• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    BIOMODAL HIGH DENSITY POLYETHYLENE RESINS AND COMPOSITIONS WITH IMPROVED PROPERTIES AND METHODS OF PRODUCING AND USING THE SAME. The present description relates to biomodal high density polyethylene polymer compositions with improved high melt resistance and good processability comprising a base resin which has a density of about 845 kg / m (3) to about 955 kg / m (3), and comprises an ethylene polymer (A) having a density of at least about 968 kg / m (3), in an amount ranging from 45% to 55% by weight and an ethylene polymer (B) having a density less than the polymer density (A) in which said composition has a complex viscosity at a shear rate of 0.01 at rad / s ranging from about 200 to about 450 kPa.if a complex viscosity at a the shear rate of 100 rad / s ranging from about 1900 to 2500 Pa.s. The present description also relates to methods of producing and using the present compositions, and articles made from the composition, and preferably, tubes and accessories.
    公开号:BR112014016166B1
    申请号:R112014016166-6
    申请日:2012-12-21
    公开日:2021-02-09
    发明作者:Joshua Allen Cottle；Mark Anthony Gessner；Robert Ernest Sander；Luc Dheur
    申请人:Ineos Olefins & Polymers Usa, A Division Of Ineos Usa Llc；
    IPC主号:
    专利说明:

    [001] This application claims the priority of the provisional US patent application number 61 / 631,209 filed on December 29, 2011, the description of which is expressly incorporated herein by reference in its entirety.
    [002] The present description refers to polyethylene resins, more particularly those that are suitable for use as tubes, tube connections or fittings, and the process for producing such resins. The present description also refers to the use of polyethylene compounds comprising such resins for the manufacture of tubes or tube accessories, and the accessories themselves.
    [003] For many applications of high density polyethylene (HDPE), polyethylene with greater strength, strength and resistance to breaking under environmental stress (ESCR) is desirable. In the context of the manufacture of large wall thick pipe, increased melt resistance helps prevent the polymer material from flowing downstream due to the effects of gravity. Bending materials produce a tube with thicker tube walls over the bottom of the tube and a thinner distribution of the wall over the top of the tube. Industrial pipe standards define limits for maximum allowable variation in wall thickness. Thus, use of polymers with high curvature characteristics can result in the production of tubes that do not fit or are not able to meet certain standards. An increase in the melt resistance of the polymer, and in turn a reduction in curvature, can be accomplished by a long chain branching in the polymer. The long branch prevents the material from bending as the material exits the tube extruder, before it enters the vacuum cooling tank.
    [004] The present description is also aimed at compositions with a good resistance to curvature. The description is also directed to the composition suitable for applications where greater melt resistance with low shear of the molten polymer would be beneficial including blow molding, extruded sheet and film applications. In one embodiment, the compositions of the present description are used for the production of tubes and fittings. Tube resins require high rigidity (resistance to breakage deformation), combined with high resistance against slow crack growth, as well as rapid crack propagation producing impact resistance. Polyethylene tubes are widely used since they are lightweight and can be easily joined by fusion welding. Polyethylene pipes also have good flexibility and impact resistance, and are corrosion free. However, unless they are reinforced, they are limited in their hydrostatic resistance by the inherent low breaking stress of polyethylene. It is generally accepted that the higher the density of the polyethylene, the greater the long-term hydrostatic resistance. ISO 9080, ISO 12162, ASTM D883 ASTM D3350 describe tube classifications according to PE100 and PE471 specifications.
    [005] A requirement for such tubes is to have very good long-term strength as measured by the “Minimum required strength” (MRS) rating. Extrapolation according to ISO 9080 shows that they have a stress at 20 ° C / 50 years extrapolated to an expected lower level (97.5% confidence level - "LPL") of at least 8 and 10 MPa; such resins have an MRS rating of MRS 8 or MRS 10 and are known as PE80 and PE100 resins respectively. Another requirement for such tubes is to have very good long-term strength as represented by the Hydrostatic Design Base (HDB). Extrapolation according to ASTM D2837 shows that they have a 23 ° C / 100,000 hours interception of at least 1,530 psi (10.55 MPa). Such resins would have an HDB rating of 1600 psi (11.03 MPa) and are known as PE3608 or PE4710 resins depending on other characteristics of the short-term material such as density and resistance to stress cracking. In one embodiment, the present description is directed to tubes manufactured with the compositions and polyethylene resins of the present description. In one embodiment, the tubes produced with the resins and compositions of the present description meet the specifications of PE100. In one embodiment, the tubes produced with the compositions and resins of the present description meet the specifications of PE4710. These are polyethylene resins, which, when used to form tubes of specific dimensions, survive a long-term pressure test at different temperatures for a period of 10,000 hours. The density of the current basic powder used in the production of a PE100 or PE4710 compound ranges from about 0.945 g / cm3 to about 0.955 g / cm3, preferably from about 0.947 to 0.951 g / cm3, and preferably is about 949 g / cm3 . In certain embodiments, polyethylene resins contain conventional amounts of black pigments and exhibit densities ranging from about 0.958 to about 0.961 g / cm3.
    [006] In one embodiment, the present description is also directed to polymer compositions with a good resistance to curvature. In one embodiment, the compositions and resins of the present description could be used for applications where resistance to the melting of high density polyethylene is important, including blow molding, extruded sheet, and film applications. In another embodiment, this description is also directed to tubes manufactured with the composition and polyethylene resin of the present description having a diameter greater than 60.696 cm and a wall thickness greater than 5.71 cm. Larger diameter thick tubes generally require high density polyethylene (HDPE) with high melt resistance. High melt-resistant polymer can be supplied by the long chain branch in the polymer that prevents the material from being bent as the material exits the tube extruder, before it enters the vacuum cooling tank. High density polyethylene resins with a curvature with poor melt resistance, start to flow downstream due to the effects produced by gravity, producing tubes with non-uniform wall distributions. Bending materials produce a tube with thicker walls at the bottom of the tube and a thinner wall distribution at the top of the tube. Industrial pipe standards define the limits of maximum allowable variation in wall thickness. Low bending behavior for most pipe extrusion applications can be predicted by a complex viscosity of the material measured at a frequency of 0.01 rad / s at a temperature of 190 ° C (n * o, hi). Examples of tubes with low bending behavior but poor mechanical properties have been discussed in the art in WOo8oo6487, EP-i.i37.7o7 and EP-B-i.655.333. The compositions of the present description exhibit excellent mechanical properties, such as resistance to breaking under tension, resistance to deformation and resistance to the rapid propagation of cracks.
    [007] In another modality, the present description is related to the tube having resistance to breaking under very high environmental stress (PEioo-RC). Pipes with these characteristics are suitable for pipe laying techniques such as installations without sand, or when the pipe is in contact with aggressive media such as detergents. For example, the German PASio75 (Public Application Scheme for pipe installation without sand) requires the following properties for pipes to be marked with PEioo-RC (for break resistance): FNCT> 876o h to 8 ° C under 4 MPa in 2 % of Arkopal Nl00, load site test> 3760 h at 80 ° C under 4 MPa in 2% of Arkopal Nloo and NPT> 876o h at 8 ° C [i76 ° F], 9.2 bar (920 kPa). The compositions of the present description meet the requirements for the classification of PEi00-RC. Pipes with good mechanical properties are known in the art, for example, in WO08006487 and EP i.985.660.
    [008] In one embodiment of the present description, crosslinking is used to improve the melt resistance of polymer compositions while retaining good processability and mechanical properties. In one embodiment, crosslinking of the polymer with the addition of peroxide is used to achieve the properties of the present composition. Methods for increasing the melt resistance of HDPE compositions by using thermally decomposing initiators, such as peroxides, have been discussed in the art in US Patent No. 4,390,666, WO 08/006487, WO 9747682, WO 2011 / 090846, US patent No. 4,390,666, WO 2008/083276, WO 2009/091730, publication of US patent application No. 2007/0048472, WO 2006/036348, EP1969018, publication of US patent application No. 2008/0161526 and publication of US patent application No. 2011/0174413. In one aspect, the present description is also directed to processes and methods for making a bimodal high density polyethylene pipe resin with increased melt resistance while maintaining processability and retaining the characteristic properties of PE100 and USPE4710 materials.
    [009] Processability of a polymer composition can be characterized by its viscosity at a given shear stress that could be experienced during the extrusion of the tube. This processability can be predicted by viscosity measurements, such as complex viscosity at 100 rad / s (n * 100) for pipe extrusion and / or a fluidity index test, such as HLMI. Processability for most tube extrusion applications can be predicted by a complex viscosity of the material at a frequency of 100 rad / s at a temperature of 190 ° C. Processability can be measured directly in pipe extrusion equipment by the productivity and amperage load required to produce a given pipe size.
    [0010] The complex viscosity at 100 rad / s (n * ioo) more closely represents the shear rate submitted on the material during the extrusion of the tube. Viscosity is the prediction of processability, that is, demand for extrusion energy and ultimately productivity. Within the context of the present description, the complex viscosity at 100 rad / s (n * iQü) can also be referred to as the processing viscosity. A polymer composition with a lower processability viscosity value could be easier to process, or requires less energy or amperage to achieve the same productivity (lbs / hour), when compared to a composition with a high processability viscosity value. If a material's processability viscosity is too high or the material is too viscous, the energy required to achieve a desired throughput rate may be beyond the capacity of the extrusion equipment. In this case, the total productivity for that resin would be the limiting factor, and extrusion rates would have to be lowered until the line's energy demand was within the equipment's capacity. For pipe extrusion resins, a resin with good processability is generally expected to have a complex viscosity at 100 rad / s ranging from about 1,900 to about 2,600 Pa.s
    [0011] In a first aspect, the present description provides a bimodal high density polyethylene polymer composition comprising a base resin that has a density of about 945 kg / m3 to about 955 kg / m3, preferably 946 kg / m m3a 951 kg / m3, more preferably 947 kg / m3 to 951 kg / m3, and comprises an ethylene polymer (A) having a density of at least 968 kg / m3, preferably above 970 kg / m3, more preferably above 971 kg / m3 in an amount ranging from about 45 to about 55% by weight, preferably 47 to about 53%, preferably about 48 to about 52% by weight, even more preferably from about 49, 5 to about 51.5% by weight, and an ethylene polymer (B) having a density lower than the density of polymer A, wherein said composition has a complex viscosity at a shear rate of 0.01 rad / s ranging from about 200 to about 450 kPa.s, preferably from about 220 to about 450 kPa.s, even more preferably d and about 220 to about 420 kPa.if a complex viscosity at a shear rate of 100 rad / s ranging from about 1900 Pa.s to about 2600 Pa.s, preferably from about 2,000 to about 2,500 Pa. s, more preferably from about 2,100 to about 2,450 Pa.s.
    The MI5 melt index of the polyethylene composition is preferably from about 0.1 to about 0.5 g / 10 min, preferably from 0.20 to 0.45 g / 10 min, more preferably from 0, 2 to 0.4 g / 10 min. For the purposes of the present description, the HLMI, MI5 and MI2 fluidity indices are measured according to IS01133 at a temperature of 190 ° C under loads of 21.6 kg, 5 kg and 2.16 kg, respectively.
    [0013] The SHI pseudoplasticity index is the proportion of the viscosity of the polyethylene composition at different shear stresses. In the present description, shear stresses at 2.7 kPa and 210 kPa are used for the calculation of SHI2.7 / 210 which can be considered as a measure of the amplitude of the molecular weight distribution. The SHI2.7 / 210 of the composition preferably ranges from about 60 to about 115, preferably from about 65 to 105, more preferably from about 75 to 95.
    [0014] The composition preferably has a G '(G "= 3000) (Pa) ranging from about 1600 to about 2500, preferably from about 1650 to about 2400, more preferably from about 1700 to about of 2200.
    [0015] The composition preferably has a complex viscosity at a constant shear stress of 747 Pa (n * 747), preferably about 400 kPa.s to about 1300 kPa.s, preferably 500 to 900 kPa.s , and more preferably 550 to 900 kPa.s. In one embodiment, the composition has a n * 747 viscosity ranging from about 650 to about 900 kPa.s.
    [0016] The composition preferably has a zero shear viscosity (n * c), preferably greater than about 500 kPa.s, preferably greater than 650 kPa.s, and more preferably greater than 800 kPa.s . In one embodiment, the composition has a viscosity n * 0 ranging from about 800 to about 1,200 kPa.s.
    [0017] The base resin may optionally further comprise a small fraction of prepolymerization in an amount of 5% or less based on the total polyethylene. Alternatively or additionally it may also comprise a fraction of high molecular weight polymer, having an average weight molecular weight greater than the average weight molecular weight of the components (A), (B) or the prepolymer, in an amount of 5 % by weight or less based on total polyethylene.
    [0018] It is generally preferred that the ratio of polymer (A) to polymer (B) in the base resin is between 45:55 and 55:45, more preferably between 47:53 and 53:47, and even more preferably between 48 : 52 and 52:48, regardless of the presence or absence of additional polyethylene fractions.
    [0019] The shape of the molecular weight distribution curve, that is, the appearance of the graph of the fraction by weight of the polymer as a function of its molecular weight, of a multimodal polyethylene such as the base resin will show two or more maximums or at least be distinctly enlarged compared to the curves for the individual fractions. For example, if a polymer is produced in a sequential multi-stage process using reactors coupled in series with different conditions in each reactor, each of the polymer fractions produced in the different reactors will have its own molecular weight and molecular weight distribution average. The molecular weight distribution curve of such a polymer comprises the sum of the individual fractions curves, typically producing a curve for the multimodal polymer having a substantially single peak or two or more distinct maximums. A "substantially single peak" may not follow a Gaussian distribution, it may be broader than a Gaussian distribution might indicate, or it may have a flatter peak than a Gaussian distribution. Some substantially unique peaks may have a tail on each side of the peak. In some embodiments, it may be possible mathematically to solve a "substantially single peak" on a molecular weight distribution curve in two or more components of different methods.
    [0020] It is particularly preferred that the ethylene polymer (A) is a homopolymer, and the ethylene polymer (B) is a copolymer of ethylene and a C4-C8 alpha-olefin.
    [0021] As used in this description, the term "homopolymer" is understood to mean an ethylene polymer composed essentially of monomer units derived from ethylene and substantially devoid of monomer units derived from other olefins, which correspond to a comonomer content of less than about 0.15 mol%. The term "ethylene copolymer and a C4-C8 alpha-olefin" is understood to mean a copolymer comprising monomer units derived from ethylene and monomer units derived from a C4-C8 alpha-olefin and, optionally, at least one other alpha -olefin. C4-C8 alpha-olefin can be selected from olefinically unsaturated monomers comprising 4 to 8 carbon atoms, such as, for example, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3 - and 4-methyl-1-pentene and 1-octene, Preferred alpha-olefins are 1-butene, 1-hexene and 1-octene and more particularly 1-hexene. Most preferred comonomers are C6-C8 alpha-olefins, the most preferred comonomer is 1-hexene.
    [0022] The other alpha-olefin which may also be present in addition to C4-C8 alpha-olefin is preferably selected from olefinically unsaturated monomers comprising from 3 to 8 carbon atoms, such as, for example, propylene, 1-butene , 1-pentene, 3-methyl-1-butene, 3- and 4-methyl-1-pentents, 1-hexene and 1-octene.
    [0023] The content in the composition of monomer units derived from C4-C8 alpha-olefin, hereinafter called the co-monomer content is preferably from about 0.3 to 0.65 mol%, preferably from about 0.4 to 0.65 mol%, and even more preferably from about 0.4 to 0.6 mol%. The copolymer content (B) of monomer units derived from C4-C8 alpha-olefin is generally at least 0.6 mol%, in particular at least 0.8 mol%. The copolymer co-monomer content (B) is usually at most 1.5 mol%, preferably at most 1.1 mol%.
    [0024] In one embodiment of the present description, the polymer (A) has an MI2 ranging from about 200 to 600. In one embodiment of the present polymer (A) has an MI2 ranging from about 300 to 500 g / min. In one embodiment, the polymer density (A) preferably ranges from about 968 kg / m3 to 975 kg / m3. The density of the polymer (A) most preferably ranges from about 970 kg / m3 to 974 kg / m3 and from 971 to 974 kg / m3. The copolymer density (B) preferably ranges from about 915 kg / m3 to 935 kg / m3, and from about 920 kg / m3 to about 930 kg / m3.
    [0025] If polymers (A) and (B) are produced separately and then mixed, it is possible to directly measure the fluidity index, density and comonomer content of both polymers. However, if the multimodal polymer is produced in a multi-stage process in which one polymer is produced before the other, then the second polymer is produced in the presence of the first polymer, the fluidity index, density and comonomer content of the second polymer cannot be measured, and instead for the purposes of this description, they are defined as follows.
    [0026] The flow rate of the second polymer is defined as that measured for the second polymer when produced separately under the same polymerization conditions as used to produce the multimodal based resin. In other words, the second polymer is produced separately using the same catalyst and under the same polymerization conditions as those employed in the second multimodal polymerization reactor and its flow rate is then measured. The density of the second polymer is defined as that calculated from the ratio: density (resin) =% by weight (1) * density (1) +% by weight (2) * density (2), where (1) and (2 ) are, respectively, the first and second polymers.
    [0027] The comonomer content of the second polymer is defined as that calculated from the relationship: comonomer content (resin) =% by weight (1) * comonomer content (1) +% by weight (2) * comonomer (2) where (1) and (2) are the first and second polymers, respectively.
    [0028] If the multimodal polymer is produced with a "multiple catalyst system", such as a bimetallic catalyst, it is possible to produce both polymers (A) and (B) in the same reactor. In such a case, it is not possible to directly measure the properties of either polymer (A) or polymer (B). Therefore, in this case, the properties of both polymers (A) and (B) are defined as those obtained when they are prepared separately using the individual catalysts of the "multiple catalyst system", and under the same polymerization conditions as those used for produce the multimodal polymer.
    [0029] In one embodiment, a multimodal composition of the present description comprises a base resin which has a density ranging from about 947 to about 951 kg / m3, and which comprises an ethylene polymer (A) having a hair density minus 971 kg / m3 in an amount ranging from about 48 to about 52% by weight, an ethylene polymer (B) having a density of about 920 to about 930 kg / m3, in an amount ranging from about from 52 to about 48% by weight, and said composition having a comonomer content ranging from about 0.30 to about 0.65 mol% G '(G "= 3000) (Pa) between 1700 and 2200 Pa., A complex viscosity at a shear rate of 100 rad / sec ranging from about 2100 to about 2450 Pa.s, a complex viscosity at a shear rate of 0.01 rad / s ranging from about 220 to about 420 kPa.s.
    [0030] In other embodiments, the polymer compositions may additionally comprise components without departing from the scope of the present description. In particular, the composition can contain conventional additives in an amount of up to about 10% by weight, preferably up to about 5% by weight and more preferably up to about 3% by weight based on the total weight of the composition. Such additives include stabilizers (oxidizing agents and / or anti-UV agents), anti-static agents, processing aids, as well as pigments. The composition can also contain up to 10% by weight of another polyolefin, preferably another polyethylene.
    [0031] As used in the present description, "multiple catalyst system" refers to a composition, mixture or system including at least two different catalyst compounds, each having the same or a different metal group, including a "double catalyst ", for example, a bimetallic catalyst. Use of a multiple catalyst system allows the multimodal product to be produced in a single reactor. Each catalyst compound other than the multiple catalyst system can be produced on a support particle, in which case a double (bimetallic) catalyst is considered to be a supported catalyst. However, the term bimetallic catalyst also broadly includes a system or mixture in which one of the catalysts resides in a collection of support particles, and another catalyst resides in another collection of support particles. Preferably, in the latter case, the two supported catalysts are introduced into a single reactor, either simultaneously or sequentially, and polymerization is conducted in the presence of the bimetallic catalyst system, i.e., the two collections of supported catalysts. Alternatively, the multiple catalyst system includes a mixture of unsupported catalysts in the form of a suspension or solution.
    [0032] In an embodiment according to the present disclosure, the multimodal polyethylene base resin is preferably obtained by the multi-stage polymerization of ethylene, typically using a series of reactors. A multi-stage process is a polymerization process in which a polymer comprising two or more fractions is produced by producing at least two polymer fractions in separate reaction stages, usually with different reaction conditions at each stage, in the presence of the product of the reaction from the previous stage. The polymerization reactions used at each stage may involve homopolymerization reactions or conventional ethylene copolymerization, for example, polymerizations in gas phase, suspension phase, liquid phase, using conventional reactors, for example, recirculation reactors, phase reactors gas, batch reactors, etc.
    [0033] It is preferred that the polymer (A) is produced in the first reactor, and that the polymer (B) is produced in a subsequent reactor. However, this order can be reversed. If the base resin includes a prepolymer, this is done in a reactor preceding the first reactor. It is preferred that all reactors are suspension reactors, in particular, suspension recirculation reactors. In one embodiment, the preferred multi-stage polymerization process includes in a first reactor, ethylene is polymerized in suspension in a first mixture comprising a diluent, hydrogen, a catalyst based on a transition metal and a co-catalyst, to form 30 to 70% by weight with respect to the total weight of the composition of an ethylene homopolymer (A); said first mixture is extracted from said reactor and is subjected to a pressure reduction, in order to degass at least a portion of the hydrogen to form at least a partially degassed mixture, and, said at least partially degassed mixture, together with ethylene and alpha-olefin C4-C8 and, optionally, at least one other alpha-olefin, are introduced into a subsequent reactor and suspension polymerization is carried out in order to form from 30 to 70% by weight, in relation to the total weight of the composition, of a copolymer of ethylene and alpha-olefin C4-C8.
    [0034] In one embodiment, a component (A) of low molecular weight ethylene polymer (LMW) is produced in a first reactor and a component (B) of high molecular weight ethylene polymer (HMW) is added in a second reactor. Within the context of the present description the terms "component (A) of the ethylene polymer LMW", "component (A) of the ethylene polymer" or "ethylene component LMW" can be used interchangeably. Likewise, within the context of this description the terms "component (B) of the ethylene polymer HMW", "component (B) of the ethylene polymer" or "ethylene component HMW" can also be used interchangeably. component (A) of ethylene polymer LMW for the final bimodal HDPE polymer is in an amount ranging from 45% to 55% by weight, preferably from 47 to 53% by weight, preferably from 48 to 52% by weight, and even more preferably from 49.5 to 51.5% by weight.In one embodiment, polymerization occurs in both reactors in the presence of hydrogen, and the ratio of molar hydrogen concentration in the first reactor to the molar hydrogen concentration in the second reactor is from 250: 1 to 350: 1.
    [0035] The description also provides a process for obtaining a pipe or pipe fitting, comprising the steps of polymerizing ethylene and optionally comonomer, mixing the polyethylene composition, and then extruding or injection molding the composition to form an article. In most embodiments according to the present description, the step of polymerizing ethylene preferably forms a multimodal polyethylene.
    [0036] The catalyst employed in the polymerization process to produce the polyethylene based resins used in the compositions of the description can be any catalyst (s) suitable for the preparation of such polyethylenes. If polyethylene is bimodal, it is preferred that the same catalyst produces both low and high molecular weight fractions. For example, the catalyst can be a metallocene catalyst or Ziegler-Natta catalyst. Preferably, the catalyst is a Ziegler-Natta catalyst.
    [0037] In the case of a Ziegler-Natta catalyst, the catalyst used comprises at least one transition metal. Transition metal means a metal in groups 4, 5 or 6 of the Periodic Table of the Elements (CRC Handbook of Chemistry and Physics, edition 75, 1994-95). The transition metal is preferably titanium and / or zirconium. A catalyst comprising not only the transition metal, but also magnesium is preferably used. Good results have been obtained with catalysts comprising: from 5 to 30%, preferably from 6 to 22%, more preferably 8 to 18% by weight of transition metal, from 0.5 to 20%, preferably from 2 to 18% , more preferably 4 to 15% by weight of magnesium, from 20 to 70%, preferably 30 to 65%, more preferably 40 to 60% by weight of halogen, such as chlorine, from 0.1 to 10%, preferably from 0.2 to 8%, more preferably from 0.5 to 5% by weight of aluminum; the general balance consisting of elements resulting from products used for its manufacture, such as carbon, hydrogen and oxygen. These catalysts are preferably obtained by co-precipitation of at least one transition metal composition and one magnesium composition by means of a halogenated organoaluminium composition. Such catalysts have been described in U.S. Patent Nos. 3,901,863; 4,292,200 and 4,617,360. The catalyst is preferably introduced only in the first polymerization reactor, that is, there is no introduction of fresh catalyst in the later polymerization reactor. The amount of catalyst introduced into the first reactor is generally adjusted to obtain an amount of at least 0.5 mg of transition metal per liter of diluent. The amount of catalyst does not normally exceed 100 mg of transition metal per liter of diluent.
    [0038] In one embodiment, a preferred catalyst contains 8 to 18% by weight of transition metal, 4 to 15% by weight of magnesium, 40 to 60% by weight of chlorine and 0.5 to 5% by weight of aluminum, and have a residual organic radical content in the precipitated catalyst of less than 35% by weight. These catalysts are also obtained by co-precipitation of at least one transition metal compound and one magnesium compound by means of a halogenated organoaluminium compound, but with a transition metal to magnesium ratio of no more than about 1: 1. For further discussion on this catalyst see EP-B-2.021.385 which is incorporated in its entirety.
    [0039] A preferred catalytic system for use in the process of the present description comprises a catalytic solid comprising magnesium, at least one transition metal selected from the group consisting of titanium and zirconium and halogen, prepared successively by reacting, in a first step (i) at least one magnesium compound (M) chosen from organic magnesium compounds containing oxygen with at least one compound (T) selected from the group consisting of zirconium and organic tetravalent titanium compounds containing up to one liquid complex to be obtained; treating, in a second stage, the complex obtained in the first stage with an aluminum compound containing halogen of formula AlRnX3- n, where R is a hydrocarbon radical comprising up to 20 carbon atoms, X is a halogen and n is less than 3, and an organometallic compound of a metal chosen from lithium, magnesium, zinc, tin or aluminum.
    [0040] The preparation of the solid catalytic complex comprises step (ii), the main function of which is to reduce the valence of the transition metal and simultaneously additionally halogenate, if necessary, the magnesium compound and / or the transition metal compound : thus, the majority of alkoxy groups still present in the magnesium compound and / or in the transition metal compound are replaced by halogens, such that the liquid complex obtained after step (i) is transformed into a catalytically active solid. The reduction and possible subsequent halogenation are carried out simultaneously using the halogen-containing aluminum compound which thus acts as a reductive halogenating agent. The treatment using the halogen-containing aluminum compound in step (ii) of the catalytic solid preparation can be carried out by any suitable known means, and preferably, gradually adding the halogen-containing organo-aluminum compound to the liquid complex obtained in step (i). The temperature at which step (ii) is carried out must not exceed 60 ° C, temperatures of no more than 50 ° C being the most advantageous. The preferred temperature range is 25 to 50 ° C, with the most preferred range being 30 to 50 ° C. The co-catalyst used in the process is preferably an organoaluminium compound. Non-halogenated organoaluminium compounds of formula AlR3 where R represents an alkyl group having from 1 to 8 carbon atoms are preferred. In one embodiment, triethyl aluminum and triisobutyl aluminum are preferred.
    [0041] In one embodiment, the multi-stage polymerization process described above for producing the description composition uses a Ziegler-Natta catalyst. In such a case, the polymerization temperature is generally 20 to 130 ° C, preferably at least 60 ° C, and generally does not exceed 115 ° C. The total pressure at which the process is carried out, in general, is 0.1 MPa to 10 MPa. In the first polymerization reactor, the total pressure is preferably at least 2.5 MPa. Preferably, it does not exceed 5 MPa. In another polymerization reactor, the total pressure is preferably at least 1.3 MPa. Preferably, it does not exceed 4.3 MPa.
    [0042] The polymerization period in the first reactor and in the other reactor is, in general, at least 20 minutes, preferably at least 30 minutes. The polymerization period generally does not exceed 5 hours, and preferably does not exceed 3 hours. In this process, a suspension comprising the resin of the description is collected at the outlet of the other polymerization reactor. The composition can be separated from the suspension by any known means. Generally, the suspension is subjected to a pressure expansion (final expansion) to eliminate the diluent, ethylene, alpha-olefin and hydrogen from the composition.
    [0043] In one embodiment, the material modified by decomposable thermal initiators such as a peroxide according to the present description can be used in the production of thick walled pipe within those industrial standards, while still meeting or exceeding the standards of PEl00 and PE4710 , and while maintaining good processability.
    [0044] In one embodiment, the polymer compositions according to the present description are cross-linked, usually in a mixing step after production. The polymer composition can be cross-linked using decomposable thermal initiators. The bimodal resin flake produced in the reactor or reactors acts as the base material to be modified. This material is fed to the extrusion equipment together with the additive package and the decomposable thermal initiators. The extrusion equipment melts the HDPE flake and disperses the additives and decomposable thermal initiators. Consistency of the polymer and additive feed determines how dispersed the polymer / additive / thermal initiators mixture is dispersed. The temperature and residence time in the mixture and in the extruder cause the decomposable thermal initiators to react with the base polymer.
    [0045] In one embodiment, crosslinking of the polymer is done using decomposable thermal initiators. The crosslinking of the polymer is controlled by the addition of the initiator in the form of powder or liquid to the additive premix fed to the extruder, simultaneously with polyethylene powder. The decomposable thermal initiator can be added as a pure compound or it can alternatively be dispersed in another polymer such as a masterbatch, typically polyethylene or polypropylene. The type of initiator is selected according to its half-life curve over time as a function of temperature.
    [0046] Decomposable thermal initiators are known in the art, such as azobisisobutyronitrile (AIBN), peroxy compound, such as diacyl peroxides, acetyl alkylsulfonyl peroxides, dialkyl peroxydicarbonates, OO-tert-alkyl-tert-alkylperoxyesters, monoperoxycarbonates acyl, di (tert-alkylperoxy) ketals, di (tert-alkyl) peroxides, tert-alkyl hydroperoxides, and ketone peroxides, redox initiators, and the like.
    [0047] In one embodiment, preferred peroxy compounds comprise diacyl peroxides, such as dibenzoyl peroxide BPO, di (2,4-dichlorobenzoyl) peroxide, diacetyl peroxide, dilauroyl peroxide, didecanoyl peroxide, diisonanoyl peroxide and peroxide succinic acid; peroxy esters, such as di-tert-butyl diperoxyphthalate, tert-butyl perbenzoate, tert-butyl peracetate, tert-amyl perbenzoate, 2,5-di (benzoylperoxy) -2,5-dimethyliexane, tert-butyl acid peroximal, tert-butyl peroxyisobutyrate, tert-butyl-peroxy-2-ethylhexanoate (tert-butyl peroctoate), tert-amyl peroctoate, 2,5-di (2-ethylhexanoylperoxy) -2,5-dimethylhexane, peroxypivalate tert-butyl, tert-amyl peroxypivalate, tert-butyl peroxineodecanoate, tert-amyl peroxineodecanoate, a-cumila peroxineodecanoate; diperoxicetals, such as ethyl-3,3-di (tert-butylperoxy) -butyrate, ethyl 3,3-di (tert-butiperoxy) -butyrate, 4,4-di (tert-butylperoxy) n-butyl valerate, 2 , 2-di (tert-butylperoxy) butane, 1,1-di (tert-butylperoxy) cyclohexane, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, and 1,1 di (tert-amylperoxy) cyclohexane; dialkylperoxides, such as 2,5 (tert-butylperoxy) -2,5-dimethyl-3-hexino, di-tert-butyl peroxide, tert-butyl-accumila peroxide, 2,5-di (tert-butylperoxy) - 2,5-dimethylhexane, a-a'-di (tert-butyl-peroxy) -1,3- and 1,4-diisopropylbenzene, and dicumyl peroxide; peroxydicarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxy dicarbonate, and di (4-tert (-butylcyclohexyl) peroxy) , and tert-alkylhydro peroxides, such as tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, 2,5-dihydroxiperoxy-2,5-dimethylhexane, pinane hydroperoxide, para-menthane hydroperoxide, and hydroperoxide diisopropylbenzene.
    [0048] In some embodiments of the present description, peroxy initiators are selected from: 2,5-dimethyl-2,5 di (tert-butylperoxy) hexino-3; 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane; di-tert-butyl peroxide; 1,3-1,4-di-tert-butylperoxyisopropylbenzene; tert-butylcumylperoxide; dicumylperoxide; 3,3,6,6,9,9-hexamethyl-1,2,4,5 tetracyclononane; 4,4-di-tert-butyl peroxy-n-butylvalerate; 1,1-di-tert-butyl peroxycyclohexane; tert-butyl peroxybenzoate; dibenzoyl peroxide; di- (2,4-dichlorobenzoyl) peroxide; di (p-chlorobenzoyl) peroxide; 2,2-di (tert-butylperoxy) butane; ethyl-3,3-bis (tert-butylperoxy) butyrate. In one embodiment, the compositions and resins according to the present description are treated with 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and bis (tert-butylperoxyisopropyl) benzene.
    [0049] In a preferred embodiment of the present description the polymer is treated with 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, commercially available under the names Trigonox 101 and Pergaprop Hx 7.5 PP, adhered to a PP surface flake at a concentration of 7.5% by weight. In some embodiments, the amount of pure peroxy initiator used in the crosslinking process ranges from about 50 ppm to about 150 ppm by weight, and preferably from about 50 ppm to about 100 ppm by weight. Preferably, the amount of peroxide is sufficient to ensure that the resulting polyethylene composition has the desired complex viscosity at a low shear rate (no, oi). The amount of peroxy initiator required to obtain the desired value depends, in part, on the melt resistance of the original non-cross-linked polyethylene as well as on the type of peroxide used and the mixing conditions, more specifically on the melting temperature and residence time in the extruder, as these factors will influence the crosslinking efficiency.
    [0050] The ideal level of peroxide charge may vary depending on the melting resistance of the starting material and the type of organic peroxide used. Materials with low shear viscosities less than 200,000 Pa.s generally do not have the melt strength capable of producing the thick-walled pipe with wall distributions within industry specifications. In one embodiment, the peroxide load is controlled to obtain material that exhibits low shear viscosities at 0.01 rad / s not greater than about 450,000 Pa.s. In one embodiment, the preferred amount of peroxide used is less than 150 by weight. It is possible to produce thick-walled tubes with materials that have low shear viscosities greater than 450,000 Pa.s, but the increased low shear viscosity of the material would not produce an additional advantage, the use of additional peroxide can become cost prohibitive, cause problems of processing in the final product (such as decreased productivity and undesirable surface imperfections), and can cause degradation of physical property. Examples of possible processing problems associated with the use of higher levels of peroxide include the presence of excess gel in the material, causing the surfaces to become rough and weak points in the piping that can lead to early failures in the pressure pipe.
    [0051] The polyethylene powder produced in a polymerization process such as that described above is fed to the extrusion equipment together with the additive package and the peroxide. The extrusion equipment melts into the powder and disperses any additives and peroxide. The peroxide must be well dispersed within the molten polymer, at sufficiently hot temperatures and sufficient residence times to completely initiate the peroxide and allow the consequent radical chain reactions to occur to an extent sufficient to produce the desired effect. The peroxide must be well dispersed within the molten polymer, at sufficiently hot temperatures and residence times long enough to completely initiate the peroxide and allow the consequent radical chain reactions to occur in an amount sufficient to produce the desired effect of increased melt strength and retained processability. The additive's feed hardware must be able to feed a consistent amount of peroxide to provide a consistent (homogeneous) modified product.
    [0052] If the peroxide carrier with a particle size more similar to the other additives being added to the molten HDPE could be used, the additives could all be combined in a larger pouch, allowing the additive feeder to feed on larger rates with less variability to produce better control of organic peroxide addition rates. Also the type of peroxide used and the vehicle used to transport the peroxide can be changed (liquid, PP flake, HDPE flake). Organic peroxide and its vehicle could be replaced with functional alternatives. If available, an HDPE flake or pellet could be used as a vehicle for the peroxide, a pure liquid peroxide could be used, as well as other forms of the desired peroxide. Other organic peroxides that could be used include dicumyl peroxide, tert-butylcumyl peroxide, 1,3-1,4-Bis (tert-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (tert-butylperoxyl) hexino , and others. Such substitution materials, while not changing the basic description, would result in the possible need for a recalculation in target concentrations of peroxide and other reactive extrusion conditions, such as the residence time required to achieve the proper mixture.
    [0053] Stricter controls and better methods of adding peroxide can improve the properties of the compositions according to the present description. Extrusion temperature and residence time allow the peroxide to react complementarily once it is added to the base resin flake. Temperatures must be high enough and the peroxide must remain in contact with the polymer long enough for branching of the long chain to occur. The peroxide used can be added as either a solid or a liquid.
    [0054] The extrusion equipment could also be replaced or changed to use very different types of commercially available polymer extrusion equipment. The extrusion equipment used must be capable of providing sufficient heating, residence time and shear (operation) being given to the polymer.
    [0055] If the extrusion temperature is too high, the peroxide could be consumed before being able to be well dispersed in the polymer matrix, especially if it came into contact with a heated surface before being mixed with the polymer. The peroxide reaction should start, but not react with the polymer chains. The desired increased melt strength should not be achieved in the polymer. If this occurred, reduced long chain branching should occur and the low shear viscosity of the bulk HDPE material should not be sufficient. Extrusion temperatures can impact the crosslinking process. In one embodiment, the crosslinking according to the present description is carried out at a temperature less than about 320 ° C. In one embodiment, the crosslinking according to the present description is carried out at a temperature less than about 280 ° C (550 ° F). The minimum residence time at a certain temperature depends on the half-life of the peroxide at that temperature. The half-life at a given temperature will boo with the type of peroxide used.
    [0056] Compositions produced according to some modalities of the present description can be mixed with the usual processing additives for polyolefins, such as stabilizers (antioxidants and / or anti-UV agents), antistatic agents and processing aids, as well as pigments .
    [0057] Tubes produced from the compositions according to some modalities of the description preferably have one or more of the following properties rated 10 in MRS, or better as defined by the standard ISO / TR 9080 or a listing of PE4710 by ASTM D883 and ASTM D3350.
    [0058] Unless otherwise specified, all numbers expressing quantities of ingredients, reaction conditions, and other properties or parameters used in the report and claims are to be understood as being modified in all cases by the term "about". All numeric ranges here include all numeric values and ranges of all numeric values within the described range of numeric values. By way of non-limiting illustration, concrete examples of certain modalities of the present description are provided below. EXAMPLES Testing methods Flow rate
    [0059] Flow rates have been determined according to IS01133 or ASTM D1238 and the results are reported in g / 10 min, but both tests will provide substantially the same results. For polyethylene a temperature of 190 ° C is applied. MI2 is determined under a load of 2.16 kg, MI5 is determined under a load of 5 kg and HLMI is determined according to a load of 21.6 kg. Density
    [0060] Density of polyethylene was measured according to ISO 1183-1 (Method A) and the sample plate was prepared according to ASTM D4703 (Condition C) where it was cooled under pressure at a cooling rate of 15 ° C / min from 190 ° C to 40 ° C. Comonomer content
    [0061] The C4-C8 alpha-olefin content is measured by 13CNMR according to the method described in J.C. Randall, JMS- Rev. Macromol. Chem. Phys., C29 (2 & 3), p. 201-317 (1989). The content of units derived from C4-C8 alpha-olefin is calculated from measurements of the integrals of the characteristic lines of that particular C4-C8 alpha-olefin, compared to the integral of the characteristic line of the ethylene-derived units (30 ppm). A polymer composed essentially of monomer units derived from ethylene and a single C4-C8 alpha-olefin is particularly preferred. Resistance to environmental stress cracking (ESCR)
    [0062] Resistance to environmental stress breaking (ESCR) is determined by the pipe notch test (NTP). The pipe notch test was carried out according to ISO 13479: 1997 in a tube with a diameter of 110 mm and a thickness of 10 mm (SDR 11). The test was performed at 80 ° C at a pressure of 9.2 bar (920 kPa). Resistance to breakage by tension (PENT)
    [0063] Another method for measuring resistance to environmental stress cracking is the Pennsylvania Notch Stress Test (PENT), ASTM DL473. PENT is the accepted North American standard by which pipe resins are tested to classify their ESCR performance. The molded plate is given a notch to specific depth with a knife and tested at 80 ° C under a stress of 2.4 MPa to accelerate the failure mode due to stress breaking of a material. The time in which the species fails, breaks completely or stretches over a certain length, is used for its ESCR classification. A PE4170 by definition must not fail before 500 hours. Materials described in that patent should be tested over 10,000 hours without fail and considered high performance materials. Resistance to rapid crack propagation (CPR)
    [0064] Resistance to rapid crack propagation (CPR) is measured according to the S4 method described in the ISO 13477 standard. The critical temperature was determined in a tube with a diameter of 110 mm and a thickness of 10 mm (SDR 11) in a constant pressure of 5 bar (500 kPa). The critical temperature is defined as the lowest break temperature above the highest break propagation temperature; the lower the critical temperature, the better the resistance to rapid crack propagation. Deformation resistance
    [0065] Deformation resistance is measured according to ISO 1167 in a 50 mm diameter tube and 3 mm thick tubes (SDR 17) to determine the life span before failure at a temperature of 20 ° C and 80 ° C ° C and a tension between 5 and 13 MPa. Fungal rheology at constant shear rate
    [0066] Dynamic rheological measurements to determine the n * complex viscosities as a function of the shear rate are performed according to ASTM D 4440, in a dynamic rheometer (eg ARES), such as a rotary rheometer model 5 Ares, Rheometrics, with parallel plates of 25 mm in diameter in a dynamic mode under an inert atmosphere. For all experiments, the rheometer has been thermally stabilized at 190 ° C for at least 30 minutes before the insertion of the adequately stabilized compression-molded sample (with anti-oxidant additives), in the parallel plates. The plates are then closed with a normal positive force recorded on the meter to ensure good contact. After about 5 minutes at 190 ° C, the plates are lightly compressed and the excess polymer on the circumference of the plates is cut. Another 10 minutes is allowed for thermal stability and for normal force to decrease to zero. That is, all measurements are taken after the samples have been equilibrated at 190 ° C for about 15 minutes and are performed under total nitrogen inerting.
    [0067] Two deformation sweep (SS) experiments are initially performed at 190 ° C to determine the linear viscoelastic deformation that could generate a torque signal that is greater than 10% of the smallest transducer scale, over the full frequency range (for example, 0.01 to 100 rad / s). The first SS experiment is carried out with a low applied frequency of 0.1 rad / s. This test is used to determine the sensitivity of torque at low frequency. The second SS experiment is carried out with a high applied frequency of 100 rad / s. This ensures that the selected applied deformation is well within the linear viseoelastic region of the polymer so that oscillatory rheological measurements do not induce structural changes to the polymer during the test. In addition, a time scan (TS) experiment is performed with a low applied frequency of 0.1 rad / s on the selected strain (as determined by the SS experiments) to check the stability of the sample during testing.
    [0068] The frequency sweep (FS) experiment was then carried out at 190 ° C using the strain level appropriately selected above among the dynamic frequency range of 10-2 to 100 rad / s, under nitrogen. The dynamic rheological data so measured was analyzed using the rheometer software (ie, Rheometrics RHIOs V4.4 or Orchestrator Software) to determine the elastic fusion module (G '(G ”= 3000) at a value (G”) of viscous modulus of the reference cast of G ”= 3000 Pa. If necessary, values were obtained by interpolation between the available data points using the Rheometrics software.
    [0069] The term "storage module" G '(w), also known as "elastic module", which is a function of the applied oscillation frequency, w, is defined as the stress in the phase with the deformation in a sinusoidal deformation divided by deformation; while the term "viscous modulus", G "(w), also known as" loss modulus ", which is also a function of the applied oscillatory frequency, w, is defined as the 90 degree stress out of phase with the deformation divided by deformation. Both of these modules, and other linear, dynamic rheological viscoelastic parameters, are well known in the art, for example, as discussed by G. Marin in "Osciliatory Rheometry", Chapter 10 of the book in Rheological Measurement, edited by AA Collyer and DW Clegg, Elsevier, 1988. Fusion rheology at constant shear stress
    [0070] The rheological properties of a material at low shear rates were measured to better understand the material as it bends under gravitation forces. The constant stress test was used to determine the complex viscosity n * at low shear stress. The experiments were conducted using an ARES G2 manufactured by TA Instruments. In this transient experiment, the sample was placed under a low shear stress, where the viscosity was no longer dependent on the shear stress. In this region at very low shear stresses, the shear rate is also expected to be very low, much lower than the complex viscosity measured at 0.01 rad / s, and the viscosity in the region is expected to be independent of the shear rate. . Conformity is a function of shear stress and time and is defined as the deformation ratio depends on time over a constant stress. the experiments were carried out at low values of shear stress, where conformity to the deformation became independent of the shear stress and linear with time allowing the determination of the zero shear viscosity. The unserved slope of the compliance graph can be defined as the zero-shear viscosity of the material and can be seen in Table 1. The experiments were carried out at 190 ° C under nitrogen using a parallel plate 25 mm in diameter. The distance between the parallel plates during pexertion was 1.7 mm ± 1%. Tension control loop parameters were performed and calculated before the test using a strain range in the linear viscoelastic region. A total time of 6 minutes was used to condition the sample and transducer. A low shear stress of 747 Pa is then applied to the sample and maintained for 1800 seconds. After that time the sample viscosity was measured. The zero shear viscosity is determined from the conformity of the time-dependent strain. Preparation of the black composition
    [0071] The manufacture of a base I resin comprising ethylene polymers was carried out in suspension in isobutane in two recirculation reactors, connected in series and separated by a device that makes it possible to continuously reduce the pressure. Isobutane, ethylene, hydrogen, triethyl aluminum and the catalyst were continuously introduced into the first recirculation reactor and the polymerization of ethylene was carried out in this mixture in order to form the homopolymer (A). This mixture, additionally comprising the homopolymer (A), was continuously extracted from said reactor and was subjected to a reduction in pressure, to remove at least a portion of the hydrogen. The resulting mixture, at least partially degassed of hydrogen, was then continuously introduced into a second polymerization reactor, at the same time as ethylene, 1-hexene, isobutane and hydrogen, and the polymerization of ethylene and hexene was carried out in the same way in order to form the ethylene / 1-hexene copolymer (B). The suspension comprising the composition comprising ethylene polymers was continuously extracted from the second reactor and this suspension was subjected to a final reduction in pressure, in order to extract the isobutane and the reactants present (ethylene, hexene and hydrogen) and recover the composition in the form of a dry powder, which was subsequently treated in a purge column in order to remove most of the process components captured in the polymer particles. Catalysts were used as described in EP-B-2,021,385. Other polymerization conditions and copolymer properties are shown in Table 1.
    [0072] Additives were incorporated into the powder particles and subsequently intensively mixed together before feeding the mixing equipment, a conventional twin screw extruder. The additives included at least one acid neutralizer such as calcium stearate or zinc stearate in an amount between 500 and 2000 ppm or a mixture of both, and at least one antioxidant in the process like Irgafos 168 in an amount between 500 and 2500 ppm and at least one thermal antioxidant such as Irganox 1010 in an amount between 500 and 2500 ppm. Small amounts of processing aid, such as SOLEF 11010/1001, can be added. Additives also include carbon black in an amount of 2.0 to 2.4% by weight. A thermal decomposition agent, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (DHBP) is optionally incorporated into the feed via 7.5% by weight of a polypropylene masterbatch.
    [0073] This mixture of flake / additives / peroxide enters the mixing section of the extruder where the material is heated, melted, and mixed together. The time that the material spends in the mixing and extrusion sections is considered the residence time of the reaction. The other pelletizing conditions and properties of the pelleted resin are specified in Table 2. Table 1 Polymerization conditions and properties for base polymer I

    * Measured according to ISO1133 Table 2 Pelletizing conditions and properties of pelleted resins


    * measured according to ISO1133 Preparation of natural composition
    [0074] The manufacture of a base II resin was carried out as described for the base I resin above. The polymerization conditions and properties of the copolymer are shown in Table 3.
    [0075] 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane (DHBP) was incorporated into the powder particles and subsequently intensively mixed together before in a Farrel FCM mixer. The balance of the additive formulation (primary antioxidant, etc.) is added through a separate feeder at the same location. This mixture of flakes / additives / peroxide enters the mixer where the material is heated, melted and mixed together. A strip of polymer then leaves the mixer through the orifice and is fed into the extruder. The material is transported to the matrix and then pelleted. The processing time in the mixer and extruder is defined as the residence time.
    [0076] Table 4 presents data for re-labeled samples and non-cross-linked samples. These predictive rheological tools show no statistically significant difference in the processing parameters, while a significant change in the low shear viscosity is present. To confirm the predictive measurement for processability and to show that no loss in processability has been experienced comparisons of the processivity tube extrusion measurements are mustard in Table 4. In addition, the predictive mediation for melt strength has been examined and confirmed by the extrusion data of the tube offered by the cross-linked and non-cross-linked samples. Improvements in wall thickness and similar processability show that a modified peroxide resin will exhibit improved melt strength with no loss of processability as expected from predictive rheological results. Table 3 Polymerization conditions and properties for base polymer II
    * Measured according to ASTM D1238 Table 4

    * Measured according to ASTM D1238.
    权利要求:
    Claims (19)
    [0001]
    1. Composition of bimodal high density polyethylene polymer, characterized by comprising a base resin which has a density of 946 to 951 kg / m3 and comprises an ethylene polymer (A) having a density above 970 kg / m3 in a varying amount between 47 and 53% by weight and an ethylene polymer (B) having a density less than the density of the polymer (A), wherein said composition has a complex viscosity at a shear rate of 0.01 rad / s ( 190 ° C) between 220 and 450 kPa.if a complex viscosity at a shear rate of 100 rad / s (190 ° C) ranging from 2000 to 2500 Pa.s, where the composition has an elastic melting modulus (G '(G ”= 3000) in a value (G”) of the viscous modulus of the reference cast of G ”= 3000 Pa ranging from 1650 to 2400 Pa, and when produced in a tube it has a tensile strength greater than 9,000 h as determined by the pipe notch test according to ISO 13479: 1997.
    [0002]
    2. Polymer composition according to claim 1, characterized in that the composition exhibits a viscosity at a constant shear stress of 747 Pa (n * 747) ranging from 400 kPa.s to 1300 kPa.s.
    [0003]
    3. Polymer composition according to claim 1 or 2, characterized by the fact that the composition has a G '(G "= 3000) (Pa) between 1700 and 2200 Pa.
    [0004]
    Polymer composition according to any one of claims 1 to 3, characterized in that the composition exhibits an MI5 melt index ranging from 0.1 to 0.5 g / 10 min.
    [0005]
    Polymer composition according to any one of claims 1 to 4, characterized in that the composition has a co-monomer content ranging from 0.3 to 0.65 mol%.
    [0006]
    Polymer composition according to any of claims 1 to 5, characterized by the fact that it still comprises peroxide in an amount ranging from 50 ppm to 150 ppm.
    [0007]
    7. Polymer composition according to any one of claims 1 to 6, characterized by the fact that when produced in a tube it has an MRS rating of 10 or better or an HDB of 1600 psi (11.03) at 23 ° C or best.
    [0008]
    Tube, characterized by comprising a polymer composition as defined in any one of claims 1 to 7.
    [0009]
    Polymer composition according to any one of claims 1 to 8, characterized in that the composition exhibits a SHI2.7 / 210 pseudoplasticity index of 60 to 115.
    [0010]
    Process for producing a bimodal high density polyethylene composition with improved high melt resistance as defined in any one of claims 1 to 9, characterized by comprising: preparing a bimodal high density polyethylene base resin comprising an ethylene polymer (A) having a density above 970 kg / m3 in an amount ranging from 47% to 53% by weight and an ethylene polymer (B) having a density less than the density of polymer A, where the composition has a density of 946 kg / m3 to 951 kg / m3; feeding the high density polyethylene polymer composition into an extrusion device; feeding peroxide in an amount ranging from 50 ppm to 150 ppm on the weight of the resin in the extrusion device; and mixing the polymer composition and the peroxide in the extrusion device until substantially homogeneous, wherein the resulting composition exhibits a complex viscosity at a shear rate of 0.01 rad / s (190 ° C) ranging between 220 and 450 kPa. a complex viscosity at a shear rate of 100 rad / s (190 ° C) ranging from 2000 to 2500 Pa.s.
    [0011]
    11. Process according to claim 10, characterized in that the peroxide is an organic peroxide, and additionally in that the organic peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di (tert-butylperoxyl ) hexane, dicumyl peroxide, tert-butylcumyl peroxide, 1,3-1,4-bis (tert-butylperoxy isopropyl) benzene, and 2,5-dimethyl-2,5-di (tert-butylperoxyl) hexino.
    [0012]
    Process for producing a bimodal high density polyethylene (HPDE) composition with improved high melt resistance as defined in any one of claims 1 to 9, characterized by comprising: preparing a bimodal HDPE polymer flake comprising a polymer component of low molecular weight ethylene (A) (LMW) and a high molecular weight ethylene polymer component (B) (HMW) in a multi-reactor cascade process, in which polymerization is carried out in the presence of hydrogen, and which the molar hydrogen concentration ratio in the reactor that produces the LMW component (A) to the molar hydrogen concentration in the reactor that produces the HMW component (B) ranges from 250: 1 to 350: 1; feeding the HDPE polymer flake into an extrusion device; feeding a reactive agent to the extrusion device; and mixing the bimodal HDPE polymer flake and the active agent in the extrusion device until homogeneous.
    [0013]
    13. Process according to claim 12, characterized by the fact that the reactive agent is mixed with the bimodal HDPE polymer flake in the extrusion device at temperatures up to 228 ° C until homogeneous to increase the long chain branching within the HDPE composition while maintaining the processability of the HDPE composition, where processability is measured by a pseudoplasticity index at 2.7 kPa and 210 kPa from 60 to 115, a complex viscosity at 100 rad / s ranging from 2000 Pa.s to 2500 Pa. a high charge melting index ranging from 6 to 11 g / 10 min.
    [0014]
    Process according to either of Claims 12 and 13, characterized in that the polymer component HMW is polymerized in the presence of 1-butene, 1-hexene, or 1-octene.
    [0015]
    15. Process according to any one of claims 12 to 14, characterized in that the mass ratio of the LMW component (A) to the bimodal composition varies from 49.5% to 51.5%.
    [0016]
    16. Process according to any one of claims 12 to 15, characterized in that the reactive agent is organic peroxide and that the organic peroxide is also selected from the group consisting of 2,5-dimethyl-2,5-di (tert -butylperoxyl) hexane, dicumula peroxide, tert-butylcumyl peroxide, 29,3-29,4-bis- (tert-butylperoxy-isopropyl) benzene, and 2,5-dimethyl-2,5-di (tert-butylperoxyl ) hexine.
    [0017]
    17. Process according to claim 16, characterized in that the organic peroxide is fed into the extrusion device in an amount ranging from 50 ppm to 150 ppm.
    [0018]
    18. Process according to any one of claims 12 to 17, characterized in that the composition exhibits an MI5 melt index ranging from 0.1 to 0.5 g / 10 min.
    [0019]
    19. Process for producing a bimodal high density polyethylene (HDPE) composition with improved melt strength as defined in any one of claims 1 to 9 to produce a large diameter tube, characterized by comprising: preparing an HDPE polymer flake bimodal comprising a low molecular weight ethylene homopolymer (LMW) component and a high molecular weight ethylene polymer (HMW) component in a multi-reactor cascade process, the HMW component having an average molecular weight greater than LMW component; feeding the HDPE polymer flake into an extrusion device; introduce the thermal decomposition agent continuously in the extrusion device; and mixtures the thermal decomposition agent within the bimodal HDPE polymer flake in the extrusion device at temperatures up to 288 ° C until homogeneous to increase the long chain branching within the HDPE composition, while maintaining processability of the HDPE composition, in which Processability is measured by the pseudoplasticity index at 2.7 kPa and 210 kPa from 60 to 115, a complex viscosity at 0.01 rad / s (190 ° C) ranging from 220 to 450 kPa.if a complex viscosity at a rate of shear of 100 rad / s (190 ° C) ranging from 2000 to 2500 Pa.se a high load melt index ranging from 6 to 11 g / 10 min.
    类似技术:
    公开号 | 公开日 | 专利标题
    US10787563B2|2020-09-29|Bimodal high-density polyethylene resins and compositions with improved properties and methods of making and using the same
    US8653201B2|2014-02-18|Ethylene polymer composition
    EP1812629B2|2016-09-28|Drawn tapes, fibre and filaments comprising a multimodal polyethylene resin
    US20120148775A1|2012-06-14|Ethylene polymer composition
    EP3077714B1|2018-11-14|Pipe comprising a metallocene-catalyzed polyethylene resin
    JP2019526684A|2019-09-19|Multimodal polyethylene pipe
    JP2013227545A|2013-11-07|Polyethylene for pipe and joint, and molded product thereof
    JP2021509931A|2021-04-08|Bimodal polyethylene resin and pipes made from this bimodal polyethylene resin
    JP6177323B2|2017-08-09|Film composition
    RU2644948C2|2018-02-15|Compositions of ethylene-based polymer with improved technological characteristics
    US9169378B2|2015-10-27|Polymer composition for blow moulding
    US10563053B2|2020-02-18|Partially-crosslinked polyethylene formulations and methods of making same
    US20210009792A1|2021-01-14|Bimodal high-density polyethylene resins and compositions with improved properties and methods of making and using the same
    US20210171749A1|2021-06-10|Improving rheological properties of thermoplastic polyolefin compositions
    JP2020094153A|2020-06-18|Resin composition mainly comprising ethylenic polymer powder, and molded article comprising the same
    同族专利:
    公开号 | 公开日
    BR112014016166A2|2017-06-13|
    WO2013101767A2|2013-07-04|
    CN104684989A|2015-06-03|
    ES2831165T3|2021-06-07|
    EP2798002A2|2014-11-05|
    RU2014131120A|2016-02-20|
    WO2013101767A3|2015-06-25|
    US20180127573A1|2018-05-10|
    CN104684989B|2018-01-09|
    EP2798002B1|2020-08-19|
    BR112014016166A8|2017-07-04|
    RU2629120C2|2017-08-24|
    IN2014CN04881A|2015-09-18|
    US20150025195A1|2015-01-22|
    US10787563B2|2020-09-29|
    EP2798002A4|2016-11-02|
    US9873782B2|2018-01-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS64985B2|1981-08-14|1989-01-10|Asahi Chemical Ind|
    CZ5693A3|1992-01-23|1993-10-13|Himont Inc|Elastic yarn of polypropylene polymer and articles made therefrom|
    FI108452B|1996-06-07|2002-01-31|Borealis Polymers Oy|Ethylene polymer product with a broad molar mass distribution, production and use thereof|
    SE9803501D0|1998-10-14|1998-10-14|Borealis Polymers Oy|Polymer composition for pipes|
    EP1201713A1|2000-10-27|2002-05-02|ATOFINA Research|Polyethylene pipe resins and production thereof|
    EP1201711A1|2000-10-27|2002-05-02|ATOFINA Research|Polyethylene pipe resins and production thereof|
    AT301163T|2001-08-17|2005-08-15|Dow Global Technologies Inc|BIMODAL POLYETHYLENE COMPOSITION AND OBJECTS THEREOF|
    EP1359192A1|2002-04-30|2003-11-05|Solvay Polyolefins Europe-Belgium |Polyethylene pipe resins|
    GB0418581D0|2004-08-20|2004-09-22|Solvay|Polymer composition|
    US20060047076A1|2004-08-31|2006-03-02|Scheie Andrew J|Solid state modification of multimodal polyethylene|
    ES2291798T3|2004-11-03|2008-03-01|Borealis Technology Oy|MULTIMODAL POLYETHYLENE COMPOSITION FOR PIPES.|
    US20070048472A1|2005-08-30|2007-03-01|Krishnaswamy Rajendra K|Polymeric pipe and method of making a polymeric pipe|
    EP1760096A1|2005-09-05|2007-03-07|INEOS Manufacturing Belgium NV|Polymer composition|
    US7238754B1|2005-12-12|2007-07-03|Equistar Chemicals, Lp|Solid state process to modify the melt characteristics of polyethylene resins and products|
    EP1860126A1|2006-05-26|2007-11-28|INEOS Manufacturing Belgium NV|Polyolefin powder|
    RU2009104345A|2006-07-12|2010-08-20|Инеос Мэньюфекчуринг Белджиум Нв |COMPOSITION OF POLYMER ETHYLENE|
    US20080161526A1|2006-12-29|2008-07-03|Fina Technology, Inc.|Cross-Linked Polyethylene Resin for Large Part Blow Molding|
    PL1985660T5|2007-04-25|2013-09-30|Borealis Tech Oy|Pipe comprising super slow crack growth resistant polyethylene|
    US20090035545A1|2007-07-30|2009-02-05|Fina Technology, Inc.|Polyethylene films with improved bubble stability|
    US7767767B2|2007-10-01|2010-08-03|Equistar Chemicals, Lp|Modification of polyethylene with ozone|
    US20090182100A1|2008-01-14|2009-07-16|Guenther Gerhard K|Process for the production of polyethylene resin|
    ES2363653T3|2008-07-16|2011-08-11|Borealis Ag|HIGH-RIGID HETEROPHASE POLYMERIC COMPOSITION.|
    CN102666701B|2009-11-23|2016-01-20|陶氏环球技术有限责任公司|Composition, film and preparation method thereof|
    US20110174413A1|2010-01-20|2011-07-21|Fina Technology, Inc.|Modification of Polyethylene Pipe to Improve Sag Resistance|
    WO2013101767A2|2011-12-29|2013-07-04|Ineos Olefins & Polymers Usa, A Division Of Ineos Usa Llc|Biomodal high-density polyethylene resins and compositions with improved properties and methods of making and using the same|
    RU2644948C2|2013-02-14|2018-02-15|ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи|Compositions of ethylene-based polymer with improved technological characteristics|WO2013101767A2|2011-12-29|2013-07-04|Ineos Olefins & Polymers Usa, A Division Of Ineos Usa Llc|Biomodal high-density polyethylene resins and compositions with improved properties and methods of making and using the same|
    CN105579496B|2013-09-30|2018-12-07|陶氏环球技术有限责任公司|A method of for improving polyvinyl resin, concentrate composition and the melt strength of polymer composition|
    US9783662B2|2013-10-30|2017-10-10|Abu Dhabi Polymers Co. LtdL.L.C.|Polyethylene composition suitable for injection moulding applications|
    EP2894195B1|2013-12-23|2016-09-14|Abu Dhabi Polymers Company Limited |Polyethylene composition for pipe applications with improved sagging properties|
    US9828451B2|2014-10-24|2017-11-28|Chevron Phillips Chemical Company Lp|Polymers with improved processability for pipe applications|
    EP3088458B1|2015-04-27|2017-08-16|Abu Dhabi Polymers Company LimitedL.L.C.|Polyethylene composition suitable for pipe applications|
    EP3109275B1|2015-06-22|2017-08-09|Abu Dhabi Polymers Company LimitedL.L.C.|Polyethylene composition for pipe applications with improved sagging and extrusion properties|
    US10377527B2|2015-06-22|2019-08-13|Bastian Solutions, Llc|Composite concrete pallet|
    PL3394168T3|2015-12-21|2020-11-16|Dow Quimica Mexicana S.A.De C.V.|Partially-crosslinked polyethylene formulations and methods of making same|
    EP3464439A1|2016-05-26|2019-04-10|Borealis AG|Molecular modification of polyethylene resin|
    EP3472239B1|2016-06-17|2020-05-13|Borealis AG|Bi- or multimodal polyethylene with low unsaturation level|
    CA3028257A1|2016-06-23|2017-12-28|Borealis Ag|Pipe produced from modified polyethylene|
    US10501613B2|2016-07-29|2019-12-10|Equistar Chemicals, Lp|Low-sag polyethylene pipes and methods thereof|
    WO2018046668A1|2016-09-12|2018-03-15|Thai Polyethylene Co., Ltd.|Bimodal polyethylene composition and pipe comprising the same|
    ES2746570T3|2016-09-12|2020-03-06|Thai Polyethylene Co Ltd|Multimodal polyethylene screw cap|
    EP3293209B1|2016-09-12|2019-08-14|Thai Polyethylene Co., Ltd.|Multimodal polyethylene thin film|
    EP3293214B1|2016-09-12|2019-12-25|Thai Polyethylene Co., Ltd.|High performances multimodal ultra high molecular weight polyethylene|
    EP3293206B1|2016-09-12|2019-10-23|Thai Polyethylene Co., Ltd.|Multimodal polyethylene pipe|
    US11149102B2|2017-03-10|2021-10-19|Sumitomo Chemical Company, Limited|Film|
    CN110603269A|2017-03-29|2019-12-20|埃克森美孚化学专利公司|Foamable high-density polyethylene composition and articles made therefrom|
    US10550252B2|2017-04-20|2020-02-04|Chevron Phillips Chemical Company Lp|Bimodal PE resins with improved melt strength|
    EP3450127A1|2017-09-01|2019-03-06|Basell Polyolefine GmbH|Process for preparing a polyolefin composition|
    EP3710528A1|2017-11-17|2020-09-23|Total Research & Technology Feluy|Polyethylene resin and caps or closures made therefrom|
    WO2019121234A1|2017-12-18|2019-06-27|Basell Polyolefine Gmbh|Polyethylene composition having environmental stress cracking resistance|
    US10590213B2|2018-03-13|2020-03-17|Chevron Phillips Chemical Company Lp|Bimodal polyethylene resins and pipes produced therefrom|
    CN108569012A|2018-03-20|2018-09-25|福建师范大学福清分校|A kind of easily heat-sealing of mill mist type can in print PE films and preparation method|
    EP3774929B1|2018-04-12|2022-02-02|SABIC Global Technologies B.V.|Polyethylene composition|
    EP3774930B1|2018-06-21|2021-10-20|Basell Polyolefine GmbH|Suspension process for preparing ethylene copolymers in a reactor cascade|
    US10301218B1|2018-09-07|2019-05-28|King Saud University|Low cement content strain-hardening cementitious composite|
    CN110540690A|2019-09-04|2019-12-06|浙江大学|Double-peak high-density polyethylene resin and preparation method thereof|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-18| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2020-12-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 21/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161631209P| true| 2011-12-29|2011-12-29|
    US61/631,209|2011-12-29|
    PCT/US2012/071432|WO2013101767A2|2011-12-29|2012-12-21|Biomodal high-density polyethylene resins and compositions with improved properties and methods of making and using the same|
    [返回顶部]