according to the present invention preferably has an impact resistance at 0° C. of at least 10 kJ/m2, more preferably at least 14 kJ/m2, and most preferably at least 15 kJ/m2.
The slow crack propagation resistance is determined according to ISO 13479:1997 in terms of the number of hours the pipe withstands a certain pressure at a certain temperature before failure. A pressure pipe made of the multimodal polymer composition according to the present invention preferably has a slow crack propagation resistance of at least 1000 hrs at 4.0 MPa/80° C., and more preferably at least 500 hrs at 4.6 MPa/80° C.
The modulus of elasticity is determined according to ISO 527-2 (with test specimen 1B). A pressure pipe made of the multimodal polymer composition according to the present invention preferably has a modulus of elasticity of at least 800 MPa, more preferably at least 950 MPa, and most preferably at least 1100 MPa.
A pressure pipe made of the multimodal polymer composition of the present invention is prepared in a conventional manner, preferably by extrusion in an extruder. This is a technique well known to the skilled person an no further particulars should therefore be necessary here concerning this aspect.
It is previously known to produce multimodal, in particular bimodal, olefin polymers, such as multimodal polyethylene, in two or more reactors connected in series. As instance of this prior art, mention may be made of EP 517 868, which is hereby incorporated by way of reference as regards the production of multimodal polymers.
According to the present invention, the main polymerisation stages are preferably carried out as a combination of slurry polymerisation/gas-phase polymerisation. The slurry polymerisation is preferably performed in a so-called loop reactor. The use of slurry polymerisation in a stirred-tank reactor is not preferred in the present invention, since such a method is not sufficiently flexible for the production of the inventive composition and involves solubility problems. In order to produce the inventive composition of improved properties, a flexible method is required. For this reason, it is preferred that the composition is produced in two main polymerisation stages in a combination of loop reactor/gas-phase reactor. Optionally and advantageously, the main polymerisation stages may be preceded by a prepolymerisation, in which case up to 20% by weight, preferably 1-10% by weight, more preferably 1-5% by weight, of the total amount of polymers is produced. The prepolymer is preferably an ethylene homopolymer (HDPE). At the prepolymerisation all of the catalyst is preferably charged into a loop reactor and the prepolymerisation is performed as a slurry polymerisation. Such a prepolymerisation leads to less fine particles being produced in the following reactors and to a more homogeneous product being obtained in the end. Generally, this technique results in a multimodal polymer mixture through polymerisation with the aid of a Ziegler-Natta or metallocene catalyst in several successive polymerisation reactors. Chromium catalysts are not preferred in connection with the present invention. In the production of, say, a bimodal polyethylene, which according to the invention is the preferred polymer, a first ethylene polymer is produced in a first reactor under certain conditions with respect to hydrogen-gas concentration, temperature, pressure, and so forth. After the polymerisation in the first reactor, the polymer including the catalyst is separated from the reaction mixture and transferred to a second reactor, where further polymerisation takes place under other conditions. Usually, a first polymer of high melt flow rate (low molecular weight, LMW) and with no addition of comonomer is produced in the first reactor, whereas a second polymer of low melt flow rate (high molecular weight, HMW) and with addition of comonomer is produced in the second reactor. As comonomer of the HMW fraction various alpha-olefins with 4-8 carbon atoms may be used, but the comonomer is preferably selected from the group consisting of 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The amount of comonomer is preferably such that it comprises 0.1-2.0 mol %, more preferably 0.1-1.0 mol % of the multimodal polyethylene. The resulting end product consists of an intimate mixture of the polymers from the two reactors, the different molecular-weight-distribution curves of these polymers together forming a molecular-weight-distribution curve having a broad maximum or two maxima, i.e. the end product is a bimodal polymer mixture. Since multimodal, and especially bimodal, ethylene polymers, and the production thereof belong to the prior art, no detailed description is called for here, but reference is had to the above mentioned EP 517 868.
As hinted above, it is preferred that the multimodal polyethylene composition according to the invention is a bimodal polymer mixture. It is also preferred that this bimodal polymer mixture has been produced by polymerisation as above under different polymerisation conditions in two or more polymerisation reactors connected in series. Owing to the flexibility with respect to reaction conditions thus obtained, it is most preferred that the polymerisation is carried out in a loop reactor/a gas-phase reactor. Preferably, the polymerisation conditions in the preferred two-stage method are so chosen that a comparatively low-molecular polymer having no content of comonomer is produced in one stage, preferably the first stage, owing to a high content of chain-transfer agent (hydrogen gas), whereas a high-molecular polymer having a content of comonomer is produced in another stage, preferably the second stage. The order of these stages may, however, be reversed.
In the preferred embodiment of the polymerisation in a loop reactor followed by a gas-phase reactor, the polymerisation temperature in the loop reactor preferably is 92-98° C., more preferably about 95° C., and the temperature in the gas-phase reactor preferably is 75-90° C., more preferably 82-87° C.
A chain-transfer agent, preferably hydrogen, is added as required to the reactors, and preferably 200-800 moles of H2/kmoles of ethylene are added to the reactor, when the LMW fraction is produced in this reactor, and 0-50 moles of H2/kmoles of ethylene are added to the gas phase reactor when this reactor is producing the HMW fraction.
As indicated earlier, the catalyst for polymerising the multimodal polyethylene of the invention preferably is a Ziegler-Natta type catalyst. Particularly preferred are catalysts with a high overall activity as well as a good activity balance over a wide range of hydrogen partial pressures. Furthermore, the molecular weight of the polymer produced by the catalyst is of great importance. As an example of a preferred catalyst may be mentioned the catalyst disclosed in FI 980788 and its corresponding PCT application PCT/FI99/00286. It has surprisingly been found that when using this catalyst in a multistage process, it is possible to obtain the polymer having the characterstics described above. This catalyst also has the advantage that the catalyst (procatalyst and cocatalyst) only needs to and, indeed, only should be added in the first polymerisation reactor. The preferred catalyst according to FI 980788 and its corresponding PCT application FI99/00286 will be described in more detail below.
FI 980788 and its corresponding PCT application PCT/FI99/00286 discloses a process for the production of a high activity procatalyst, characterized by the steps of reacting a support comprising a magnesium halide compound having the formula (1):
wherein each same or different R is a C1-C20 alkyl or a C7-C26 aralkyl, each same or different X is a halogen, and n is an integer 1 or 2, an alkyl metal halide compound having the formula:
a) according to PCT application PCT/FI99/00286
wherein Me is B or Al, R being the same or different is a C1-C10 alkyl, X being the same or different is a halogen, n is an integer of 1 to 5 and m is an integer of 1 or 2, or, preferably,
b) according to FI 980788
wherein Me is B or Al, each same or different R1 is a C1-C10 alkyl, each same or different X1 is a halogen, n1 is an integer 1 or 2, and m1 is an integer 1 or 2, a magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide, aid magnesium composition having the empirical formula (3):
wherein each same or different R2 is a C1-C20 alkyl, each same or different R3 is a C1-C20 alkyl or a C1-C20 alkyl having a hetero element, and n2 is between 0.01 and 1.99, and a titanium halide compound having the formula (4):
wherein each same or different R4 is a C1-C20 alkyl, each same or different X2 is a halogen, n3 is 0 or an integer 1-3, and Ti is quadrivalent titanium.
By "magnesium composition" above is meant a mixture or a compound. Note that formula (3) is an empirical formula and expresses the molar amounts of alkyl R2 and alkoxy OR3 relative to the amount of magnesium Mg, which has been defined as 1, and differs from formulas (1), (2a), (2b) and (4), which are essentially structural formulas and express the molecular structure of reagents (1), (2a), (2b) and (4).
Preferably, the process comprises the subsequent steps of:
a) providing said support comprising a magnesium halide compound having the formula (1),
b) contacting said support comprising a magnesium halide compound having the formula (1) with said alkyl metal halide compound having the formula (2a) or (2b), to give a first product,
c) contacting said first product with said magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide and having the empirical formula (3), to give a second product, and
d) contacting said second product with said titanium halide compound having the formula (4).
The support used in the process is preferably in the form of particles, the size of which is from about 1 μm to about 1000 μm, preferably about 10 μm to about 100 μm. The support material must have a suitable particle size distribution, a high porosity and a large specific surface area. A good result is achieved if the support material has a specific surface area between 100 and 500 m2/g support and a pore volume of 1-3 ml/g support.
The above catalyst components (2a) to (4) are reacted with a suitable catalyst support. If the catalyst components (2a) to (4) are in the form of a solution of low viscosity, good catalyst morphology and therewith good polymer morphology can be achieved.
It is advantageous if in the magnesium halide compound having the formula (1), R is a C1-C20 alkoxy or a C7-C26 aralkoxy. However, it is preferable, if said compound (1) is a magnesium dihalide, most preferably MgCl2 for example, the support may comprise solid MgCl2, either alone as a powder, or as a powder mixture with other inorganic powders.
According to another embodiment, the support comprising a magnesium halide compound having the formula (1) comprises an inorganic oxide. Several oxides are suitable, but silicon, aluminium, titanium, chromium and zirconium oxide or mixtures thereof are preferred. The most preferred inorganic oxide is silica, alumina, silica-alumina, magnesia and mixtures thereof, uttermost preferably silica. The inorganic oxide can also be chemically pretreated, e.g. by silylation or by treatment with aluminium alkyls.
It is good to dry the inorganic oxide before impregnating it by other catalyst components. A good result is achieved if the oxide is heat-treated at 100° C. to 900° C. for a sufficient time, and thereby the surface hydroxyl groups, in the case of silica, are reduced to below 2 mmol/g SiO2.
As was said above, the support may be a mixture of said magnesium halide compound (1) and another solid powder, which preferably is an inorganic oxide. According to another aspect, the support comprises particles having a core comprising said inorganic oxide and a shell comprising said magnesium halide compound having the formula (1). Then, the support comprising a magnesium halide compound having the formula (1) and an inorganic oxide can conveniently be prepared by treating particles of the inorganic oxide with a solution of the magnesium halide and removing the solvent by evaporation.
When using a support containing both said magnesium halide compound (1) and another component, the amount of magnesium halide compound (1) is such that the support contains from 1 to 20% by weight, preferably from 2 to 6% by weight, of magnesium Mg.
The process further comprises a step of reacting an alkyl metal halide compound of the formula:
a) according to PCT application PCT/FI99/00286
wherein Me is B or Al, R being the same or different is a C1-C10 alkyl, X being the same or different is a halogen, n is an integer of 1 to 5, and m is an integer of 1 or 2, or, preferably
b) according to FI 980788
wherein Me is B or Al, each same or different R1 is a C1-C10 alkyl, each same or different X1 is a halogen, n1 is an integer 1 or 2, and m1 is an integer 1 or 2. In formulas (2a) and (2b), Me is preferably Al. Each same or different R or R1 is preferably a C1-C6 alkyl, and, independently, the preferred same or different halogen X or X1 is chlorine. n or n1 is preferably 1 and m1 is Preferably the integer 1 or 2. Most preferably, the alkyl metal halide compound having the formulas (2a) and (2b) is an alkyl aluminium dichloride, e.g. ethylaluminium dichloride (EADC).
The alkyl metal halide compound is preferably deposited on the support material. An even deposition is achieved if the viscosity of the agent or its solution is below 10 mPa.s at the temperature applied. To achieve this low viscosity the alkyl metal halide agent can be diluted by a non-polar hydrocarbon. The best deposition is however achieved if the total volume of the deposited alkyl metal halide solution is not exceeding the pore volume of the support, or if the excess of diluting hydrocarbon is evaporated away after the deposition of the alkyl metal halide. A good choice is to use a 5-25% hydrocarbon solution of ethyl aluminium dichloride. The chemical addition times and the addition techniques are preferably adjusted to give an even distribution of the chemical in the support material.
In the above mentioned preferred order of reaction steps a) to d), step b) can advantageously be performed so that undiluted alkyl metal halide (2a) or (2b) is used to treat the support comprising a magnesium halide compound having the formula (1). Alternatively, the support is contacted with a solution of the alkyl metal halide compound having the formula (2a) or (2b) in an essentially non-polar solvent, preferably a non-polar hydrocarbon solvent, most preferably a C4-C10 hydrocarbon. The concentration of the alkyl metal halide compound having the formulas (2a) or (2b) in said non-polar solvent is usually 1-80% by weight, preferably 5-40% by weight, most preferably 10-30% by weight. Advantageously, the support is contacted with a solution of said alkyl metal halide compound (2a, 2b) in a ratio mol of the alkyl metal halide compound (2a, 2 b) to grams of the support of between about 0.01 mmol/g and about 100 mmol/g, preferably about 0.5 mmol/g and about 2.0 mmol/g. The amount of reactants can also be expressed as molar ratio, whereby it is advantageous, if the molar ratio of said alkyl metal halide compound (2a, 2b) to said magnesium halide compound (1) of the support is between about 0.01 mol/mol to about 100, preferably about 0.1 mol/mol to about 10, most preferably from about 0.2 to about 3.0.
In step b), the temperature of said contacting is e.g. 5-80° C., preferably 10-50° C., most preferably 20-40° C. The duration of said contacting is 0.1-3 h, preferably 0.5-1.5 h.
In the process, the magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide having the empirical formula (3), each same or different R2 is preferably C2-C10 alkyl, most preferably a C2-C8 alkyl. Each same or different R3 is preferably a C3-C20 alkyl, more preferably a branched C4-C10 alkyl, most preferably a 2-ethyl-1-hexyl or a 2-propyl-1-pentyl.
The magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide having the empirical formula (3) can also be expressed by its preparation. According to one embodiment, it is a contact product of a dialkyl magnesium having the formula (5):
wherein each same or different R2 is defined as above, and an alcohol. Preferably, the dialkyl magnesium having the formula (5) is dibutyl magnesium, butyl ethyl magnesium or butyl octyl magnesium.
The magnesium composition can also be defined in that the magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide having the empirical formula (3) is a contact product of a dialkyl magnesium and an alcohol having the formula (6)
wherein each same or different R3 is the same as above. Preferably, the alcohol having the formula (6) is a 2-alkyl alkanol, preferably 2-ethyl hexanol or 2-propyl pentanol. It was found, that such branched alcohols gave better results than linear alcohols.
Preferably, the magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide having the empirical formula (3) is a contact product of a dialkyl magnesium and an alcohol in a molar ratio alcohol to dialkyl magnesium of 0.01-100 mol/mol, preferably 1.0-5.0 mol/mol, more preferably 1.7-2.0 mol/mol, most preferably 1.8-1.98 mol/mol. The dialkyl magnesium and the alcohol are conveniently contacted by adding the alcohol to a solution of said dialkyl magnesium in an organic solvent, e.g. a C4-C10 hydrocarbon. Then, the concentration of the solution is preferably between 1 and 50% by weight, most preferably between 10 and 30% by weight. The contacting temperature between the dialkyl magnesium and the alcohol is preferably 10-50° C., preferably from about 20° C. to about 35° C.
In step c) of the above mentioned preferred order a)→d) of the process, the contacting product of the support with the alkyl metal halide compound (2) (=said first product) is contacted with said magnesium composition containing magnesium bonded to a hydrocarbyl and magnesium bonded to a hydrocarbyl oxide and having the empirical formula (3).
Preferably, said first product is contacted with said magnesium composition (3) in a ratio moles of magnesium/g of the support between 0.001-1000 mmol/g, preferably 0.01-100 mmol/g, most preferably 0.1-10 mmol/g (g of the support means, in the case of said first reaction product, the support which was used as starting material for the first reaction product).
A good deposition of said magnesium composition as a solution is achieved if the volume of the magnesium composition (3) solution is about two times the pore volume of the support material. This is achieved if the concentration of the composition in a hydrocarbon solvent is between 5-60% in respect of the hydrocarbon used. When depositing the magnesium composition on the support material its hydrocarbon solution should have a viscosity that is lower than 10 mPa.s at the temperature applied. The viscosity of the magnesium complex solution can be adjusted for example by the choice of the group R4 in the formula (3), by the choice of the concentration of the hydrocarbon solution, by the choice of the ratio between the magnesium alkyl and the alcohol or by using some viscosity lowering agent. The titanium compound can be added to the support material with or without a previous drying of the catalyst to remove the volatile hydrocarbons. Remaining hydrocarbons can if desired be removed by using slight underpressure, elevated temperature or nitrogen flash.
In the process, the transition metal compound is a titanium halide compound having the formula (4). R4 is preferably a C2-C8 alkyl, most preferably a C2-C6 alkyl. X2 is preferably chlorine and, independently, n3 is preferably 0. Said titanium halide compound having the formula (4) is advantageously titanium tetrachloride.
According to one embodiment, in addition to said titanium compound having the formula (4), a titanium compound having the formula (7):
wherein each same of different R5 is a C1-C20 alkyl, preferably a C2-C8 alkyl, most preferably a C2-C6 alkyl, each same or different X3 is a halogen, preferably chlorine, n4 is an integer 1-4, and Ti is quadrivalent titanium, is reacted. The titanium compound (7) always has at least one alkoxy group, which helps dissolving the titanium compound (4) which does not necessarily have alkoxide, into an organic solvent before the contacting. Naturally, the more alkoxide groups compound (4) has, the less is the need for compound (7). If compound (7) is used, the preferable combination is that of titanium tetrachloride and a titanium tetra C1-C6 alkoxide.
In step d) of the preferred step sequence a)→d), said second product is advantageously contacted with the titanium compound having the formula (4) in a ratio moles of said titanium compound/g of the support of 0.01-10 mmol/g, preferably 0.1-2 mmol/g. Preferably, said second reaction product is contacted with said titanium compound (4) in a ratio moles of said titanium compound (4)/total moles of the magnesium of 0.05-2 mol/mol, preferably 0.1-1.2 mol/mol, most preferably 0.2-0.7 mol/mol. The temperature is usually 10-80° C., preferably 30-60° C., most preferably from about 40° C. to about 50° C., and the contacting time is usually 0.5-10 h, preferably 2-8 h, most preferably from about 3.5 h to about 6.5 h.
Above, the process for the preparation of a high activity catalyst component for the production of olefin polymers of different molecular weight and homogenous consistence, have been described in detail.
The catalyst component has high activity both when producing low melt flow rate ethylene polymer and high melt flow rate polymer. High molecular weight polymer has high melt viscosity, i.e. low melt flow rate, and low molecular weight polymer has low melt viscosity, i.e. high melt flow rate.
Simultaneously or separately, it preferably produces ethylene homopolymer and copolymer with low gel content. Most preferably it produces ethylene homopolymer having a gel number, expressed as number of gel spots/sq.m in a film prepared from the material, of 0. This means, that by the standards used, the catalyst components can be used to produce totally homogenous (gelless) low and high molecular weight ethylene polymer.
The alkyl metal halide compound of the formula (2) can, if used, act completely or partially as a cocatalyst. However, it is preferable to add a cocatalyst having the formula (9):
wherein R6 is a C1-C20 alkyl, preferably a C1-C10 alkyl, most preferably a C2-C6 alkyl such as ethyl, X is halogen, preferably chlorine, n is 1 to 3, more preferably 2 or 3, most preferably 3, to the polymerization mixture. The cocatalyst having the formula (9) can be used irrespective of whether said alkyl metal halide compound (2) is used or not.
Although the invention has been described above with reference to a specified multimodal polyethylene, it should be understood that this multimodal polyethylene may include various additives such as fillers, etc. as is known and conventional in the art. An especially important additive is carbon black which is used to colour the pipe black. It should be noted that some additives may have a significant effect on the properties of the polymer. Thus, the density of the black compound is typically significantly higher than the density of the reactor product. Further, the pipe made of the specified multimodal polyethylene may be a single-layer pipe or form part of a multilayer pipe including further layers of other pipe materials.
Having thus described the present invention it will now be illustrated by way of non-limiting examples of preferred embodiments in order to further facilitate the understanding of the invention.
Complex Preparation
8.6 g (66.4 mmol) of ethyl-1-hexanol was added slowly to 27.8 g (33.2 mmol) of a 19.9% by weight solution of butyl octyl magnesium. The reaction temperature was kept under 35° C. This complex was used in catalyst preparations. The molar ratio of 2-ethyl-1-hexanol to butyl octyl magnesium was 2:1.
Catalyst Preparation
3.7 g (1.0 mmol/g carrier) of 20% ethyl aluminium dichloride was added to 5.9 g of Sylopol 5510 silica/MgCl2 carrier and the mixture was stirred for one hour at 30° C. 5.7 g (0.9 mmol/g carrier) of complex prepared according to "Complex preparation" was added and the mixture was stirred for 4 hours at 35-45° C. 0.6 g (0.55 mmol/g carrier) of TiCl4 was added and the mixture was stirred for 4 hours at 35-45° C. The catalyst was dried at 45-80° C. for 3 hours. The composition of the catalyst obtained was Al 1.8%, Mg 3.9% and Cl 18.5% by weight.
Into a 50 dm3 loop reactor was added 7.0 g/h of catalyst prepared according to Example 1, 2 kg/h of ethylene, 20 kg/h of propane and 1 g/h of hydrogen. The operating temperature was 80° C. and the operating pressure 65 bar.
The slurry was taken out of the reactor and led into a 500 dm3 loop reactor. The reactor was operated at 95° C. temperature and 61 bar pressure. The rate of polymer production was 35 kg/h and the MFR2 of the polymer produced was 280 g/10 min. No comonomer was fed into the loop reactor.
From the loop reactor the polymer was transferred into a gas phase reactor where the polymerisation was continued. The reactor was operated at 85° C. and 20 bar pressure. Ethylene, hydrogen and 1-butene were fed into the reactor to obtain such conditions that the rate of polymer production was 41 kg/h, the MFR5 of the polymer produced was 0.24 g/10 min and the density was 0.951 kg/dm3.
The polymer was then compounded with 5.7% by weight of a carbon black master batch. The MFR5 of the compounded material was 0.17 g/10 min and the density was 0.960 kg/dm3.
The polymerisation data are collected in Table 1.
The procedure of Example 2 was repeated with the exception that 1-hexene was used as comonomer in the gas phase reactor. The data are collected in Table 1.
Loop H2/C2
Loop MFR2
g/10 min
Fin. resin
Fin. resin
The properties of the materials A-D after being compounded with CB master batch are shown i Table 2.
Resin with
g/10 min
g/10 min
η2.7 kPa
G′5 kPa Pa
η747 Pa
mm/10 min
4.6 Mpa h
Tcrit ° C.
It is evident from Table 1 that the resins A-D according to the present invention all have very low gravity flows, below 0.1 mm/10 min, and high viscosities at the low shear stress of 747 Pa (η747 Pa) of more than 650 kPa.s, i.e. the resins have good non-sagging properties. In addition, pipes made of the resins A-D have excellent physical properties, such as resistance to slow crack propagation, a low Tcrit for rapid crack propagation and good impact strength at 0° C.
The properties of some commercial bimodal PE100 materials E-G are shown in Table 3.
MFR5 g/10 min
MFR21 g/10 min
η2.7 kPa kPa.s
G′5 kPa Pa
η747 Pa kPa.s
Gravity flow
mm/10 min
Notch/4.6 Mpa
Tcrit ° C.
The materials E-G all show excellent strength properties but inferior sagging tendencies.
The properties of some commercial monomodal PE materials H-K are shown in Table 4.
MFR5 g/10 min
MFR21 g/10 min
η2.7 kPa kPa.s
SHI2.7/210 kPa
G′5 kPa Pa
η747 Pa kPa.s
Gravity flow
mm/10 min
Notch/4.6 Mpa
Tcrit ° C.
As apparent from the comparative materials, it has hitherto not been found possible to combine the high strength, in terms of long term hoop stress resistance, low Tcrit in the RCP 4S-test and high impact strength, with good non-sagging property. The comparative bimodal PE100-materials all show good strength properties but have pronounced sagging tendencies, while of the monomodal materials H and I have low sagging tendency, but less good strength properties.
|Patente citada
|Fecha de presentación
|Fecha de publicación
|4 Sep 1992
|9 Nov 1993
|Nippon Petrochemicals Company, Ltd.
|Polyethylene composition
|16 Abr 1993
|26 Abr 1994
|Phillips Petroleum Company
|Polyethylene blends
|3 Jun 1992
|16 Ago 1994
|Hoechst Aktiengesellschaft
|Polyethylene molding composition
|3 Mar 1999
|6 Feb 2001
|Borealis Polymers Oy
|Multimodal polymer composition
|25 Mar 1994
|13 Oct 1994
|Borealis Polymers Oy
|Process for manufacturing olefin polymers and products prepared by the process
|Patente citante
|Fecha de presentación
|Fecha de publicación
|26 Sep 2000
|4 Nov 2003
|Nova Chemicals (International) S.A.
|Multimodal polyolefin pipe
|1 Nov 2002
|31 Ago 2004
|Mercury Plastics, Inc.
|Plastic-lined metal-encased tubing segment connector system
|16 Ago 2002
|7 Sep 2004
|Dow Global Technologies, Inc.
|Bimodal polyethylene composition and articles made therefrom
|8 Sep 2001
|11 Ene 2005
|Basell Polyolefine Gmbh
|Polyethylene molding compound suitable as a pipe material with excellent processing properties
|1 Dic 2003
|22 Mar 2005
|Univation Technologies, Llc
|Low haze high strength polyethylene compositions
|16 Oct 2001
|14 Jun 2005
|Solvay Polyolefins Europe-Belgium (S.A.)
|Polyethylene pipe
|2 Abr 2004
|31 Oct 2006
|Dow Global Technologies Inc.
|Bimodal polyethylene pipe composition and article made therefrom
|13 Ago 2004
|20 Mar 2007
|Univation Technologies, Llc
|High strength biomodal polyethylene compositions
|29 Jun 2004
|12 Jun 2007
|Equistar Chemicals, Lp
|Polymer resins with improved environmental stress crack resistance
|22 Dic 2003
|30 Oct 2007
|Univation Technologies, Llc
|Polyethylene compositions having improved tear properties
|7 Feb 2005
|25 Dic 2007
|Univation Technologies, Llc
|Polyethylene blend compositions
|30 Jun 2006
|18 Mar 2008
|Dow Global Technologies Inc.
|Bimodal polyethylene composition and articles made therefrom
|15 Oct 2002
|12 Ago 2008
|Borealis Technology Oy
|Pipe for hot fluids
|31 Oct 2007
|17 Mar 2009
|Univation Technologies, Llc
|Polyethylene blend compositions
|26 Mar 2004
|31 Mar 2009
|Borealis Technology Oy
|Polymer composition
|13 Sep 2007
|14 Jul 2009
|Univation Technologies, Llc
|Polyethylene compositions having improved tear properties
|7 Dic 2005
|29 Sep 2009
|Univation Technologies, Llc
|High density polyethylene
|3 Sep 2004
|17 Ago 2010
|Dow Global Technologies, Inc.
|Resin compositions for extrusion coating
|11 Ene 2008
|2 Nov 2010
|Dow Global Technologies
|Bimodal polyethylene composition and articles made therefrom
|24 Jun 2009
|21 Dic 2010
|Univation Technologies, Llc
|High density polyethylene and articles made therefrom
|9 Sep 2005
|28 Feb 2012
|Borealis Technology Oy
|Semiconductive polymer composition
|23 Ago 2010
|25 Dic 2012
|Dow Global Technologies Llc
|Bimodal polyethylene composition and articles made therefrom
|21 Nov 2007
|28 May 2013
|Borealis Technology Oy
|Multimodal polyethylene resin for pipe made by a single-site catalyst
|24 Jun 2010
|13 May 2014
|Basell Polyolefine Gmbh
|Polyethylene moulding composition
|3 May 2012
|23 Dic 2014
|Dow Global Technologies Llc
|Multistage process for producing ethylene polymer compositions
|5 Dic 2012
|14 Abr 2015
|Dow Global Technologies Llc
|Bimodal polyethylene composition and articles made therefrom
|17 Ago 2006
|9 Jun 2015
|Basell Polyolefine Gmbh
|Multimodal polyethylene molding composition for producing pipes having improved mechanical properties
|16 Oct 2001
|3 Jun 2004
|Andre Scheelen
|Polyethylene pipe
|8 Mar 2004
|5 Ago 2004
|Mercury Plastics, Inc.
|Process for manufacture of plastic-lined metal-encased tubing segment connector system
|2 Abr 2004
|7 Oct 2004
|Van Dun Jozef J.
|Bimodal polyethylene pipe composition and article made therefrom
|15 Oct 2002
|2 Dic 2004
|Magnus Palmlof
|Pipe for hot fluids
|22 Dic 2003
|23 Jun 2005
|Tae Hoon Kwalk
|Polyethylene compositions having improved tear properties
|12 Abr 2005
|3 Nov 2005
|Yokogawa Electric Corporation
|Waveform display apparatus
|29 Jun 2004
|29 Dic 2005
|Harilaos Mavridis
|Polymer resins with improved environmental stress crack resistance
|13 Ago 2004
|16 Feb 2006
|Kwalk Tae H
|High strength bimodal polyethylene compositions
|7 Feb 2005
|10 Ago 2006
|Kwalk Tae H
|Polyethylene blend compositions
|3 Sep 2004
|14 Dic 2006
|Oswald Thomas T
|Resin compositions for extrusion coating
|2 Nov 2005
|6 Ago 2009
|Borealis Technology Oy
|Multimodal polyethylene composition with improved homogeneity
|20 Ene 2010
|21 Jul 2011
|Fina Technology, Inc.
|Modification of Polyethylene Pipe to Improve Sag Resistance
|24 Jun 2010
|3 May 2012
|Basell Polyolefine Gmbh
|Polyethylene Moulding Composition
|14 Abr 2004
|4 Mar 2009
|A polyethylene composition with improved tear property
|17 Ago 2006
|14 May 2008
|Basell Polyolefine GmbH
|Multimodal polyethylene molding composition for producing pipes having improved mechanical properties
|31 Oct 2003
|21 May 2004
|Mercury Plastics Inc
|Plastic-lined metal-encased tubing segment connector system
|14 Abr 2004
|28 Jul 2005
|Tae Hoon Kwalk
|Polyethylene compositions having improved tear properties
|Clasificación de EE.UU.
|Clasificación internacional
|Clasificación cooperativa
|Clasificación europea
|24 Jul 2001
|23 Feb 2006
|Fee payment
Year of fee payment: 4
|18 Feb 2010
|Fee payment
Year of fee payment: 8
|21 Feb 2014
|Fee payment
Year of fee payment: 12


text:
This item is currently
Our Top Recommendations
Rave Pure Adult Water Ski Combos $159.99
HN-SQUA045 Radar
Radar Theory with Prime and ARTP Combo Water SkisItem # HN-SQUA045
Roll over to zoom
Click for full screen
- High-performance Theory ski
- Comfortable front Prime boot
- Perfect ARTP rear
- Great combo that gives you total control over your ride
- Available in a variety of sizes
Full Description
Guarantee & Returns
Similar Water Skis
OBrien World Team Slalom Ski with X-9
Rave Inflatable Ski Trainer Buds
Rave Kids Water Ski Trainers
Sponsored Links
Radar Theory with Prime and ARTP Combo Water Skis
Turn things up a notch with the Radar Theory with Prime and ARTP Combo Water Ski letting you carve through the water. The Theory ski has a lightweight AreoCore core, is 0.5 inches wider than the Stada for great acceleration and has an ideal top speed of 32 miles per hour. This combo has a Prime boot up front that has a lower cuff and Feather Frame that gives you total control over your ride. An ARTP takes the rear position featuring a floating tongue and contoured footbed.About Square OneSince its found

subset: commoncrawl


text:
The New HANGCHA CBD15-EM hand pallet truck for sale has been sold. --- We found you similar items below:
Your alert subscription is now active.
Check your email to confirm the subscription
Limit email alerts to:
The CBD15 is designed for easy and heavy use ( 2 hours per day) for the transport of goods within the company on smooth floors and no crossing ramp . Its compact design allows its use in tight spaces. In combination with an integrated charger, gel battery allows flexible use without adding water into the battery.
fork length - 1.2 m.


text:
WITN Classifieds - Eastern NC Classifieds - Greenville NC, Jacksonville NC, New Bern, Kinston, Washington NC Classifieds
Updated: 04/02/2012 -
Updated: 04/02/2012 -
Updated: 10/14/2014 - Dr. Martin Luther King, Jr. was a pivotal figure in the Civil Rights Movement. His life and works are still remembered and honored still today. Martin Luther King, Jr. Day was established as a national holiday in the United States in 1986.
Updated: 01/17/2011 - Dr. Martin Luther King Jr.'s "I Have Dream" speech is one of the most famous speeches in the history of the United States. The speech gave hope to Civil Rights supporters and remains a defining moment in the movement.
Updated: 03/26/2012 - The many notable achievements of Dr. Martin Luther King Jr. ... He was a voice for those that did not have one; he changed the course of history and is remembered for the cause he fought so hard for: equality for all.
Updated: 01/14/2012 - Resources to learn more about Dr. Martin Luther King, Jr. and the national holiday that celebrates his achievements.
Updated: 09/11/2010 - Related resources to learn more about the terrorist attacks on September 11th, 2001. View photographs from that day, read survivors' stories, and find out more about the memorials constructed at the locations where the attacks took place, nine years ago.
Updated: 09/11/2008 - Remembering September 11th - Memorials and Tributes remembering the victims and survivors of the attacks.
Updated: 08/14/2012 - In 2003, in response to the Sept. 11, 2001 attacks, several government agencies were split up and recombined to form the Department of Homeland Security.
Updated: 09/09/2010 - It is a day that we will never forget ... Learn more about that fateful September day in a chronological timeline of events.
Updated: 09/11/2008 -
Posted: 08/15/2008 - WITN Live test
Updated: 09/25/2008 - WITN Live Stream
Updated: 05/02/2008
- Click here
to look at local races and for results as soon as they become available.
Updated: 02/09/2015 - Gray Television: Items Prohibited for Sale on Online Classifieds
Updated: 09/08/2008 -
Updated: 08/12/2010 -
Updated: 07/01/2009 - To leave your condolences for Maria's family, enter your comments below.
Updated: 07/01/2009 -
Posted: 09/03/2007 -
Updated: 07/28/2010 -
Updated: 06/29/2015 -
Updated: 08/07/2007 -
Updated: 05/21/2007 - News Tip Line
Updated: 08/10/2007 - Check out all of WITN's blogs!


text:
The most recent figures from Japanese sales tracking authority Media Create show that the 3DS has sold 12,752,731 units in the island nation. By contrast, the Wii has sold 12,698,878 units. As GamesIndustry points out, with the 3DS enjoying its golden years and the Wii slowly fading from memory, it seems likely that the handheld will maintain its lead.
There are many reasons for the success of the 3DS, but most notable is the sales juggernaut known as Monster Hunter 4. Japan apparently loves murdering giant beasts, as the game has remained in Media Create's top sales spot since its debut. Buoyed by this hyper-popular game, the 3DS managed to sell 159,388 units in Japan during the week of September 16 alone - an impressive feat, given that total hardware sales for the period were only 187,773.
Buy from $200
- Key specs
- Reviews • 104
- Prices
- Discussions
- Game format Downloadable, Cartridge
- Online features Multiplayer, Store, Browser
- Direction control D-pad, Thumb stick
- Motion controls Accelerometer, Camera / optical
- Camera Internal
- Dimensions 0.8 x 5.3 x 2.9 in
- Weight 8 oz
- Released 2011-03-27
Nintendo Wii console


text:
Company information
Lead generation & marketing
Online promotion
Aiken Communications, Inc. wholesales electrical equipment cable clamp and staple, transformer bushings, harness board nails, din rail...
AVI Graphicx, Inc. provides wrap, tag, label, seal, bag printing, security, financial instruments printing, textile printing, ...
Provence Printing, Inc. provides screen printing, offset printing, letterpress printing and lithographic printing.
Ameriserv, Inc. specializes in providing Embossing, Planning or layout of graphic production, Typesetting, Digital printing, ...
Commercial printing, nec
Book printing
Printing trades machinery
Commercial printing, lithographic
Automotive and apparel trimmings
National Computer Corp., Inc. is a provider of custom computer programing service and other computer related products.
Books: Publishing, or Publishing and Printing
Newspapers: Publishing, or Publishing and Printing
Magazines: Publishing Only, Not Printed on Site
Manifold business forms
Coated and laminated paper, nec
Bruccoli Clark Layman, Inc. is a producer of camera-ready copy for reference works. They manufacture, promote and sell their books.
Affections Internationale is a commercial printing company that prints catalogs, brochures and postcards. The company provides ...
Newspapers, Publishing and Printing
Atlantic Publication Group, LLC is a publishing and electronic communications industries, producing a variety of magazines, newspapers...
Harris, J K & Co., LLC offers mortgage, insurance, small business, taxation policy, tax research, investment tax credit and tax ...
Communigraphics, Inc. provides commercial art and graphic design services and manufactures signs and advertising specialties, trimming...
offset Printing
Forms, Business: Lithographed
Commercial Printing, NEC
FB Johnston is the single source for your graphics needs for Original Equipment Mancfacturers, Point-of-Purchase and Fleet Graphics.
Frequent updates ensuring high quality data
Secure online payment
Help with expert advice
Dedicated customer service team


text:
Buffalo Ridge Band
Cincinnati, OH
You are using an outdated browser. Please upgrade your browser to improve your ReverbNation experience.
Buffalo Ridge Band
Cincinnati, OH
Sunday, March 17th, 2013 at 4:00pm
All Ages
St. Patty's Day @ Bucketheads.
Come enjoy more country music with Buffalo Ridge Band acoustically.
We will take a break when the selection show starts!
© 2015 eMinor Incorporated
All trademarks are the property of the respective owners. ReverbNation is not affiliated with the trademark owners.
Not listening to anything?
Try one of the ReverbNation Channels


text:
All posts under: Latest News
Game 41 Preview: Sacramento Kings at Houston Rockets
The Kings conclude a six-game trip with a visit to the lone star state.
Road Reaction Postgame Show: Sacramento Kings 114, New Orleans Pelicans 97
Recapping tonight's match-up between the Kings and Pelicans.
Sacramento Kings recall Ray McCallum from Reno
Rookie Ray McCallum is on his way to New Orleans to join the Kings after four games in the NBA Development League.
Game 40 Preview: Sacramento Kings at New Orleans Pelicans
Sacramento travel to the Big Easy to take on former Kings Tyreke Evans and crew.
Road Reaction Postgame Show: Oklahoma City Thunder 108, Sacramento Kings 93
Recapping tonight's road match-up between the Kings and Thunder.
Carl Landry returns for the Sacramento Kings
Veteran forward Carl Landry returns from a season-long injury
Sacramento Kings coach Michael Malone fined for verbal abuse of ref
Malone receives a disciplinary action from the NBA for berating an official.
Game 39 Preview: Sacramento Kings at Oklahoma City Thunder
Previewing tonight's road match-up between the Kings and Thunder.
Road Reaction Postgame Show: Memphis Grizzlies 91, Sacramento Kings 90
Recapping today's road match-up between the Kings and Grizzlies.


text:
Holiday Inn Express Delafield
No prices found through our partners. Please contact the business directly or check some of our recommended alternatives.
How has this hotel rated in the past?
Travelers also recommend:
- More recommendations
TravelPod Member ReviewsHoliday Inn Express Delafield
Very Freindly
This review is the subjective opinion of a TravelPod member and not of TravelPod.com.
TripAdvisor Reviews Holiday Inn Express Delafield
Travel Blogs from Delafield
Day 7, And on the 7th day I rested, lol
... So much history and so many Bikes it is incredible that they are still here, Including serial Number 1. While it is a restored bike and has parts that are inaccurate, It has number 1 stamped on a few parts, hence the name, while it may no be the first, it is the oldest Harley in existence. the war bikes, the famous bikes, the custom bikes and the prototype bikes make this an awesome place to melt away a few hours. Then in the next building is a display of ...
What am I doing here?
... track of from Falls BC to the Needham's compound. My personal bag had only about 35 pounds total so then I began the process of ensuring that i got as close to 50 pounds as possible by packing extra ministry items like hymn books or food items. My ministry bag consisted mainly of harmonicas, Deet and generator parts (I think that's what they were) :)
After my two bags were packed as close to 50 pounds as possible (49.5 and 50.1 to ...
Test post! Welcome
... family! I'll be returning June 29th late at night. I hope you enjoy reading all about my adventures! I'm not sure when I'll have time to post or take pictures, but I'll try to keep you all updated. See you all in 2 weeks! ...
A Day in Milwaukee
... a free beer. The glass was to be turned in at the end of the tour for a free pint glass. We also got coupons for free beers at several local pubs, There were five beers on tap: Wheat Monkey Ale, Fixed Gear American Red Ale, Wisconsinite Summer Weiss, Snake Chaser Irish Style Stout and Pumpkin Lager. Derek and Larry got to taste them all as I gave them each 1 of my tokens. I used my other two tokens to get a bottle of Golden Maple ...
City on lake Michigan
... skyline, we headed towards the nearest Walmart to park up. Unfortunately, the one we got to first was having some ground works done and weren't allowing any overnight parking. So we drove across the road to McD's to use their internet to find another one. Another one located, we headed off and thankfully this one was ok and there were a few others there too. So we settled in for the night and got off to bed.


text:
Iron Fist Boxing
Today, you've decided to take your fighting career to a new level. Training hard for the World circuit, your arms ache as you pummel the punching bag, building the muscles, focus and technique that you'll need to win. Nothing and no one else exists in this moment, it's just you and the sound of your gloves slapping the bag. You're going to be the next champ if it kills you. And it might. Iron Fist Boxing is the original, real-time 3D MMA fighting app. Don't be fooled by imitations, if you want authentic, heart-racing action, incredible next generation graphics and the absolute ultimate in gaming challenge. Game Features: • Experience high quality audio and real time 3D on Windows Phone 8 • Enjoy 6 game modes: Story mode, sparring, training and introducing the Speed Bag training, Punching Bag training and Punch-o-Meter. • Story mode: Experience a new world career in Brazil, Canada, Thailand, and USA. • Training mode: Train yourself for the Story mode. • Speed bag mode: Hit a speed bag as fast as you can. • Punching bag: Hit a punching bag in a given same sequence. • Punch-o-Meter: Hold you device and hit as hard as you can. • Sparring mode: Fight against a random fighter. • Play up to 32 characters with MMA combat styles and more: Boxing, Muay Thai, Savate, Kick Boxing, Brawler and Full Contact. • Gain access to new costumes and new attacks. • New camera views, characters can now move on the ring, many super moves and dodges added.More
Ratings and reviews
Average customer rating
Rating snapshot
You are unable to rate or review as you do not own this game.
Your review
Developer Response
Thanks. Your review will post soon.
There was an error posting your review. Please try again later.
1-10 of 24 reviews
Don't know if it's the demo or just buggy... Closes alot. Still fun thoughMore
- Yes (0)
- No (0)
Nice game ..lower the price a little bit and you will sold more.More
- Yes (0)
- No (0)
Fun gameMore
- Yes (0)
- No (0)
Try it, I thought it was no fun at allMore
- Yes (0)
- No (0)
Would like to know how to start career mode overMore
- Yes (2)
- No (0)
This game is awesome, I wish the were more fighter beat em up games.More
- Yes (0)
- No (0)
I hate your guts and I don't want no problems with your family of all households in the same year that was it about the same thing as being one day with your own personal information.More
- Yes (0)
- No (2)
Pretty neat game. It deserves more exposure. -update- you might want to nerf the computer. they have unlimited stamina, they take far less damage, extremely unforgiving.More
- Yes (0)
- No (0)
Love it!!!!😈😈😈😈😈😈More
- Yes (0)
- No (0)
Wow...... I will,buy this for sureMore
- Yes (0)
- No (0)
1-10 of 24 reviews
Iron Fist Boxing
App details
- Publisher
realtech VRMore
- Category
- Approximate size
53.43 MBMore
- Age rating
For ages 13 and upMore
- Supported processors
- Supported languages
English (United States)
- Learn more
- Additional terms
- More
- Capabilities
Use an anonymous Microsoft accountUse your musicUse the media items that are currently playingUse your device network servicesUse any of your Windows Phone sensors
Version notes
In this update • Bug fixes and improvements for every Windows Phone devices and better performance.


text:
More TV viewers tuning in online
Steve Henn
Jul 30, 2008 Twenty percent of TV viewers are tuning in exclusively on their computers, leaving networks and advertisers scrambling to find a way to capture the evolving market. Steve Henn reports.
A search engine that redefines 'cuil'
Janet Babin
Jul 28, 2008 As of today, Google has a new rival. But even with a broader search index, can Cuil (pronounced "cool") take on the Web's Goliath? Janet Babin tests the engine and gauges the results.
The insecurities of online banking
Jul 25, 2008 A University of Michigan researcher found 75 percent of banks he studied had dangerous design flaws in their Web networks that could leave customer data open to cyber-thieves. Mitchell Hartman has more on how to stay safe.
Companies quiet about DSL sans phone
Jul 24, 2008 Want a high-speed DSL connection without the landline phone service? It's available, but don't expect the phone company to advertise it. Katie Macpherson reports.
New jingles may be coins in your pocket
Jul 21, 2008 About $21 billion was spent on online advertising last year. Almost half went to search engines, with Google getting the lion's share. But commentator and economist Ian Ayres says you, too, may be able to get in on the action.
Yahoo adds Icahn to board
Dan Grech
Jul 21, 2008 Activist investor Carl Icahn is the newest member of Yahoo's board. Though a proxy showdown for control of the company seems to be averted, Icahn still has big plans for Yahoo. Dan Grech reports.
Week on Wall Street
Jul 18, 2008 Stockbroker and business analyst David Johnson chats with host Kai Ryssdal about what happened on Wall Street this week and what may lie ahead.
EA's Spore makes gamers the creators
Sep 22, 2011 Electronic Arts is about to release a new life-simulation game called Spore that takes players from a single-cell organism to interplanetary societies. GamePro Media's George Jones explains to Kai Ryssdal.
Making political points, not profits
John Dimsdale
Jul 17, 2008 With 2,000 left-of-center bloggers descending on Austin, Texas, this week for a gathering called Netroots Nation, we asked Marketplace's John Dimsdale to look into whether political blogging has profit-making potential.
Online humor is a serious business
Jeff Tyler
Sep 22, 2011 JibJab has transformed its animated political satire into a brand, taking it from a tiny corner of the Internet all the way to The Tonight Show. Jeff Tyler reports.


text:
With 1.7 million freelancers, we'll match you with the perfect talent.
The client has made the following changes to the job.
Job canceled.
Bidding period extended.
Client prefers freelancers from:
You are still able to submit a proposal for this job.
The client prefers freelancers from
a different location.
We are looking for Educators to Develope Real Estate Educational Courses based on the information we provide with some research involve.
Knowledge of Real Estate is an asset.
More information will be provided to qulify canidate.
Sign in or Register to see more


text:
This is an art film. Very avant garde!
Thanks for helping us associate the correct Pornstars to this video!
Help Us: Do these Pornstars appear in this video?
Pornstar Name:
Video Description:
Heres a great new camera angle for the hot tongue action that Joey loves so much. Watch while I lean over and give his thick hard cock a good sucking, biting, and licking until he shoots a nice big load of cum into my mouth. Oops! I missed some - Kisses! - Jenny
All Comments (14)
This is an art film. Very avant garde!
does she know how to suck cock...watch and learn girls!
She knows how to do it like noone else.
the best bj ever.
Jenny sucks a mean cock. I like the slow but dilederate approach she uses. It's sensual and sexy. I wish they would show her eyes and the rest of her body some so I can get the full idea of what I'm stroking to. I picture a nice healthy bush with tasty moist pussy lips, c cup tits with fancy nipples to tounge flick.
this woman is like a sucker fish, god I wish she would suck me off.
nice camera angle. his come dripped right into my face
Cut vid...maybe down too 2 minutes?
The good wife.
perfect. real cum . proper bj. just show a proper kiss after. i always do to show respect. tired of the fake cum on face routine.
lucky bastard!!!


text:
Amarela Resort
Amarela Resort
Hotel Guest Rating: 9.1/10
Barangay Libaong
Dauis, Panglao Island
Hotel Freebies Available*
• Free Internet in Room show dates
Amarela Resort
Located in Dauis, Amarela Resort is a perfect starting point from which to explore Panglao Island. Both business travelers and tourists can enjoy the hotel's facilities and services. To be found at the hotel are free Wi-Fi in all rooms, 24-hour front desk, luggage storage, Wi-Fi in public areas, car park. Designed for comfort, selected guestrooms offer internet access - wireless, internet access - wireless (complimentary), non smoking rooms, air conditioning, wake-up service to ensure a restful night. The hotel offers various recreational opportunities. Amarela Resort combines warm hospitality with a lovely ambiance to make your stay in Panglao Island unforgettable. ...read more
Amarela Resort Amenities
- 24-Hour Front Desk
- Air Conditioning
- Airport Transfer
- Babysitting
- Balcony/Terrace
- Bar
- Bbq Facilities
- Business Center
- Car Park
- Coffee/Tea Maker
- Complimentary Bottled Water
- Currency Exchange
- Daily Newspaper
- Desk
- Dvd/Cd Player
- Free Wi-Fi In All Rooms
- Hair Dryer
- In Room Safe
- Inhouse Movies
- Internet Access - Wireless
- Internet Access - Wireless (Charges Apply)
- Internet Access - Wireless (Complimentary)
- Laundry Service
- Library
- Luggage Storage
- Massage
- Meeting Facilities
- Mini Bar
- Newspapers
- Non Smoking Rooms
- Outdoor Pool
- Restaurant
- Room Service
- Safety Deposit Boxes
- Satellite/Cable Tv
- Separate Shower And Tub
- Shower
- Television
- Tours
- Water Sports (Non-Motorized)
- Wi-Fi In Public Areas
from $116
- La Pernela Beachfront Resort from $76 (0.5mi)
- French Kiss Asia Resort (0.6mi)
- Flushing Meadows Hotel from $71 (0.9mi)
- Panglao Palms Apartelle from $31 (0.9mi)
- Bohol Bee Farm Hotel (2.1mi)


text:
Women's Morning Expression SessionEvery Tuesday
10 - 11:30 a.m.
A morning attitude adjustment with art... return to your work, kids, day with a new outlook, less stress, more motivation and inpiration!
We figure out what we will do by what the group wants or needs. I do the work, you just come play.
No previous art experience needed.
Meetup has allowed me to meet people I wouldn't have met naturally - they're totally different than me.
— Allison, started Women's Adventure Travel
Meetup members, Log in
By clicking "Sign up" or "Sign up using Facebook", you confirm that you accept our Terms of Service & Privacy Policy


text:
One of my first business mistakes (and this is a big one) was agreeing to work for only ten dollars an hour. I hadn't even officially opened my web design business when a local business owner phoned to ask for help. She offered the ten dollar deal, and as I wanted to get started in […]
Blog Combining to Make Life Easier
People Who Don't Like Blogs, Who Were Attacked by Bloggers
- 1
- 2
- 3
- …
- 16
- Next Page»


text:
The Steampunk Empire
The Crossroads of the Aether
I love amakin odd items out of every day things.
Views: 30
Join The Steampunk Empire
Indeed Sir Felix, who indeed ? haha
Well yes, I mean to say, who doesn't have a few boring skulls lying about waiting to be punked into a cyberentic horror.
Welcome toThe Steampunk Empire
Sign Upor Sign In
Or sign in with:
Retro Victorian Steampunk Goggles Glasses Welding Cyber Punk Gothic Cosplay
Steampunk Goggles Glasses Vintage Victorian welding Cosplay Goth Punk Costume
Vintage Victorian Steampunk Goggles Glasses Welding Cyber Punk Gothic Cosplay
© 2015 Created by Hephzibah Marsh.
Badges |
Report an Issue |
Terms of Service
Please check your browser settings or contact your system administrator.


text:
Ken Moraif argues that "Buy and Hold" is a flawed strategy.
Click on the image above to watch his interview on Fox Business 'After The Bell'...
Financial & Retirement Planning
Your retirement should be your second childhood without parental supervision.
You should enjoy yourself -- go play, travel, have fun! Stay out late!
To do that you must have a solid financial plan that you have confidence in. Have you ever seen change like we are experiencing now? Have you ever seen deficits like we are running? Markets so volatile? The future so insecure?
If you are concerned about your financial security, please sign up for Ken's next seminar. It's designed for those of you who are at the average retirement age, which is over the age of 50. You will also get to enjoy some of the now World Famous Oatmeal Raisin and Chocolate Chunk Cookies!
Latest Email Market Alert - click here to Read
Is Bad News Good News?
October 4th, 2015 - A lot of bad economic data was greeted with an end of day rally last week. Despite that rally, the Dow is still lower than it was almost two years ago in 2013. It is hard to believe that one month could wipe out two years' worth of returns, but it does show why it is so important to have a sell strategy in place. The market has an uncanny way of losing money way faster than it makes it.Read more ...
View All Email Market Alerts
Latest Financial Tip Video - click here to Watch
Three Important Estate Documents You Need
Watch All Financial Tip Videos
Latest Press & News - click here to View
GoBankingRates.com: 10 Stock Market Predictions for 2016
"I see the Dow at 11,000 by the second half of next year," said Ken Moraif, founder and senior advisor at Dallas-based Money Matters and author of upcoming book "Buy, Hold, and Sell!" "This would be the result of a bear market brought on by a global recession."
Read the full article: http://www.gobankingrates.com/investing/10-stock-market-predictions-2016/
View All Press & News
Latest Radio Show Podcast - click here to Listen
October 10th, 2015
Listen to Our Radio Show Podcasts
Recent Financial Articles & Studies - click here for Information
Beware the Death Cross
I see signs that that a bear market is on its way. All the indicators are lining up, one after the other. The latest clue? We recently hit three death crosses in the market. Doesn't that sound awful? Well, it's not good.Read more ...
View All Articles & Studies


text:
Short version:
Out-going, sassy, nurturing, witty, athletic, adventurous, creative, ambitious, sarcastic, funny, engaging, entertaining, loyal, trustworthy, honest and straight forward. Oh, and I am a secret "Martha Stewart", damn can I decorate, cook and clean:)
Long version:
For every man that is interested in an A-typical girl, you should read on...
I love that people usually remember me after the first time they meet me. This is based on my ridiculous humor and saying all things that other people are thinking. I like to keep people entertained and sarcastic, funny comments usually do the trick.
I would also say that people remember my ambition and determination to always be moving forward. I run my own business and am extremely attracted to people that are comfortable veering off a steady path to seek out more in life. This goes for most things, including loving anything athletic. I am very into living an active lifestyle. I love to push myself to be better...
I am very comfortable with who I am and tend to like people who are confident within themselves as well. I am also a good judge of character and go with my first instincts about most things. Because of this, I have a wide circle of amazing friends that I have known for years. I consider my family the best of all those friends.
I am full of funny one-liners, but decided to be kind of straight forward in this instance.... If you are interested, you can hear all of my ridiculousness in person:)


text:
Key Lime Pie (Light)
Total Time
Prep 10 mins
Cook 20 mins
Delicious easy and light key lime pie! From R. Reisman.
Make and share this Key Lime Pie (Light) recipe from Food.com.
Ingredients Nutrition
- 354.88 ml graham cracker crumbs
- 44.37 ml granulated sugar
- 29.58 ml water
- 14.79 ml vegetable oil
- 396.89 g can low fat sweetened condensed milk
- 118.29 ml smooth 5% ricotta cheese
- 113.39 g light cream cheese, softened
- 78.07 ml fresh lime juice (approximately 2 limes)
- 9.85 ml finely grated lime rind
- 59.14 ml granulated sugar
- Preheat the oven to 375°F Spray a 9-inch pie plate with vegetable spray.
- Make crust: in a bowl, stir together the graham crumbs, sugar, water and oil until mixed. Pat the mixture onto the bottom and up the side of a prepared pan.
- Make filling: in a food processor, combine the condensed milk, ricotta cheese, cream cheese, lime juice and rind, and sugar; purée the mixture until it is smooth. Pour it into the crust.
- Place the pan in the centre of the oven and bake for approximately 20 minutes or just until the filling is set. Let the pan cool on a wire rack.
- Chill before serving.
Most Helpful
This was very light and flavorful, not nearly as creamy as "real" key lime pie, but it was deliciously satisfying if one is dieting. I cheated and used a pre-made light graham cracker crust, and reduced the sugar amount as suggested. It was lovely and tart, and a great non-guilty dessert. I made it for company, and they loved it! I did serve a dollop of light cool whip and a twirl garnish of lime on top.
a very quick and low fat key lime pie. Enjoyed it very much
This was wonderful.... This was also my first successful attempt at a graham craker crust and it didn't fall apart.... The ingredeints were perfect..... I didn't have any light cream cheese so I used two containers of key lime pie yogurt in place of it and cut the sugar to 1/8 cup to make sure it wasn't to sweet.... It turned out just right.... My DH loved it.... Of course, he had to have his dolap of cool whip on top.... Thanks for sharing....


text:
Visit our other Wisconsin Historical Society websites!
Refine or narrow your results by clicking any term in the gray boxes below.
Expand your results by removing any breadcrumb in a gray outlined box above. Click on the blue "X" to remove the term.
Narrow your results by entering a keyword into the search box above. Then click the "Search Within" checkbox, then click on the orange "Search" button.
If you did not find what you are looking for or you did not get any results, try changing your search term(s). See our Search Help page for more tips.
Date: 1945-01-04
Description: Nakoma Welfare League's traditional Twelfth Night Party at Nakoma School. Pictured are some of the people who assisted with the party arrangements: left to...
Date: 1939-12-13
Description: Window display of mannequin heads wearing hats in Sandra's Exclusive Millinery Shop, 101 State Street.
Date: 1931 ca.
Description: The Melchoir House was a popular hostelry and brewery operated by Jacob Melchoir. It later became an Indian boarding house.
Date: 1912 ca.
Description: A woman and small girl balance on a log crossing a small stream in a ravine. The trees and bushes are bare.
Date: 1953-04-13
Description: Cynthia Strassman, who will enter kindergarten next fall, is examined by pediatrician Dr. Richard B. Anderson as part of the Summer Round-Up program. The...
Date: 1913 ca.
Description: Exterior view of the Stockbridge Indian Mission with men standing near its entrance.
Date: date unknown
Description: Exterior of Eau Claire Hotel, located on the corner of South Barstow and Eau Claire Street. The view from across an intersection features the hotel buildi...
Description: Dageurreotype portrait of Dr. Chander B. Chapman of Madison. Dr. Chapman served as a regimental surgeon during the Civil War.
Date: 1959-09
Description: Carol Bryant, Robert Rancourt and Nancy Fowlkes act out a scene from "The Cold Wind and the Warm", the opening play of the Madison Theater Guild season pre...
Description: A KC-97 of the 126th Refueling Squadron, Wisconsin Air National Guard, refueling an F-84 fighter over eastern Wisconsin.
Date: 1915-04-21
Description: Three men operate a Titan 12-25(?) tractor upturning crop field with a plow as a group of men watch from behind.
Date: 1915 ca.
Description: A large group of veterans eating in the dining hall at the National Military Home, which opened in 1867. Men in white hats and uniforms serve a meal to th...
Date: 1945 ca.
Description: A simple wood frame cottage is built into the slope of the hill above Geneva Lake at Holiday Home Camp. A second building is seen in the background.
Date: 1925-02-04
Description: Farmer cultivating a field with a horse-drawn McCormick rotary hoe in front of silos and farm buildings.
Description: A farmer (possibly in Russia?) on a horse-drawn mower in a field.
Date: 1877 ca.
Description: Scene from Golden Ingots at the College of Mount Saint Vincent, founded by the Sisters of Charity of New York in 1847. Costumed students act outdoors in a...
Date: 1922
Description: View across road of the Berg & Jones Department Store, with posters in the front windows announcing an upcoming Ringling Brothers Barnum and Bailey Circus...
Date: 1929 ca.
Description: A production still for the Fox Hearst film "Romance of the Reaper". The film was produced by International Harvester to celebrate the Reaper Centennial. A...
Date: 1932 ca.
Description: Two cars are parked in a grove of trees; people sit at a picnic table in the background. There are other tables in the area, as well as benches and a trash...
Date: 1954-03-28 before
Description: Milwaukee Braves third baseman Eddie mathews demonstrates his swing during spring training.
If you didn't find the material you searched for, our Library Reference Staff can help.
Call our reference desk at 608-264-6535 or email us at:
© 1996-2015 Wisconsin Historical Society, 816 State Street, Madison, WI 53706


text:
Team USA: What lies ahead
Updated: August 20, 2010, 10:15 PM ETBy Chris Sheridan | ESPN.com
MADRID -- It's time to see how Team USA performs in a hostile environment, and time to see whether Kevin Durant can stop being too unselfish.
The Americans will face their first tough test Sunday when they play Spain, the defending world champions (ESPN3, 3 p.m. ET). But first they'll go up against Lithuania on Saturday (ESPN and ESPN3, 3 p.m. ET) in a game that does not figure to stay close for very long.
Then again, strange things never cease to happen in international basketball, ...
Read full story
You must be signed in to post a comment
You are fully responsible for the content you post. Content that includes profanity, personal attacks or antisocial behavior (such as "spamming" or "trolling"), or other inappropriate content or material will be removed. We reserve the right to block any user who violates our terms of use, including removing all content posted by that user.
2010 FIBA World Championship
- Simmons retro diary: Never bet against KD
- Sheridan: Team USA claims the gold
- Sheridan: Team USA eyes Turkey for title
- Sheridan: Team USA-Lithuania preview
- Sheridan: Team USA two wins from gold
- Sheridan: U.S. meets familiar foe in Russia
- Sheridan: USA looks Olympian in big win
- Sheridan: Perfection not on USA's mind
- Lithuania wins bronze at worlds
- Erden's last-second block seals Turkey win
- Serbia knocks out defending champ Spain
- Coach K fired up by comments on '72
- Lithuania, Argentina reach quarterfinals
- Russia knocks off Kiwis | History with USA
- Slovenia sinks 16 3-pointers, beats Australia
- Spain tops Greece; Serbia edges Croatia
- Day 6: Spain sends winless Canada home
- Day 5 Roundup: Krstic returns for Serbia
- Day 4 Roundup: France improves to 3-0
- Day 3 Roundup: Serbia cruises to win
- Day 2 Roundup: Brazil remains unbeaten
- Day 1 Roundup: France upsets Spain
- Greece, Serbia upset with post-brawl bans
- Sheridan: Can USA's B team win gold?
- TrueHoop: Ten things to wach at worlds
- Group A | Group B | Group C | Group D
- Sheridan: Team USA roster rundown


text:
Laotto, IN Office Space for Rent, Warehouses, and Retail Locations
Useful Links for Laotto:Commercial real estate agents (2) Commercial real estate companies (2) Tenant leasing requirements (0) Lease and sale comps (0)
Nearby Commercial Real Estate Listings:Auburn, IN (36)Avilla, IN (2)Churubusco, IN (4)Fort Wayne, IN (1,092)Garrett, IN (8)Huntertown, IN (4)Leo, IN (5)Waterloo, IN (5)
Showing 1 - 5 of 5 buildings with 4 total listings
Lot 4, Merchants Drive, Laotto, IN 46763
Suites ranging to 70,131 square feet.
Property is zoned for commercial or office use. Only 20 minutes north of Fort Wayne. Only 1/2 block west of heavily travelled Highwy 3 / Lima...
BND Commercial, LLC
11654 E 400 S, Laotto, IN 46763
Suites ranging to 97,975 square feet.
97,975 sq. ft. industrial space in 2 buidlings. Building #1 is 85,975 sq. ft. which includes a 4,800 sq. ft. office and 1,300 sq. ft. break room....
Corporate Commercial Group
6485 Merchants Drive, Laotto, IN 46763
Suites range from 38,560 square feet to 222,155 square feet.
This property has many possible uses and is zoned for manufacturing or industrial. Property has large overhead doors and docks can be added....
BND Commercial, LLC
Get Assistance From a Rofo Pro
Free advice on available properties in Laotto, IN.Input Your Needs
Rofo researches and displays commercial real estate listings from top brokerage firms and landlords in Laotto, IN making it easier to find available commercial space and compare current asking rental rates. In Laotto, IN there are currently and 3 warehouse spaces for rent with 2 real estate professionals to help you find the right space for you. Filter your search below and get free advice from recommended brokers in Laotto, IN.


text:
Catania purposely used the phrase "marriage equality" instead of same-sex marriage. It seems that this phrase must play better with focus groups and people who are contemplating the merits of gay marriage. Nowhere in the discussion of the council members on Tuesday was any mention made of the fact that same-sex marriage changes the definition of family, parenting, and education in our city in one fell swoop. Future concepts of family, marriage, and sex will be communicated differently because of such legislation. Neither was it mentioned that books like the Prince and the Prince, Heather has Two Mommies, or similar works will eventually be required reading for 8 year olds in the District. Imagine what sex education classes will have include in order prepare teenagers for "responsible entry" into the adult world.
Nothing was said about the devaluation of marriage that has happened in every nation where same-sex unions have received comparable status to heterosexual marriage. According to the work of Harvard trained Dr. Stanley Kurtz and others, rapid destabilization of the entire institution of marriage has been an unintended consequence of recognizing same-sex marriages.
Instead this type of meaningful conversation, Councilman Catania resorted to name calling when he declared that Marion Barry was a "bigot." To Barry's credit, the civil rights warhorse repudiated and rejected the "bigot" label. Councilman Catania quickly apologized. Instead, he implied that bigotry is the only reason that explains why thinking Americans oppose same-sex marriage. On the heels of this encounter, another council member began to describe my community pastors as "mean-spirited" and "intimidated."
The next steps in Washington, DC are simple - we must raise awareness in Congress that they can veto this bill. Further, Christians must begin to alert both Democratic and Republican congressmen about the need to vote against such measures. An immediate response from our supporters is very necessary.
Consider the following steps of action:
1. I am calling for a lobbying day in just 10 days in Washington, DC (May 20-22). We will bring over 300 ministers to DC for three days of inspiration, information, and impartation. This group will take time to lobby on the Hill and conduct prayer vigils in the city.
2. I am asking that every pastor and ministry leader notify their US Senators and Representatives that we are expecting them to veto this bill.
3. Finally, I am every American who understands the importance of protecting traditional marriage to pray every day for the legislators to realize the negative impact same-sex marriage legislation will have on our society.
The time to act is now. Let's not be caught sleeping on our watch!
Bishop Harry Jackson is chairman of the High Impact Leadership Coalition and senior pastor of Hope Christian Church in Beltsville, MD, and co-authored, Personal Faith, Public Policy [FrontLine; March 2008] with Tony Perkins, president of the Family Research Council.
Here we go: Jeb Bush's campaign weighing whether to have George W. hit the trail for him in South Carolina | Allahpundit