SA06270024B1 - Polymer composition for injection moulding - Google Patents

Abstract

Abstract: The present application relates to a polyethylene composition containing a base resin, the base resin comprising (a) one part polyethylene, (b) a second part polyethylene, wherein the melt flow rate is MFR5 /190 C for the first part is higher than the MFR5/190 C for the second part, and the FRR21/5 flow rate ratio and polyethylene composition is defined as the ratio of the MFR21.6/190 C magma flow rate to the MFR5/ 190 C, ranging from 15 to 28, the MFR5/190 C melt flow rate for polyethylene installation ranges from 0.5 to 1.1 g/10 min.

Description

Y

Polymeric composition for injection molding

Polymer Composition For Injection Molding Full Description Background for injection molding ada polymer composition The present invention relates to a polymeric composition comprising molded articles and a process for producing the composition; To inject molded materials, cinjection molding prepared finished, and to use fittings in molding fittings, especially injection fittings. Polymeric materials of pipes are often used as pipes.

Sie cgas gas liquids i.e. fluid transport “fluid transport fia for multiple purposes” ll about Shady and during that the pressure of the fluid can be adapted. cnatural gas water or natural gas varies; They typically range from transported fluid temperatures from pressure pipes to about 0°C to about 0°C. It is preferable that the 0 pressure pipes traditionally consist of epolyolefin plastic of this kind from Pie unimodal ethylene plastic, from +4¥ to +4¥. MDPE (medium density polyethylene (MDPE) density and high density polyethylene) gram/cubic centimeter (g/cm') JARS .. 7 . ("anf 0.5558 g) to 0 .547 of HDPE (high density polyethylene (HDPE) in the range of m). The term “pressure pipe” in this statement means a pipe that, when used, is subject to, i.e. the pressure inside the pipe is higher than the pressure outside (positive pressure x ga) pipe pressure. Properties of Ad central fluid pressure. For pipes subjected to internal fluid pressure, the horizon v, a specific resistance (Jad), is appropriate and should be optimized. Appropriate properties are, for example, Modulus of elasticity Jala impact strength Rapid crack propagation resistance For pipes in the form of Lila and moreover; As in, slow crack growth resistance is good. processability is general; The polymers from which the tubes are made should have processability ° or by molding extrusion Polymeric tubes are made by extrusion Loses to a much smaller extent. The traditional industrial unit for pipe extrusion includes a calibrating device, a cdie-head, a polymeric cextruder, an extruder or a cutting device, a pulling device, and a cooling equipment. refrigeration, because the baguette process is usually the preferred manufacturing method; It exemplifies the pipe okie. coiling-up Ve coiling-up The properties of the pipe materials for this method. These fittings may have a DIA three-dimensional structure in particular for the diameter of each pipe. Curved cross-shaped structure Vo preparation of fittings as well as tubes with fixed or variable diameters. And for the preparation of polymeric materials that have a complex three-dimensional structure, the injection molding method is preferred over extrusion, given that the dle to produce these materials at the production rate of cost effective means, because it is a cost-effective means, is particularly suitable for this method; rheological properties Injection molding requires mechanical properties whereas the finished material should still have excellent mechanical properties Y. official quality standards; Any mechanical properties that remain meet the official quality standards because the same pressure, Dh, for pipes. This is especially true of pipe fittings; on the pipe only, long-term internal pressure strain does not occur on the fittings connecting these pipes either. Thus, the La polymer cannot often be used

¢ Extrusion is not suitable for actual injection molding either because of its inadequate rheological properties or because of the insufficient mechanical properties of the formed product. Injection molding is an iterative process in which the polymeric material is melted and injected into the mold cavity, where the material is cooled. in the injection molding process; Mold 0 is filled and partially solidified at the same time. However, instantaneous cooling generates internal stress; Thus, the risk of stress cracking is increased. Thus, the ALG polymeric melt should have sufficient flow to fill the SUIS cavity before solidification occurs. Furthermore; If the rheological properties are not carefully and accurately modified, the resulting molded materials will have surface defects, Jie surface defects, stripes, or 10 p patterns. Desirable surface properties are Luster 5 plus a JW surface of the flow marks. Usually, the IE cavity filling step is followed by a cus packing step that applies packing pressure to ensure complete filling. and after hardening; The mold opens and the material is ejected. However, a problem that usually arises with injection molding processes is the shrinkage of the resulting material ae. and for fittings in particular which are adapted to the size of other materials such as pipes; A small shrinkage, Tan, is very important. Shrinkage is considered a complex natural phenomenon, as it does not depend only on the compressibility and thermal expansion of the polymeric material, but rather Load depends on other properties, Je, degree of crystallinity, or crystallization speed, Y. Molecular weight and sud molecular weight distribution are also important properties for shrinkage. Furthermore; The shrinkage values of the polymer may vary in different directions (tyas) for the preferred orientations of the polymer molecules. Thus lw the shrinkage values of a number of arguments should be carefully and carefully adjusted to minimize shrinkage. However, any modification of the relevant shrink media inevitably affects the mechanical properties vs.s of the resulting injection molded product. Thus, it is well known that it represents behavior

Injection molding including the shrinkage properties as well as the mechanical properties of the finished product at the same time. As indicated above; The tubes are usually made by extrusion and because of this the rheological properties of the polymeric tube materials must be suitable for such a process. And if 0 the polymeric material is chosen with care; It improves the mechanical properties of the tubes resulting from these extrusion processes. Except today cad for the different requirements in both processes; Polymers suitable for extrusion are completely unsuitable for injection molding. International Patent Publication No. 019775/00 discloses a multimodal polyethylene composition for pipes 0. The polyethylene composition shall have a ratio of -14/14 within a range of 0. to Fo denotes another broad molecular weight distribution. The International Patent Publication No. 0/7704 also discloses a multi-modal composition of polyethylene for pipes. The shear thinning index SHI, 7510 specifies within a range of 50 to doo: 0 General description of the invention: In view of the above-mentioned problems; One of the objectives of the present invention is to provide a polymeric composition that is wide for injection molding and still produces a finished product die having excellent mechanical properties; Any remaining mechanical properties meet the official pipe quality standards. Particularly one of the objects of the invention is to provide a polymeric composition for the preparation of compositions by means of injection molding; These fittings shall have mechanical properties at least equal to those of corresponding pipes and shall have little shrinkage after molding. Gig for a first face of the present invention; These objectives are achieved by supplying a composition of polyethylene that includes a base col cbase resin and the base resin includes i ( vo ) a first part of polyethylene “polyethylene” and

_

(9) A second part of cpolyethylene Cun, the melt flow rate of the first part is higher than the melt flow rate (MFRsu900c) for the second part, and the flow rate ratio is known for the installation of polyethylene as the ratio of the magma flow rate 1902:1112 to

© CMFRsj000c Magma Flow Rate Ranging from VO to YA The magma flow rate ranges

Baum 1/271 for polyethylene composition from 0.# to 011g/0min.

According to a second facet of the present invention providing a solution to the above-mentioned problems; Provide a polyethylene composition comprising a base resin; The base resin includes f ) ( 1st part polyethylene 01:60:1606m” and

“polyethylene (b) a second fraction of polyethylene 1 where the magma flow rate M,Wm 1078 for the first fraction is higher than the magma flow rate long flow in polyethylene MoI 17 for the second segment; A polyethylene composition of 0 cm or less and a transverse middle shrinkage of 00 aly spiral flow length or less.

yo. Polyethylene compositions can be prepared according to the present invention by performing a slurry polymerization process for the first polymer part in a “loop reactor”, followed by Alec polymerization that takes place in a gas phase polymerization. for the second polyethylene part; These compositions are also particularly useful for injection molding and materials made from them.

Gy 7 for both sides of the present invention; The composition of polyethylene requires that it include a base resin containing at least two parts that differ in their magma flow rate and their 1122. The magma flow rate H, F, Y 1177 is determined according to the International Organization for Standardization “0117 aul International Standards Organization ISO” condition T T and for the polymeric material with the highest magma flow rate; The lowest viscosity. Moreover lly

l The magma flow rate with average molecular weight has an inverse relationship; Any higher magma flow rate is equivalent to a lower average molecular weight and vice versa. Lady relates to the first and second part of the polymer Gy of the present invention; The average molecular weight of the first fraction is lower than the average molecular weight of the second fraction.

o The term 'base resin' means the total unit of the polymeric constituents in a polyethylene composition according to the invention; typically constituting at least 78,560 by weight of the total composition. The base resin is preferably composed of parts (a) and (b); and includes Lad optionally on a prepolymer fraction of not more than 7780, preferably not more than 000, and most preferably not more than 78 by weight of the base resin.

1 Sale calls a polyethylene composition comprising at least two parts of polyethylene Jie polyethylene the composition according to the invention; which is produced under different polymerization conditions leading to the production of different molecular weight fractions (average weight); 'multimodal' The prefix 'multi' refers to the number of different polymer parts that make up the composition. Hence a composition consisting of only two parts is called eg AE format

Bimodal Vo

The shape of the molecular weight distribution curve is shown; i.e., the appearance of the graph of the weight fraction of the polymer as a function of the molecular weight of such polyethylene polyethylene two or more extreme values or the curve is at least distinctly teddy compared with the curves for the individual fractions.

Y. For example; if the polymer is produced by a sequential multistage process using series-coupled reactors and using different conditions in each reactor; Each of the polymer fractions generated in the different reactors will have their own molecular weight and average molecular weight distribution. When recording the molecular weight distribution curve of such a polymer; The resulting single curves overlap these

A

The fractions on the molecular weight distribution curve of the total resulting polymeric product; It usually results in a curve with two or more clear maximum values. chronological order (Ja) fiji The terms "first part" and "second part" do not refer to the method of preparation but simply to the presence of at least two different parts. Thus, both fractions can be initially prepared at the same time, or the fraction having a higher molecular weight 01 (i.e. the second fraction) can be prepared first. The completion of the polymerization process for each fraction in different reactors; This is followed by (Sa and moreover; at least in a first reactor and then Lisa mixing of the resulting fractions; or alternatively a first fraction is polymerized transferred to a second reactor where the polymerization of the second fraction is carried out in the presence of the first fraction. However, it is preferable to prepare the fraction having a lower average molecular weight in an old reactor because, as will be discussed first, the first fraction is transferred to a second reactor where a polymerization process is performed for the second fraction which has a higher average molecular weight. For the first aspect of the present invention, there is a basic feature whereby the Bagg composition has a definition that is the ratio of the flow rate of FRRyps to that of polyethylene polyethylene flow rate and YA is related to 15 to the magma flow rate M,, Y1018 The magma MFRy ranges from 0 to 1 um indicates a decrease in the amplitude of the weight distribution FRR i.e. the MWD values decrease with the molecular FRRyys; and vice versa. The corresponding magma flow rates should be measured 0m101 (FRRyys) and to determine The polyethylene magma flow rate is determined for the composition of MFR, which is the processability and therefore the flowability according to 1501133 and is related to the flowability © of the polymer. and in the viscosity of the polymer. The higher the magma flow rate; Decreased viscosity and the circumstance oT is specified (ISO 1133 according to MFRsjisoec of the present invention; 6. The circumstance is specified (ISO 1133 according to 11171 ¢/1900c according to polyethylene) and the flow rate is magma moi08 for the synthesis of polyethylene minutes.and if the flow rate of 01/mg does not exceed 0.0-0.5 ad) for the first aspect of the invention within ve

Magma Tan is below a certain level; The polymeric melt does not have sufficient flowability and therefore cannot flow into the whole cavity volume within a short period of time. However, if m0,,,e exceeds Tas 14078 above Lae, the mechanical properties of the formed product are adversely affected.

lady, ° For a second facet of the invention (opal ll a polyethylene composition comprising two parts [Legis JS] fractions has a magma flow rate of different flow length in a spiral flow length not exceeding 00 cm and a Y transverse-middle shrinkage of more than .7011

The flow length in a spiral path is a potential parameter for estimating the flowability of a polymeric composition in a mold and is therefore a useful parameter in evaluating injection molding properties. The flow length in a spiral path is determined by measuring the extent to which the molten composition is forced into the spiral cavity by applying a certain pressure and temperature. and to measure the length of flow in a spiral path of the present invention; The spiral cavity is maintained at a temperature of 0 °C. after injection; Yo polymeric magma 1 solidifies on its way to the spiral track. Judy The temperature of the material reaches coe i.e. the temperature of the spiral cavity. The polymeric composition is injected into the spiral cavity at a pressure of 14,060 bar. Sy further details in the experimental part. The mean transverse contraction is measured at a temperature of ?7C. Further details are provided in the experimental part. 0 The injection molding properties and mechanical properties can be improved at the same time if the spiral path flow length and shrinkage do not exceed the limits specified above. Preferably, the median transverse contracture should be less than 71; and sale is in range from ele 71; the best is less than 70.9 and usually from 0.# to Jed and in a preferred embodiment; The flow length in the spiral path is not more than 57.5 cm; ve and it is better not to exceed 576 cm.

1 In addition; It is preferable that the flow length in the spiral path is not less than 7; cm, and it is preferable that it not be less than £2.0 cm. According to the second aspect of the invention, polyethylene, and for polyethylene compositions.

YA to 11 present; The flow rate ratio is preferably 0.78 in the range from and the magma flow rate is preferably 1018.2 in the range 0° min: 01/mg 011 to ee The following is a description of the preferred embodiments that Applicable to both the first and second sides of the present invention. According to the present invention polyethylene is preferably for polyethylene compositions up to 510 and the best in the range from YA to 01 in the range from FRRyys A for a flow rate of 0 d and it is preferable that the magma flow rate be mm,,, 1478 for polyethylene compositions to Te minutes; and better than 1 01/mg to 176 in the range of polyethylene minutes. 01/mg cA to 17 minutes or better than 101/mg vA and according to a preferred embodiment of the present invention; The shear thinning index Vo is in the range of polyethylene for polyethylene compositions SHI, shear thinning index; Better still in 0 to 15 and better; 5117 is in the range ee to 0

Eo to #1 range from The effect of sternal thinning is related to the particle weight distribution ie the sternal thinning becomes more pronounced; The more “(MWD) molecular weight distribution 0 0 the broader the molecular weight distribution. This property can be approximated by defining the so-called viscosities measured at two shear stresses as the ratio of viscosities SHI in the shear thinning index and in the present invention; Two shear stresses of 0 are used. Different shear stresses as a measure of the amplitude of the weight distribution SHI 750 kPa for the calculation of YY 5 kPa 7.” Al-Juzaini: Yo

VA

51112 7210=M*2.7/M*210 where: kPa and 7.1 = G* at complex viscosity mh*” is the complex viscosity, kPa. 101 -6* is the viscosity vehicle at 1

CYTE, as mentioned in the international patent publication, mys 0*7, was determined using rheological measurements, and rheological measurements were made. Rheometrics Physica MCR 300 0 was determined using the formula Two-plate test of nitrogen at 1968 m in a nitrogen atmosphere, strain amplitude mm. The strain capacity YO was chosen with a diameter of plate & plate test fixture, and from these measurements; Linear working range 01 was obtained with (0::) loss modulus and (0:) storage modulus. Obtaining the storage modulus as a function of frequency » or the absolute values of the modulus Compound (n*) absolute values of compound viscosity (G*) complex modulus at on viscosity of polyethylene and according to a preferred embodiment the polyethylene composition has kPa*sec; preferably Fee Pa; no More than VEY shear stress of 1 kPa * sec, and it is better not to exceed You, not more than 1 kPa * sec. The viscosity is measured at a temperature of 198 C. 0 The first one has an average weight polyethylene and can be a copolymer or a low molecular homopolymer. It is a homopolymer but preferably a ethylene homopolymer fraction the second having polyethylene Depending on a preferred embodiment the polyethylene fraction and ethylene copolymer of a high molecular weight ethylene copolymer (Boke) at least one comonomers may be used. As a comonomer, however, it is preferable to choose carbon A carbon atoms alpha-olefin “5-uh-” with; to >

VY

The 35 co-monomers of the 1-butene-octane class ©1-00160. Preferably, 1, 4-methyl-1-pentene, nitnb-1, number: 1 4-methyl-niska-1

J-octene octene-1, 1-hexene Niske-1 (ald) In order to obtain suitable mechanical properties such as improved rapid crack propagation resistance and impact strength, the amount of comonomer should range from 4 to 77.2 mol; preferably from 0 to 727.9 mol.In a preferred embodiment, 1-hexene 116606 is used as a copolymer in the amount of polyethylene (pli) to 70.5 mol of poly composition ranging from 0.4.The weight ratio of both fractions can be adjusted by Choosing the appropriate reaction conditions in each reactor.It is preferable that the weight ratio of the low-average molecular weight fraction (the first fraction) to the high-average molecular weight fraction be 0, or better yet (1-50). :)10-5406( and better (Yoo): (Ro—Yo) (Part Two) The most favorable weight ratio of Part One to Part Two is L(£Y—0A):(OA-EY). (44-207): (44-7) Moreover, it is preferable that the minimum of any measured molecular weight be

Ears and Best 78000 for polymers in Part IIb 1 and for the base resin; Density should preferably be within the range from 0.94 to “.” g nosma 0.4287 and better from 0.448 to Tafa 7 Familiar in additives Include additives (Sa) and in addition to the base resin; (such as carbon black Pigments, such as dyes, polyethylene, antioxidants, stabilizers, carbon black, UV protective agents, cantistatic agents, and antistatic agents. 106655108 M. Among the aid agents and auxiliary agents for treatment, anti-UV agents, ultraviolet 76 by weight, and it is preferable that these components not exceed IA. The total composition of polyethylene (Ly

VY

It contains polyethylene carbon black, and it is preferable that the polyethylene composition include a weight. In a preferred embodiment; shall be TE of an amount not exceeding 77 by weight; And the best is an amount that does not exceed by weight based on the total weight 77.5 (BY) the amount of carbon black within the final range. : weight and the best by weight not more than 7006 by weight. ‎ 71 final; it is preferred to be polyethylene and for the composition of polyethylene to qe g / cm "; and the best from 1956 to LAY density within the range of .' 0.7 gm noun 1 When the preferred characteristics of parts (a) and/or (b) in the composition according to the present invention are specified here, these values are generally correct for directly measurable cases of the part concerned; For example when the part is produced separately or when produced in the first stage of a multi-stage process However, it is also preferable that the base resin is produced in a multi-stage process ve where we produce parts (a) and (b) at later stages In this case, the properties of the fractions produced in the second and third step (or later steps) of the multistage process can be deduced from the polymers produced separately in one stage by using similar polymerization conditions (Jie) temperature; Partial pressures A sall/reactants dilute cdiluents Suspension medium Y Reaction time with respect to the stage in the multistage process in which the part is produced; use of a catalyst A catalyst on which there is no pre-produced polymer.Alternatively, the properties of the resulting fractions can also be calculated at a higher stage of the multi-process (Jal yall and vacuums, for example. According to B. Hagstrom in Expanded Abstracts and Final Program for the YoY Polymer Processing Conference ($3).

Ve

ARR Aug 11-19 (Gothenburg) The Polymer Processing Society

Levy

Although the properties of the products of a multi-stage process cannot be directly measured like this, the properties of parts produced at higher stages of such a multi-stage process can be determined by applying one or both of the above methods. The experienced 0 will be able to choose the appropriate method. According to the invention, polyethylene is preferable to produce a polyethylene compound so that at least one of the two parts (1) and (b) is produced, preferably part (b) in a reaction Gas-phase reaction. One of the two parts (a) and (b) is produced in a multi-lead composition, preferably ve in a cslurry reaction, and part (7) is preferred in a slurry reaction of cpolyethylene Preferably ethylene” and that one of the two parts (a) and (b) be produced; the loop reactor part is preferably a gas-phase reaction in a gas-phase reaction (=) and it is also preferable to produce Polyethylene base resin in a multi-stage process.The resulting polymer structures in polyethylene base resin Vo inssitn resulting "in the reaction site blends" such a process is also called the combinations as a multistage process and is known as the multi-stage causation A polymer consisting of two or more parts is produced by Cus polymerisation process. Each polymeric part or at least two polymeric parts are in an independent reaction stage, where they are in the presence of the reaction product produced in the previous stage (Ala je Normally the reaction conditions are different for each 0 which includes a polymerization catalyst. It is preferable that parts (a) and (b) of the polyethylene composition oli Gy be produced at different stages of the polyethylene process. It is preferable that the multi-stage process includes at least one gas-phase phase in which it preferably takes place; Production of part (b). ve vo It is also preferable that part (b) be produced at a later stage in the presence of the part that was produced at an earlier stage. Olefinic polymers in a multiphase process involving two bimodal and especially multimodal reactors connected in series.As an example of this previous technique, the following is mentioned in ONY ATA, which is incorporated in its entirety here for reference. European Patent No. as a preferred multi-stage process led including all of its preferred embodiments described for the invention. The process for producing the two parts ©017 ATA described in EP No. 0 for part A/slurry polymerisation and (b) is carried out as a combined process of slurry polymerization (00) of part B. It is preferable to perform Gas-phase polymerisation The slurry polymerization stage is before the Lind slurry in what is called a loop reactor.It is preferable to have the gas-phase polymerization stage. The main polymerization stages may be preceded by a process of 701 weights in which case no more than a prepolymerisation of up to 76 weights of the total base resin is produced. 1 weight and better from 701 to 76 weights 1 It is preferably a prepolymer and preferably a primer. In the prepolymerization process all the catalysts are charged in a loop reactor (HDPE). The prepolymerization takes place as a slurry polymerization. This pre-polymerization leads to the production of less fine particles in subsequent reactors and to a more product in the end. Lakes of metal coordination catalysts Ziegler-Natta (ZN) can be used as polymerization catalysts. ) Ziegler-Natta catalysts Jie transition metal transition non-metallocene catalysts 00-5 chrome catalysts cmetallocenes Yo

- . ..etc. The catalyst can be portable; Sle on conventional supports that include silica 511:68 Al-containing supports Al-containing supports and magnesium dichloride based supports It is preferable to use Ziegler-Natta catalysts and metallocene catalysts. metallocene, and it is better for the catalyst to be ZN, and it is better for the catalyst to be a ZN lia carried on a carrier other than AY silica, preferably a ZN catalyst based on MgCl, and it is preferable It is assumed that the Ziegler-Natta catalyst contains a metal compound from the group ; (According to the new system numbering of the International Union of Applied Chemistry 01 and the abstract IUPAC for the groups) 0 Titanium is preferred as magnesium dichloride and aluminum. The catalyst is commercially available or can be produced as TE for the following. in scientific publications or in a similar manner. For the preparation of the preferred catalyst that is suitable in the invention, reference is made to the International Patent Publication No. TA 0406 and the Vo International Patent Publication No. 714 Yeo in the name of Borealis European Patent No. or TAA 84 Finnish Patent No. 1/88 98 and European Patent No. We.

AY.

YYO incorporate the entire content of this documentation here for reference as alas reference with respect to the entire general and preferred embodiments of the catalysts described therein as well as the production methods of such catalysts. The favored Ziegler-Natta catalysts are described in particular © in European Patent No. 75 800 .. The final product formed from an initial mixture “allie” consists of polymers resulting from the two reactors, where the different curves of weight distribution JUS The molecular weight of these Tae polymers has a molecular weight distribution curve that has a wide maximum value or two maximum values; That is, the final product is a bimodal polymer mixture.

He wrapped

Preferably the polymodal base resin in the polyethylene composition according to this invention is a bimodal polyethylene mixture consisting of parts (a) and (b); It optionally additionally includes a small primer fraction in the amount described above. It is also preferable that this bimodal 0 polymeric mixture be produced by the polymerization process described above under different polymerization conditions in two or more polymerization reactors connected in series. Because of the flexibility of the reaction conditions obtained in this way; It is absolutely best to conduct the polymerization in combination from a reactor

Toroidal/gas phase reactor. Preferably, the polymerization conditions should be chosen in the preferred two-stage method

0 such that a relatively low molecular weight polymer containing no co-monomer is produced in one of the two phases; The first stage is preferred; Because of the high ratio of chain-transfer agent (lain (hydrogen gas) a high molecular weight polymer containing a co-monomer in another phase is produced; the second phase is preferred. However, the order of these phases can be reversed.

In the preferred embodiment of the polymerization process in a loop reactor followed by a gas phase reactor, the polymerization temperature in the loop reactor would preferably range from AC to 115 °C; The best is from 50 to 10 C, and the most preferred is from 97 to 1,000 C. The temperature in the gas phase reactor ranges from 700 to a Veo, and the best is from 5 to 100 C, and the most Sails range from 8 to 9 C.

1 and a transfer operator is added to the string; Hydrogen is preferred according to the need for the reactors, and it is preferable to add 001 to 800 moles of .11 / kilomol of ethylene to the reactor when producing the low molecular weight part in this reactor; Zero to ¾ mol of .11/kmol of ethylene is added to the gas-phase reactor when the high molecular weight fraction is produced in this reactor.

Ya

It is preferable that the base resin be produced in a polyethylene composition, and the best is at a rate of not less than cton/h, with a rate of not less than © ton/hour, polyethylene, ton/hour. of 0 and the composition according to the invention is produced preferably in a process comprising a synthesis step of the base resin composition; any combination; Which extrude where the compounding step 0 is usually obtained in the form of powder for the base resin extruded from the reactor in a well-known method polymer pellets and then formed in the form of pellets of polymer extruder in the technique. Optionally add additives or other polymeric components to the composition during the synthesis step in the amount described above. It is preferable to synthesize the composition according to the invention 0 resulting from the reactor in the extruder with additives in a manner known in the art. from any conventionally used extruder. lady Examples of extruders used in the synthesis step are Farrell-Pomini, Kobe steel, Japan steel works, JSW 460P (Jie Farrel-Pomini 0 400). In one embodiment, the extrusion step is performed using Production rates of not less than 0001 kg/hour in kg/hour or not less than 50000 kg/h not less than the mentioned synthesis step. The synthesis step can be accomplished with a production rate of no less than © ton/hour; DAT and in the embodiment of ton/hour or Yo or Yo ton/hour; preferably not less than 11 and preferably not less than ve to 1 ranging From Se ton/hour; not less than 50 Me ton/hour Ye to not less than to 960 ton/hour and in 01 ton/hour; preferably from © to 460 ton/hour or from 0 t/h. Yo to 01 Some embodiments from

11 tons/hour; Preferably not less than Yo and alternatively may want production rates not less than to Yo tons/hour; For example, it ranges from Ye tons/hour; and so that the YO is not less than t/h during the synthesis step. 0 of the present invention Ty is polyethylene and polyethylene synthesis is permitted according to the invention; That is, the property window by achieving these production rates within the properties window 0 for the parts and for the final basic resin with excellent homogeneity MFR with different combinations of properties, for example, but not limited to. Preferred, the mentioned specific energy income is not less than the same as the extrusion Gull biomechanical value in the step of 0 kilowatts / ton “Malta. Where it is usually the highest (maximum) magma temperature in the composition in the cracking tool

You preferably ca TOs 701 during extrusion step higher than 196 m; And appropriately between 700 m Yor to 10 m and better than that; The present invention relates to a process for producing a Sad vo polyethylene composition as described above comprising the following two steps: (i) polymerization of cethylene monomers and optionally one or more alpha-olefin co-monomers; The presence of a Ziegler-Natta catalyst to obtain a first fraction (Jil) on a homopolymer or an ethylene copolymer 7 (ii) polymerization of ethylene monomers and an alpha monomer optionally one or more alpha-olefins in the presence of a Ziegler-Natta catalyst to obtain a second fraction (b) comprising a copolymer or its ethylene copolymer The average molecular weight is higher than that for fraction ve (0) where the second polymerization step takes place in the presence of the first step polymerization product.

Y. loop reactor It is preferable to carry out the polymerization process to obtain part (a) in a loop reactor. It is also preferable to carry out the polymerization process to obtain part (b) in a gas phase reactor.

Cua prepolymerisation It is preferable that the first polymerization step be preceded by a pre-polymerization step. Weight at most, and the best as well. 0 at most, and the best. Toy 771 It is preferred to produce 0. total base resin, by weight at most, from the total base resin, 8 (ai yal). melt flow rate The first polymer with a melt flow rate is usually produced without the addition of a co-monomer in (LMW) part (a); (low average molecular weight) the first reactor; while the second polymer with a flow rate is produced Low melt (has medium) with the addition of a co-monomer in the second reactor. (HMW) high molecular weight 0 using (Kay (b) compounds); carbon Different A carbon atoms contain from 4 to alpha-olefins alpha-olefin niscum-1 clbutene nitweb-1 The copolymer is selected from the group consisting of 1-octene nitko-1 and . 4-methyl-l-pentene nitnB-1-methyl-4 ¢ 1-hexene to 77.8 mol; preferably from 1.4 and preferably the comonomer amount ranges from Vo to 77.9 mol and most preferably from ?- 1 to 7505 moles of 1 .multimodal polyethylene ALE flows molten polyethylene and shows the structure of polyethylene easily. And after improved mold cavities, which works to fill the mold cavities, flowability, you only notice a small percentage of shrinkage, cinjected melt, solidification of the injected magma, vy. In particular, in the fade of the present invention, Gay, the composition of the polymer “lg shrinkage .injection molding, injection molding processes, has mechanical properties, and moreover; The materials resulting from the molding process show similar or at least completely close to the properties of pipes prepared by extrusion; mechanical properties at positive pressure subject to positive pressure, “pressure pipes, especially” pressure pipes vo

use it. Therefore, assemblies such as pipe assemblies made of multiple compositions can be made according to the present invention. Rapid cracking or rupture intensity stress crack resistance daglia cimpact strength pall 0 .creep rupture strength rapid crack propagation (RCP) The resistance to rapid propagation of cracks can be determined 54 Ex test of the method Gy of a particular tube-shaped formulation prepared by injection molding which is protruded at Imperial College (Small Scale Steady State Alls) 150 13477 London and described by Imperial College 1 is not less than an axial length Has an axial length 0 for test 082080-54 fad gg pipe is tested mm 011 of the pipe for about outer diameter and the outer diameter is not less than 0 times the diameter of the pipe VY

RCP mm. And when determining the properties of 01 about the wall thickness, and its wall thickness is not less than according to the present invention; The outer diameter of a pipe-like fitting is chosen for a pipe-like fitting in mm. While the outer surface of the tube is 10 mm and the wall thickness is 0.11 odio, the atmospheric pressure (ambient pressure) is exposed to the surrounding pressure. The tube is pressed internally, and the internal pressure in the tube is kept constant at a positive pressure of

MPa is a megapascal. .© specific temperature da temperature of the tube and ambient devices at TES located inside the tube to prevent the shaft on the discs several co” Hag advance. > knife projectile during the tests. A decompression knife projectile is fired towards the tube near one of its ends in cwell-defined forms with well-defined shapes to start creating a fast-expanding axial assimilation (initiating zone ead) called a zone to avoid uneven deformation. abutment and provide the starting area with the rapidly running axial crack necessary for the tube. The test apparatus shall be set so that cracking begins in the material concerned; ve

YY axial crack length Several tests at different temperatures. The measuring zone: the axial crack length, which is four times the total length, is measured in the measurement area in each test and tilted axially against the set test temperature. If the length of the crack exceeds four times the diameter of the tube; The crack has spread. And if the tube achieves the test results at a certain temperature; The temperature is gradually reduced until it reaches -0 a temperature at which the tube cannot achieve the test results, but the crack spread exceeds (m7), i.e. critical temperature, and the critical temperature is 0 four times the diameter of the tube According to the ductile brittle transition temperature, the transition temperature from ductile to brittle is the lowest temperature at which the tube passes the test results. The lower the critical temperature, 150 7; the better the situation; Since it leads to an increase in the scope of use of 0 tube. Preferably the tubular formwork made of the multimodal polymer composition of the present invention has a value of 808-54 of -11m (the minimum requirement for a type Ts pipe (the minimum requirement for a pipe type a t= or less; the best is a value of ( MD PESO or less. (HD PESO 1 in accordance with Charpy Impact Strength The impact strength is determined by the Charpy Impact Strength Vo preferably for multimodal polymer compositions of the present invention 18 179 150 at kim? kJ/ M'A, which is used to prepare pipe fittings, has an impact strength of not less than zero degree, and it is better not to be less than 9 kilojoules / meter.

Gi, calibrated pipe notch test, stress crack resistance is determined in the pipe notch test, Li 13479 150. In the test, the slow growth of cracks is simulated and the breakdown time is recorded 0

SA in grooved tubes. The tests are conducted at a temperature of time to failure and a pressure of 4.7 MPa. At a pressure of 7.8 MPa PENT and measurements of slow growth of cracks are conducted (ASTM F 1473) F 1473 method ((ASTM) according to the American Society for material testing

TY

{8 Calibrated internal pressure test, and the intensity of the creeping rupture is determined in an internal pressure test, 81921, LB 1501167, and the surface properties are manually evaluated by the naked eye. The desired surface is mirror-like Jie flow patterns. It classifies and notes any surface disturbances; eld lab or other deformations. Surface roughness patterns ° Detailed description The present invention will now be explained in greater detail by reference to examples of preferred embodiments. EXPERIMENTAL PART a) Molecular weight and distribution 1. weight average molecular weight ye measured Represents the mean M, where MM, = MWD) molecular weight distribution M,, 5 number average molecular weight represents the numerical weight of the molecular weight lea molecular weight) by a constructed method According to what was mentioned in 1601453 150. And using the waters 150CV plus CV plus You instrument (diphenylbenzene, Waters supplied by Waters, 3 x HT&E styragel § s— from column Vo at solvent temperature as a solvent (TCB) trichlorobenzene and trichlorobenzene (divinylbenzene de) and the group of columns was calibrated using SVE calibration with a narrow molecular weight distribution (Mark Huings constant) using CHAPS standards universal calibration Y: Y4*Y.AY ja 5 PS J +.VYO ia *"y+*q,0¢ K Mark Howings constant: Tok is a measure of the breadth of the distribution; My and My represents the ratio between (PE Lee 58 Y. "population is affected by the opposite end of the "group spiral flow length b) the flow length in the spiral path provided with injection automat Al injection using F The flow length is measured in the spiral path

ENGEL ES 250 'plasticating screw' with forming screw mm 00 screw diameter yo

Y¢ cm 71: max. piston displacement Maximum piston displacement bar 001 ispec. injection pressure Trapezium Auk icross section 001:_helical; 0101: cross sectional area: 1 mm; cross sectional area; Cross-sectional area 7.1 Thickness: 1060 mm die and pre-chamber Temperature in advanced chamber 0

SY IXY YE [YT 6 : temperature in zone/zone 7 “/zone/zone secs pre-injection time injection cycle ? seconds: post-injection time 01 seconds cooling time injection pressure = dwell pressure stop pressure 01 revolutions/min 001 screw speed screw speed Zero bar backpressure mm before Yo It should be selected so that the spiral stops at a distance The metering path reaches the final position at the end of the stop pressure aor BIN nda ne The flow length can be specified in the spiral path Immediately after the injection process. Helical trajectories are calculated at least. 01) An average value of the measured values

Shrinkage c) Shrinkage supplied by DIGIMATIC INDICATOR Shrinkage measured using an instrument and for calibration; Uses a standard plate. 10111710770 Corporation Mitutoyo Corporation Y. mm. The Ar x 0 mm operation is carried out, and it has a size of dimensions made of steel, standard plate, measured at a temperature of 77 C during the first 96 hours after injection. To measure, the standard plate is placed in the device in the direction of ctransverse shrinkage, and then; The zero position plate is placed and the transversal direction is fixed mm in the device. And to measure the median transverse shrinkage of 88 x mm 10 the dimensionless test ve

Yo The test plate is placed in the device so that the side away from the ctransverse middle shrinkage .middle stop is located at the middle barrier gate mark The plate used for shrinkage measurements by injection molding Smads using the following media: injection molding 1410 m: melttemperature ° a © + mold temperature JE 001 flow front velocity

Tes Return pressure (specific): +94 and decreases to 01 seconds Return pressure time: Ye seconds Cooling time: Ve

The machine used for injection molding was ENGEL ES 250 and all other physical properties were measured as indicated above.

Yu Examples 1 ged according to the present invention in polyethylene a multimodal synthesis of the first polyethylene was prepared in a loop reactor; This is followed by a two-step process Jeli polymerization; An additional step 0 takes place in the gas phase reactor. A prepolymerization was carried out before the reaction step in the reactor as the co-monomer of the high weight fraction 1-Hexene Niske-1. The resulting particle was used in the gas-phase reactor. The content of the co-monomer in the resulting polymer (trademark) (Lynx chloride catalyst 2007" was 001 and as a catalyst; use Lys 001). States (Pasadena Engelhard Corporation and marketed by Engelhard Corporation 1. USA) The reaction conditions are summarized in Table J11: “The gnsorc index was determined, and the density was determined; ... Er007” Its shear stress at shear stress viscosity eta (5111), the viscosity shear thinning index of 67 la Pa, and the flow length in the spiral path of the resulting composition. Extruded in the form of a tube and measurements of the spreading strength of test 54 were carried out; stress crack strength; creep strength of rupture and Tig rapid growth of cracks.

PENT slow cracking

Cay Bll and determined the intensity of Charpy impact and shrinkage on injection molded panels according to Y. 7 in Table Lue Experimental mentioned above and the results ?ged according to the present invention in polyethylene prepared multi-modal composition of polyethylene annular; This is followed by a two-step Jolie polymerization process; So that the first reaction step takes place in an additional gas-phase reactor. A prepolymerization was performed prior to the reaction step in the vo reactor

Yv as the comonomer of the high-weight fraction 1-Hexene Niske-1-cyclo. The resulting particle was used in the gas-phase reactor. The content of the co-monomer in the resulting polymer, and the reaction conditions are summarized in 1. The same catalyst used in the example Lys 7.1 1. Table ¢ (SHI) FRRyys shear lamination index was used. » sMFRspgoec Density specified; Pa; And the flow length in the spiral path is VEY viscosity Eta at shear stress of . for the resulting assembly. The results are shown in the table, then the polymer composition was formed by extrusion in the form of a tube, and the spread resistance measurements were carried out for test 54; stress crack resistance; The intensity of creeping rupture and the rapid growth of cracks, Gis

PENT slow cracking Ve Charpy impact intensity and shrinkage on injection molded panels under Cag 7 experimental conditions mentioned above and results shown in Table 1 Comparative example in a two-step process; cycloethylene, followed by an additional polymerization step in the first olin reactor in Joli so that step 10 of the gaseous phase takes place. A prepolymerization was performed prior to the reaction step in the loop reactor. It was used as the comonomer in the resulting high molecular weight fraction in 1-Butene netweb-1 wt. #7001 gas-phase reactor. The content of the co-monomer in the resulting polymer was as described in the European patent, Ziegler-Natta, and a Ziegler-Natta type catalyst (MFRs/g0c) was used. The density was determined 1. The reaction conditions are summarized in Table TAA 954/9 No. 7 The viscosity Eta at a shear stress of (SHI) +0 and “12” Ry8©” shear laminating index Pa, and the flow length in the helical path of the resulting structure. The results are shown in Table 7. VEY YY

Ya

Then the polymer composition was shaped by extrusion in the form of a tube, and measurements of the resistance to spreading, the intensity of the creeping rupture, and the rapid growth (glean) of cracks were carried out according to test 54; Crack resistance

PENT slow cracking under Lig conditions Charpy impact intensities and shrinkage were determined on injection molded panels 7. Experimental results mentioned above in Table Aue and results 0 Comparative example? The format is polyethylene such that the first reaction step takes place in a loop reactor; Followed by an additional polymerization step in a gas phase reactor. A prepolymerization was performed prior to the reaction step in the loop reactor. It was used as the co-monomer in the high molecular weight fraction produced in the 1-Hexene Niske-1 01a NZO 77.1 gas phase reactor. The content of the co-monomer in the resulting polymer was as described in the European patent, Ziegler-Natta, and a Ziegler-Natta catalyst was used, and the density was determined; Rama’a 1. The reaction conditions are summarized in Table TAA 1/94, the viscosity number Eta at a shear stress of “(SHI) shear lamination index FRRyys” and “Ria 1” 477 la Pa; and the length of flow in the spiral path of the resulting structure. The results are shown in Table 1. Then, the polymer composition was formed by extrusion in the form of a tube, and the spread resistance measurements were carried out for test 54; stress crack resistance; Intensity of creeping rupture and rapid growth of cracks

PENT Slow Cracking, Charpy Impact Intensity and Shrinkage on Injection Molded Plates under Conditions Cada 7

XY experiment mentioned above and the results are shown in the table

And the table: 1 | Saqqa | me [re] cue temperature ("” 2 2 2 l cog 01 Ya Yu MFR; q Co ees reactor silat 1 temp ( qo 0 q0 ie 0 a mol/kmol TY.£0.YY.

MFR; .1190°¢ LA EE I is a gaseous-phase reactor v mol/kmol Aa mol/kmol. / 7 17

B Table 7: Example 1 Comparison example (| Example YARD 1/10 CAA ee a 1 0 / min : MFR 0 v4 yy 21.5/190°C a 7g/10min Density | Output (LY) Composition density (Sel) ER (kPa *sec) Flow length in the spiral path (Charpy shock pad at V0.4 7 yY.) 74 ; seminal zero (kJ/value RP according to test 84)' stress-cracking resistance L s.d., for tubular indentation test at 1> 1/4 a NEMA 7 MPa (PENT h at Y.A MPa Yo..< 15 01 h Internal pressure test 0.1 MPa (14 hours (continuous v4 J tT) ( ) ) and © Ova 0.0 MPa (7 hours (continuous 4 £ J tT ) ( ) ( ) .0 free 7 MPa (hr 07 (continuous) 07 (continuous contraction) xi all 1 2 u middle transverse VA Vv CLAY CAN 1 a compressive 0 | hard | d 0 | hm 0 EE (continuous): denote However, these measurements have not been completed yet, but Baha's work continues, meaning that the final values may be higher than that.

Claims (1)

1 Elements of protection 1-1 polyethylene composition containing base resin Y and base resin containing 1) A first part of polyethylene f ¢ (b) a second part of polyethylene ° where the melt flow rate of Mo17 for the first part is higher than the MFRs/900c melt flow rate for the second part; The flow rate ratio 7 for the composition of epolyethylene is defined as the ratio A of the melt flow rate without irrigation to the melt flow rate of 9 Moi71 where it ranges from “YA (B10) MFR 900c melt flow rate Ve for polyethylene composition ranges from +0 to 101g/10min. aS BY 1 polyethylene composition containing base resin Y and base resin containing a) A first part of polyethylene and ¢ (b) a second part of polyethylene ° where the melt flow rate m108 of the first part is higher than the MFRggec melt flow rate of the second part; The polyethylene-7 composition shall have an OO & spiral flow length of centimeter (cm) A or less and a transverse middle shrinkage of 9 011 or less. 1 ¥— Wy polyethylene composition for Claim 1 where YY. YA to Yo from FRRyys flow rate ratio Y flow rate ratio 1 ;- polyethylene composition according to protection element oY element protection Y where the magma flow rate ranges melt flow rate 1/17 for composition of v polyethylene from 0.*# to 011g/0min. 1 0— polyethylene composition in accordance with any of the foregoing claims; where the FRRyys flow rate ratio ranges from 01 to XT 71-1 polyethylene composition according to any of the foregoing Y-pale protections; The MFR 900c melt flow rate for v polyethylene synthesis ranges from 0.68 to 0.88 g/10 min. —V 1 polyethylene composition in accordance with any of the preceding Claims 7; dua Jay composition has shear thinning index (SHI) v defined as the ratio of viscosity at a shear stress of Y.V ¢ Kilopascal (kPa) to viscosity at a shear stress o of 701 kPa ckilopascal ranging from 01 to 60. 1 - Polyethylene Composition polyethylene composition according to Clause Gua 1. The Y shear thinning index ranges from 11 to 40. 1 4- A polyethylene composition in accordance with any of Element 7 of the foregoing protection; where the composition has a composition of viscosity eta 1 at ga) 68:5 ss and VEY is pascal (Pa) 00 ¢ kilopascal *second (kPa*s) or less. 1 ) = polyethylene composition in accordance with any of the foregoing Claims Y; where the second part of polyethylene (b) is a Y copolymer of ethylene 56 and at least one comonomer. -11 1 polyethylene composition according to the claim Ov where the comonomer is selected from the group consisting of 1-butene 4-methyl-1-pentene nitnb-1- Litham-4 ¢I-hexene Nisc-1 v and 1-octene .1-octene -1"-1 polyethylene composition according to claim VY wherein the comonomer is 1-Hexene Sis 1-hexene 1-octane and .l-octene -0 1 polyethylene composition according to any of the claims 01 ey to OY wherein the amount of comonomer in a polyethylene composition ranges from +f to 77.5 mol. 1-06 polyethylene composition according to any claim Y from 01 to OY in which compound 1-hexene p:*”.1 is present as monomer 0” > Contributing comonomer in the amount of +f 7009 moles of polyethylene composition .polyethylene t -15 1 polyethylene composition pursuant to any of the preceding Claims Y wherein the first part of polyethylene 0 is a polymer .ethylene (LY! from a homopolymer v polyethylene composition of a polyethylene composition production 05m for the production of lee -11 1 of any of the foregoing claims the following two steps include lag Y (i) polymerization of 8 monomers of ethylene 1 and one or more comonomers of alpha-olefin ° optionally" in the presence of a Ziegler-nata catalyst Natta catalyst 1 for first part 00) comprising 7 homopolymer or copolymer of A ethylene 9 0 monomers <i jase polymerizing of ethylene Ve and one or more alpha-olefin co-monomers 18e1e-ctm1e_optionally; In the presence of a Ziegler-Natta catalyst \Y alm plea to obtain a second fraction (b) comprising a homopolymer or a copolymer (ye copolymer Vt ethylene) having an average The average molecular weight is higher than that of part 1 (1) where the polymerisation step 4) is performed in the presence of the polymerization product \Y adie produced from the first step. Polymerization where the polymerization process is performed 1 for the protection element Gg process 1-11 process 1 loop reactor to obtain part (A) in a ring reactor Y 1e—YA the Gy process of claim 11 or claim VY in which the polymerization process to obtain part B is performed in a gaseous reactor Ye .gas phase reactor ton v where YA precedes step 1 to 11 of any of the protectors of Gg process Ades -14 1 .prepolymerisation Polyethylene cinjection molded article Injection molded Bale —Y 1 Ao to 1 claim of pale of any polyethylene Y of claim 17; where injection molded article -71 1 fitting is a combination of article 1 where it is YY) according to the claim injection molded article injection molded article -8 1 pipe fitting Is a pipe fitting fitting Composition: according to any element injection molded article to prepare an injection molded material process — YY process 1 The process includes an injection molding step Cus YY to 010 protection elements at least one Y. injection molding 1 according to any of the polyethylene protection elements;