EP1401624A2 - Verdichtung von polyäthylenfusseln hoher dichte - Google Patents
Verdichtung von polyäthylenfusseln hoher dichteInfo
- Publication number
- EP1401624A2 EP1401624A2 EP02764622A EP02764622A EP1401624A2 EP 1401624 A2 EP1401624 A2 EP 1401624A2 EP 02764622 A EP02764622 A EP 02764622A EP 02764622 A EP02764622 A EP 02764622A EP 1401624 A2 EP1401624 A2 EP 1401624A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyethylene
- molecular weight
- fluff
- pellets
- fines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/08—Making granules by agglomerating smaller particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
- B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
- B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Definitions
- the field of this invention is a method of agglomerating polymers and fines that does not degrade the material.
- fine powders are defined here as polymer particles having a diameter of less than 125 microns: they are unavoidable and are produced as a byproduct during polymerisation.
- the suppression of fines was successfully achieved by extrusion of the fluff to produce pellets thereby allowing high feed rate in downstream equipment: a 10 to 30 % increase in the throughput has been observed with pelletised material.
- That method however presents several drawbacks: - it requires extrusion capability thereby increasing the cost, and - most importantly, it degrades the properties of the material, such as the melt flow index and the dynamic rheology, especially in the case of high molecular weight polyethylene. It is believed that the shear forces are responsible for the degradation of the extruded material.
- a compaction method has been disclosed in U.S. 5,393,473. That application discloses the compaction of ultra-high molecular weight polyethylene, alone or as a mixture with other polyethylene.
- the compaction machine has a die geometry that allows good density of the compacted pellets.
- the polyethylene being produced with a Ziegler-Natta catalyst, shows little degradation as expected.
- the compaction method and equipment are disclosed for example in several patents to Amandus Kahl:
- - DE-3344044 that discloses an additional step of precompaction before the actual compaction step
- - DE-3432780 that discloses a method for wetting the material during compaction
- fluff of high density polyethylene produced with a chromium catalyst or a metallocene catalyst degrades easily when mechanically extruded to form pellets; there is thus a need to produce these materials under a less degraded form.
- the present invention provides a process for agglomerating a fluff comprising one or more polymer(s), optionally, one or more polymer fines and optional additives, said fluff having a high load melt index (HLMI) of from 0.1 to 20 g/10 min, and preferably from 0.1 to 10 g/10 min, by submitting said fluff to a mechanical force at a temperature sufficient to soften and deform the polymer grains.
- HLMI high load melt index
- a fluff is defined here as the distribution of polymer grains exiting the reactor.
- the optional additives are pigments, fillers, colorant or any other usual additive.
- the resulting agglomerated polymer pellets are substantially free of degradation.
- the polymers present in the fluff can be selected from polyethylene, polypropylene, PVC and polystyrene.
- one polymer is an olefin, more preferably, it is polyethylene, and most preferably it is high molecular weight, high-density polyethylene.
- the polymer fluff comprises preferably from 80 to 100 wt% and more preferably from 80 to 95 wt% of a first high molecular weight high-density polyethylene, prepared by Ziegler- Natta or chromium or metallocene catalysis, but preferably prepared by chromium or metallocene catalysis, and from 20 to 0 wt% and more preferably from 20 to 5 wt% of a second polyethylene of low or medium density prepared by any method known in the art, but preferably prepared by metallocene catalysis.
- the temperature of the agglomerated polymer pellets is of from 85 to 150 °C, preferably of from 90 to 125 °C and more preferably of from 90 to 112 °C.
- the temperature of the agglomerated pellets is from at least 90 °C up to 125 °C.
- the polyethylene fluff used in the preferred embodiment of the present invention, has a density of from 0.94 to 0.97g/cm 3 as measured at 23 °C following the method of standard test ASTM D 1505.
- the high load melt index (HLMI) is of from 0.1 to 20 g/10 min and preferably of from 0.1 to 10 g/10 min, as measured at 190 °C following the method of standard test ASTM D 1238 under a load of 21.6 kg.
- the weight average molecular weight is in the range of 200,000 to 400,000.
- the polyethylene fluff can be selected to be suitable for blow moulding, or for injection moulding, or for roto-moulding.
- a chromium-based catalyst i.e. a catalyst known in the art as a "Phillips catalyst”
- a chromium-based catalyst enables the production of polyethylene having desirable physical and rheological properties.
- Chromium-based catalysts can be used to polymerise HOPE and in particular to produce high density polyethylene having high resistance to environmental stress cracking.
- EP-A-0,291 ,824, EP-A- 0,591 ,968 and US-A-5, 310,834 each disclose mixed catalyst compositions, incorporating chromium-based catalysts, for the polymerisation of polyethylene.
- the chromium-based catalyst can be tailored to prepare polymers having specific properties: it can be supported on an inorganic support and undergo various treatments such as titanation, reduction and/or activation.
- the HDPE can also be polymerised with a metallocene catalyst capable of producing a mono- or bi- or multimodal distribution, either in a two step process such as described for example in EP-A-0,881 ,237, or as a dual or multiple site catalyst in a single reactor such as described for example in EP-
- Any metallocene catalyst known in the art can be used in the present invention. It is represented by the general formula:
- Cp is a cyclopentadienyl ring
- M is a group 4b, 5b or 6b transition metal
- R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms
- X is a halogen
- (CsR'k) is a cyclopentadienyl or substituted cyclopentadienyl
- each R' is the same or different and is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms are joined together to form a C4-C6 ring
- R" is a C- ⁇ -C-4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical bridging two (C- ⁇ R'k) rings
- Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having 1-20 carbon atoms or halogen and can be the same or different from each other
- Q' is an alkylid
- the metallocene may be supported and an active site must be created by adding a cocatalyst having an ionising action.
- alumoxane is used as cocatalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
- one or more aluminiumalkyl may be used as cocatalysts.
- the density of polyethylene is regulated by the amount of comonomer injected into the reactor during the polymerisation procedure.
- comonomer examples include 1-olefins butene, hexene, octene, 4-methyl-pentene, and the like, the most preferred being hexene.
- the densities of polyethylene used in the preferred embodiment of the present invention range from 0.940 g/cm 3 to 0.970 g/cm 3 .
- the melt index of the metallocene polyethylene is regulated by the amount of hydrogen injected into the reactor.
- the melt indices useful in the present invention range from 0.1 g/10min to 20 g/10 min, and preferably from 0.1 to 10 g/10 min.
- the HDPE can be produced using a conventional Ziegler-Natta catalyst or a supported Ziegler-Natta catalyst comprising metallocene sites such as described for example in EP-A-0,585,512.
- the high molecular weight, high-density polyethylene is blended with another polyethylene of low, or medium molecular weight prepared with any catalyst system. Preferably, it is blended with a medium molecular weight metallocene polyethylene.
- the metallocene polyethylene resin used in the present invention can be prepared with either a single site metallocene catalyst or with a multiple site metallocene catalyst and it has therefore either a monomodal or a multimodal molecular weight distribution.
- the molecular weight distribution is of from 2 to 20, preferably, of from 2 to 7 and more preferably of from 2 to 5.
- the material prepared from the fluff of one or more polymer(s), the fines and optional additives, is then cycled through the compactor.
- it is cycled only once through the compactor but it may be cycled more than once if desirable, thereby allowing for a longer time spent under pressure and for a higher heat build up.
- the agglomeration procedure does not produce polymer granules with suitably low level of attrition if the operational temperature is too low. It is nevertheless desirable to maintain the temperature as low as possible during compaction in order to avoid extensive melting of the material. Indeed, if the material melts extensively, it acts like glue that builds up on the walls of the compactor.
- the necessary level of temperature varies with the nature of the polymer: it is defined here as the temperature at which the external surface of the polymer grains in the fluff starts softening.
- a minimum temperature of 90 °C is necessary in order to produce granules that resist attrition after a single cycle through the compactor.
- the die hole diameter of the compactor can be adjusted by changing the die plate depending on the desired diameter of the agglomerated pellets: it varies from 2 to 5 mm and is preferably about 3 mm.
- the land length of the die holes can also be adjusted in order to alter the residence time and hence the hardness of the pellets. It is of from 10 mm to 60 mm.
- the ratio between diameter and length of the die must be adjusted for optimal agglomeration conditions and is preferably of from 1 :4 to 1 :12, most preferably from 1 :5 to 1 :7.
- Additives can be used as binders but the degree of compaction is not substantially improved by such addition.
- the polymer and fines can thus advantageously act as their own binder and the resulting agglomerated product is therefore not degraded during the compaction process.
- the low and very low density density polyethylene (LDPE and VLDPE) and the metallocene linear low density polyethylene (mLLDPE) are known to have a low melting point and they can also be used as binders: very small amounts of less than 5 wt% are necessary.
- fines defined here as particles having a diameter of less than 125 microns, can be used as binders in the agglomeration procedure. They can originate from the same HDPE as that used in the compaction procedure or they can come from another HDPE. Preferably, they originate from the same HDPE. Small amounts of less than 5 wt% are necessary.
- fines originating from other polyethylenes are used as binder they do not need to be produced by the same polymerisation method as that of the polyethylene to be compacted.
- the fines are of the same material as the material to be agglomerated and are produced in situ during the polymerisation procecedure.
- the polymer pellets obtained by the present agglomeration method were tested for degradation. Very little degradation is observed as evidenced by melt flow index measurements, antioxidant consumption, dynamic rheology and molecular weight as measured by gel permeation chromatography.
- the dynamic rheology is measured using the method of the rheological dynamic analysis. It is a measure of the resistance to flow of material placed between two parallel plates rotating with respect to each other with an oscillatory motion.
- the apparatus comprises a motor that transmits a sinusoidal deformation to the sample.
- the sample then transmits the resulting constraint, said resulting constraint being also sinusoidal.
- the material to be studied can be a solid attached between two anchoring points or it can be melted between the two plates.
- the dynamic rheometer allows the simultaneous measurement of both the elastic modulus and the viscous modulus of the material. Indeed, the resulting sinusoidal constraint is displaced by a phase angle ⁇ with respect to the imposed deformation and it is mathematically possible to decompose the resulting sinusoid into:
- the complex modulus is given by the formula
- G ⁇ / ⁇
- the complex viscosity is defined as G / ⁇ .
- G' and G" can be measured for different values of ⁇ . The measurements were carried out under the following operating conditions:
- the elastic component G ! and the viscous component G" are graphed as a function of frequency ⁇ .
- the point of intersection between the elastic and viscous curves, called the cross-over point (COP), is characterised by a frequency ⁇ c and a viscosity component G c .
- the cross-over point is characteristic of each polymer and is a function of the molecular weight and of the molecular distribution.
- the antioxidant consumption is a measure of the level of degradation.
- the quality of compaction is measured by the attrition test developed internally.
- the samples are divided into N equal parts over a sample divider. Each part is then re-mixed during 5 minutes in a small laboratory tumbling mixer.
- the attrition test is then performed twice on each part as follows. - Using a standard vibrating sieve analysis equipment (Fritsch- Retch) with a sieve having square apertures of 1600 microns, the weight % of material lost through the sieve is determined after 3, 10 and 30 minutes. - The severity of the impact and therefore of the attrition conditions can be altered by adding 10 spherical balls.
- the severity of the impact and therefore of the attrition can be fine-tuned by varying the density, the nature and the number of the spherical balls.
- the present test has been performed with 10 spherical balls of Zirconium oxide having a diameter of 8 mm.
- the degree of attrition of the material is represented by the slope of the curve representing the percentage of weight loss as a function of vibration time.
- the degree of attrition is and remains much smaller for the material that has been cycled through the compactor under a high temperature, than for the material cycled once at lower temperature.
- Two starting fluff materials have been compacted: - a pure high molecular weight high-density polyethylene (HDPE) having a HLMI of 2.2 g/10 min and a density of 0.953 g/cm 3 , and produced by chrome catalysis stabilised with an antioxidant package, - a blend of 90 wt% of the same high molecular weight high-density polyethylene and 10 wt% metallocene polyethylene (HDPE+mPE) having a HLMI of 26 g/10 min and a density of 0.934 g/cm 3 .
- the blend was obtained by dry blending without additional additivation.
- RDA ⁇ c represents the frequency of the cross-over point between the elastic and viscous viscosity curves
- RDA G c represents the viscosity at the cross-over point between the elastic and viscous viscosity curves.
- the compacted material is not degraded by the compaction and it keeps its HLMI, contrary to the extruded material that has a much smaller HLMI value.
- the dynamic rheology test also exhibits a low degree of degradation for the agglomerated material in clear contrast with the extruded pellets prepared either with the laboratory polyethylene or with the plant polyethylene.
- the agglomerated fluff is suitable for many applications such as large barrels for carrying dangerous cargo, jerricans, drums or intermediate bulk containers (IBC).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02764622A EP1401624A2 (de) | 2001-07-02 | 2002-07-02 | Verdichtung von polyäthylenfusseln hoher dichte |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP01202536 | 2001-07-02 | ||
EP01202536A EP1273413A1 (de) | 2001-07-02 | 2001-07-02 | Verdichtung von Polyäthylenfusseln hoher Dichte |
PCT/EP2002/007358 WO2003004238A2 (en) | 2001-07-02 | 2002-07-02 | High density polyethylene fluff compaction |
EP02764622A EP1401624A2 (de) | 2001-07-02 | 2002-07-02 | Verdichtung von polyäthylenfusseln hoher dichte |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1401624A2 true EP1401624A2 (de) | 2004-03-31 |
Family
ID=8180576
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01202536A Withdrawn EP1273413A1 (de) | 2001-07-02 | 2001-07-02 | Verdichtung von Polyäthylenfusseln hoher Dichte |
EP02764622A Withdrawn EP1401624A2 (de) | 2001-07-02 | 2002-07-02 | Verdichtung von polyäthylenfusseln hoher dichte |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01202536A Withdrawn EP1273413A1 (de) | 2001-07-02 | 2001-07-02 | Verdichtung von Polyäthylenfusseln hoher Dichte |
Country Status (4)
Country | Link |
---|---|
EP (2) | EP1273413A1 (de) |
JP (1) | JP2004533348A (de) |
AU (1) | AU2002328840A1 (de) |
WO (1) | WO2003004238A2 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ2013676A3 (cs) * | 2013-09-03 | 2015-03-11 | Polymer Institute Brno, Spol. S R. O. | Polyolefinový prášek, způsob jeho výroby a použití |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1470850A (en) * | 1972-12-01 | 1977-04-21 | Allied Chem | Moulding poder |
DE3405185C2 (de) * | 1984-02-14 | 1987-02-26 | Plüss-Staufer AG, Oftringen, Aargau | Vorrichtung zur Herstellung von Kompaktlingen aus Polymeren und Additiven |
JPS61501695A (ja) * | 1984-03-29 | 1986-08-14 | アメリカン ヘキスト コ−ポレイシヨン | 改良されたポリエチレン成形組成物およびその製法 |
US5484620A (en) * | 1990-12-22 | 1996-01-16 | Schenk-Filterbau Gesellschaft Mit Beschrankter Haftung | Method of manufacturing stabilizing and/or filtering aids for use in the processing of liquids, especially beverages |
AU662202B2 (en) * | 1992-02-24 | 1995-08-24 | Montell North America Inc. | Polyolefin compositions having good transparency and impact resistance |
DE4210351A1 (de) * | 1992-03-30 | 1993-10-07 | Hoechst Ag | Verfahren zum Pelletieren von ultrahochmolekularem Polyethylen |
DE4211529A1 (de) * | 1992-04-06 | 1993-10-07 | Herding Entstaubung | Filterelement mit einem formstabilen, durchlässig-porösen Kunststoff-Formkörper |
SG70124A1 (en) * | 1997-09-26 | 2000-01-25 | Gen Electric | Method for making thermoplastic resin pellets |
-
2001
- 2001-07-02 EP EP01202536A patent/EP1273413A1/de not_active Withdrawn
-
2002
- 2002-07-02 WO PCT/EP2002/007358 patent/WO2003004238A2/en not_active Application Discontinuation
- 2002-07-02 EP EP02764622A patent/EP1401624A2/de not_active Withdrawn
- 2002-07-02 JP JP2003510231A patent/JP2004533348A/ja active Pending
- 2002-07-02 AU AU2002328840A patent/AU2002328840A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO03004238A3 * |
Also Published As
Publication number | Publication date |
---|---|
WO2003004238A3 (en) | 2003-03-27 |
WO2003004238A2 (en) | 2003-01-16 |
JP2004533348A (ja) | 2004-11-04 |
EP1273413A1 (de) | 2003-01-08 |
AU2002328840A1 (en) | 2003-01-21 |
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