WO2005054315A1 - Copolymere d'ethylene - Google Patents

Copolymere d'ethylene Download PDF

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Publication number
WO2005054315A1
WO2005054315A1 PCT/EP2004/012484 EP2004012484W WO2005054315A1 WO 2005054315 A1 WO2005054315 A1 WO 2005054315A1 EP 2004012484 W EP2004012484 W EP 2004012484W WO 2005054315 A1 WO2005054315 A1 WO 2005054315A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene copolymer
catalyst
silica
iso
escr
Prior art date
Application number
PCT/EP2004/012484
Other languages
English (en)
Inventor
Lada Kurelec
Godefridus Arnoldus Henricus Nooijen
Kathleen Ann Vandewiele
Robert Harm Groeneboom
Thomas Maria Gerardus Aarts
Matthijs Kessel Van
Antonius Bernardus Johannes Kroezen
Rutgerus Antonie Jacobus Postema
Peter Tackx
Original Assignee
Sabic Polyethylenes B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP03078768.3A external-priority patent/EP1535937A1/fr
Application filed by Sabic Polyethylenes B.V. filed Critical Sabic Polyethylenes B.V.
Publication of WO2005054315A1 publication Critical patent/WO2005054315A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers

Definitions

  • the invention relates to an ethylene copolymer having a density higher than 940 kg/m 3 .
  • the invention also relates to an olefin polymerisation process for the preparation of ethylene copolymers having a density higher than 940 kg/m 3 by polymerising ethylene and at least one olefin comonomer having between three and ten carbon atoms per molecule in a single reactor in the presence of a silica-supported chromium-containing catalyst and an alkyl- containing promoter
  • high density polyethylene homopolymer and copolymer is rather tough at room temperature.
  • HDPE high density polyethylene
  • ESCR Environmental Stress Crack Resistance
  • a pre-crack leads to stress concentration, which results in the formation of the deformation zone (or yield zone).
  • This zone consists of miniscule cavities (voids), which will grow and join up to form an essentially fibrillar structure usually referred to as craze.
  • the fibrils within a craze will extend over time until a failure criterion is satisfied and consequently the material will fail.
  • This process of fibrillar extension and subsequent weakening is generally accepted to be a rate-determining step controlling the overall slow crack propagation in polyethylene. This step is governed by the disentanglement process of (tie) molecules. The more tie molecules present, the more stress can be supported and consequently the higher the resistance against a chain detaching from a crystal.
  • the ability of releasing a chain from a crystal will also highly depend on crystal strength, which is determined by the crystal's perfection and thickness. Given this slow crack propagation mechanism in polyethylene, the molecular parameters leading to high ESCR are the same parameters which will lead to an increased number of tie molecules. On the other hand it is desirable that the finished products also retain desirable stiffness, which is predominantly determined by crystallinity and/or crystal size. The two requirements for the desired molecular structure (high crystallinity and a large number of tie molecules) are conflicting as the formation of an increased number of tie molecules will result in lower crystallinity (i.e. lower stiffness). Polyethylene having a lower density possesses a higher ESCR.
  • the density of polyethylene may be controlled by the addition of an -olefine, which leads to products possessing short chain branching.
  • the incorporation of short chain branches will enhance ESCR by forcing molecules to crystallize in different lamellar crystals and consequently leads to an increased number of tie molecules. This is especially the case if short chain branches are predominantly incorporated in the long molecular chains.
  • the comonomers may be incorporated in the low molar mass tail and their amount will decrease with increasing molar mass values.
  • HLMI high-load melt index
  • the density is between 945 kg/m 3 and 956 kg/m 3 .
  • the density is between 945 kg/m 3 and 956 kg/m 3 and the HLMI/MI ratio is between 5 and 8.
  • the density is between 950 kg/m 3 and 955 kg/m 3 .
  • the ESCR is between 100 and 500 hours and more preferred between 120 and 250 hours.
  • the high- load melt index is between 2 and 15 g/10 min. and more preferred between 6 and 1 1 g/10 min. According to a further preferred embodiment of the invention the high-load melt index is between 7 and 10 g/10 min. According to a preferred embodiment of the invention the die swell at 1600 s "1 is lower than 3.6. According to a preferred embodiment of the invention M w / M n is between 29 and 45.
  • the single reactor ethylene copolymer is characterised with the following properties: a density of between 950 and 955 kg/m 3 , an ESCR of between 120 and 250 hours, - a high-load melt index (HLMI) between 7 and 10 g/10 min., a die swell at 1600 s "1 lower than 3.6 and M w / M n between 29 and 45.
  • the ethylene copolymer according to the present invention has a unique combination of ESCR and die swell properties.
  • the copolymer according to the invention possesses a superior
  • ESCR in comparison with the commercially available products in the same density range.
  • An olefin polymerization process for the preparation of polyethylene takes place in the presence of a catalyst.
  • the selection of this catalyst is most important because the physical properties, in particular the mechanical properties, of a polyethylene resin depend amongst others upon the applied catalyst system. Different catalyst systems will result in different molecular weight distributions in the polyethylene obtained.
  • the chromium-containing catalysts also referred to as a "Phillips catalyst”
  • the chromium-containing catalysts may enable the production of polyethylene having desirable physical and rheological properties.
  • a chromium-containing catalyst contains a support.
  • the support is a silica with a large surface area (SA ), typically larger than 200 m 2 /g, and a large pore volume (PV) , typically larger than 0.8 cm 3 /g.
  • SA surface area
  • PV large pore volume
  • the support may be modified so as to include cogels such as for example silica-titania or silica-alumina and by the replacement of silica by alumina or amorphous aluminium phosphates.
  • the support may comprise a tergel which is produced by mixing a chromium source with the silica and titania compound.
  • the chromium-containing catalyst may also be doped with chemical compounds containing for example aluminium, titanium, phosphorus, boron or fluor by impregnation of the porous chromium-containing supports with solutions of such compounds.
  • chemical compounds containing for example aluminium, titanium, phosphorus, boron or fluor by impregnation of the porous chromium-containing supports with solutions of such compounds.
  • modified chromium-containing catalyst systems to improve the properties of the polyethylene.
  • the present invention also relates to the olefin polymerization process for the preparation of the ethylene copolymers by polymerizing ethylene and at least one olefin comonomer having between three and ten carbon atoms per molecule in a single reactor in the presence of a silica-supported chromium- containing catalyst and an alkyl-containing promoter.
  • the invention is characterised in that the silica-supported chromium-containing catalyst is an unmodified silica-supported chromium catalyst having an average pore diameter (PD) larger than 15 nanometers and in that the specific surface area is at least 550 m 2 /gram.
  • the unmodified silica-supported chromium catalyst is a silica- supported chromium-containing catalyst that does not contain titanium, aluminium, phosphorus, boron or fluor. (There may be present very small amounts as a result of trace impurities in the production process of the catalyst but there are no metals present which have been added)
  • the polymerization of ethylene takes place in a diluent at a temperature of between 90°C and 1 10°C.
  • Suitable diluents include, for example, isobutane and propane.
  • the polymerization may also take place in a gas-phase process.
  • the average pore diameter is between 16 and 20 nanometers and more preferably between 16 and 18 nanometers.
  • the amount of chromium in the catalyst is generally at least
  • the average particle size (D 50 ) of the catalyst is between 50 and 150 micrometers.
  • the catalyst is activated before being applied in the polymerization reaction.
  • the activation may take place under different conditions.
  • the activation generally takes place at an elevated temperature, for example, at a temperature above 450°C.
  • the activation may take place in different atmospheres, for example in dry air.
  • the activation takes place at least partially under an inert atmosphere preferably consisting of nitrogen. At the same time the temperature is raised slowly. It has been found to be advantageous to change from the nitrogen atmosphere to an atmosphere of dry air at a temperature of at most 700°C.
  • the alkyl-containing promoter is an alkyl boron compound.
  • the alkyl boron compound is triethyl boron. If triethyl boron is used as a promoter, generally the boron concentration in the polymerization reactor is at least about 0.25 ppm of boron based on the diluent. Preferably, the concentration is at least 0.30 ppm of boron and more preferably the concentration is at least 0.40 ppm boron.
  • the polymerization takes place in the presence of a comonomer with 3 to 10 carbon atoms such as for example propylene, 1 -butene, 1-pentene, 1- hexene and/or 1 -octene.
  • a comonomer with 3 to 10 carbon atoms such as for example propylene, 1 -butene, 1-pentene, 1- hexene and/or 1 -octene.
  • Preferred comonomers are 1 -butene and 1 -hexene. Comparison of the ESCR of a copolymer with 1 -hexene and the
  • ESCR of a copolymer with 1 -butene indicates that the ESCR of a copolymer with 1 -hexene is generally higher than the ESCR of a copolymer with 1 -butene which conclusion is with respect to HDPE most prominently for the range between 940 and 950 kg/m 3 .
  • the product according to the invention possesses unique ESCR and die swell properties in comparison with the commercially available products in the same density range.
  • the high ESCR values are attributed to the presence of the favourable morphology having high density of tie molecules. Creation of such morphology is a consequence of the unique molecular structure, namely comonomer incorporation, which is unusual for the heterogeneous catalyst systems used in a single reactor system.
  • FIG. 1 is a cumulative TREF (temperature rising elution fractionation) plot comparing three grades having a density of 952 kg/m 3 : 1. a polymer according the invention, designated as 1 , 2. a polymer produced with a state of the art chromium containing catalyst, designated as 2; and 3. a polymer produced in a two-stage reactor, designated as 3.
  • TREF temperature rising elution fractionation
  • the X-axis represents the elution temperature (°C) and the Y-axis represents IR signal/total area.
  • the products according to the present invention possess the highest amount of the branched material, as evidenced by the shoulder in the temperature range from 80°C to 90°C.
  • the amount of the fraction between 80°C and 90°C, which corresponds to the branching degree between 5-10 CH 3 /1000C, is highest for the polymer according to the present invention.
  • the chemical composition distribution (CCD) has been determined by TREF according to the method of Wild ( Advances in Polymer Science 98, Springer- Verlag Heidelberg, 1990).
  • the total comonomer incorporation (short chain branching) per fraction was measured by NMR.
  • the single reactor chromium catalyst-based ethylene copolymers according to the present invention may be extruded or blow-moulded into articles such as for example bottles, containers, fuel tanks and drums, or may be extruded or blown into films.
  • the ethylene copolymers according to the present invention may be used to produce for example bottles and jerry cans having for example a capacity of between 1 and 30 litres, composite packages with plastic receptacles for household and industrial chemicals and dangerous goods.
  • the ethylene copolymers according to the present invention are highly suited for use in the production of containers.
  • the ethylene copolymers according to the invention may be combined with additives such as for example lubricants, fillers, stabilizers, antioxidants, compatibilizers and pigments.
  • the additives used to stabilize the copolymers may be, for example, additive packages including hindered phenols, phosphites, antistatics and stearates.
  • US-A-6174981 and US-A 6465586 describe a polymerisation process for ethylene and comonomers in the presence of a catalyst system comprising chromium supported on a silica-titania support and a trialkylboron compound.
  • the present invention is directed to the polymerisation of ethylene and an olefin comonomer in the presence of an unmodified silica-supported chromium wherein the unmodified silica-supported chromium catalyst is a silica-supported chromium-containing catalyst that does not contain any amounts of titanium.
  • US-A- 6465586 discloses a boron concentration in the polymerization reactor between 0,01 and 0,20 ppm of boron based on the diluent whereas in the present invention preferably, the boron concentration in the polymerization reactor is at least 0.25 ppm of boron , and more preferably at least 0,30 ppm of boron, based on the diluent.
  • the invention will be elucidated by means of the following non- limiting examples.
  • the characteristics of polyethylene obtained in the examples l-lll were determined as follows: - The high-load melt index (HLMI) of polyethylene was measured according to ISO 1133 on pellets at 190°C with a test weight of 21.6 kg and the melt index (Ml) was measured according to ISO 1133 on pellets at 190°C with a test weight of 10.0 kg The density of polyethylene was measured according to ISO 1183 (with additional annealing step) (30' boiling and cooling in water). The crack resistance of polyethylene was measured by the Environmental Stress Cracking Resistance ESCR according to the DSM test method STAC 100-1106. This method was performed at elevated temperature (75 ⁇ 0.3°C) in a surfactant (Rhodacal DS10; 5 g/l).
  • HLMI high-load melt index
  • Ml melt index
  • the density of polyethylene was measured according to ISO 1183 (with additional annealing step) (30' boiling and cooling in water).
  • the crack resistance of polyethylene was measured by the Environmental Stress Cracking Resistance ES
  • Plates having well defined dimensions were subjected to a stress lower than the yield stress (3 N/mm 2 ).
  • the sample in powdered or granular form
  • the samples for the ESCR measurement were punched out of the pressed plate (dimensions: 6.5 x 12.7 x 1 mm).
  • the samples were notched in the middle (parallel with the short edges) with the notching apparatus (notch through the sample). Notch length was 1.95 ⁇ 0.02 mm.
  • the test was performed on four samples and the average value was reported. The time recorded as an ESCR value is the time needed for the material to fracture.
  • the polydispersity of polyethylene is defined as M w /M n .
  • M w and M n were determined by size exclusion chromatography (SEC) measurement. See pages 242-244 of "Handbook of Polyethylene, structure, properties and applications " (by Andrew Peacock, Dekker, New York , 2000)
  • SEC size exclusion chromatography
  • Dextmdate diameter of extrudate right below the die streng [mm]
  • Die swell (SR) 2 - 1
  • the chemical composition distribution (CCD) was determined by TREF according to the method of Wild (Advances in Polymer Science 98, Springer- Verlag Heidelberg, 1990).
  • Example I Ethylene and 1 -butene were copolymerized in a liquid-filled 5-liter continuous stirred tank reactor (CSTR) in isobutane at 4.6 MPa in the presence of an unmodified silica supported chromium catalyst supplied by PQ Corporation.
  • CSTR liquid-filled 5-liter continuous stirred tank reactor
  • the catalyst was characterised as follows: The pore volume of the catalyst was 2.65 cm 3 /g and the surface area was 610 m 2 /g. The catalyst contained 1.1 wt% of chromium.
  • the catalyst was activated in a fluid bed in dry air (water content less than 1 ppm) at 550°C for 4 hours. During the activation procedure nitrogen was used instead of air at temperatures lower than 320 °C. Triethylboron (TEB) was used as a promoter.
  • TEB Triethylboron
  • the polyethylene powder was stabilized with 1500 ppm of Irganox B225 and 500 ppm of PEG 9000 and pelletized in a twin-screw extruder at 245 °C.
  • the polyethylene pellets had the following characteristics: density : 952.3 kg/m 3 ESCR: 128 hours high-load melt index: 8.7 g/10 min. die swell 1600 s "1 : 3.00 M w / M n : 40
  • Example II Ethylene and 1-butene were copolymerized in a liquid-filled 5- liter CSTR in isobutane at 4.6 MPa in the presence of the silica supported chromium catalyst according to Example I.
  • the catalyst was activated in a fluid bed in dry air (water content less than 1 ppm) at 550°C for 4 hours. During the activation procedure nitrogen was used instead of air at temperatures lower than 320 °C.
  • Triethylboron (TEB) was used as a promoter.
  • Isobutane (2781 g/h), ethylene (1254 g/h), hydrogen (0.54 g/h), TEB (52 g/h of 200 ppm solution) and 1 -butene (20.2 g/h) were continuously fed to the reactor at 101.0 °C.
  • the catalyst feed to the reactor was controlled in order to maintain a constant ethylene concentration in the reactor of 9.7 mol%.
  • the polymer yield was 1105 g/h.
  • the catalyst activity (determined by XRF analysis of the polymer) was 2300 grams of polyethylene powder per gram of catalyst.
  • the polyethylene powder was stabilized with 1500 ppm of Irganox B225 and 500 ppm of PEG 9000 and pelletized in a twin-screw extruder at 245°C.
  • the polyethylene pellets had the following characteristics: density : 952.5 kg/m 3 ESCR: 204 hours high-load melt index: 8.5 g/10 min. die swell 1600 s "1 3.45 - M w / M n : 44
  • Example III Ethylene and 1 -butene were copolymerized in a liquid-filled 5- liter CSTR in isobutane at 4.6 MPa in the presence of the catalyst applied in Example II.
  • This catalyst was activated in a fluid bed in dry air (water content less than 1 ppm) at 550°C for 2 hours. During the activation procedure nitrogen was used instead of air at temperatures lower than 320 °C.
  • Triethylboron (TEB) was used as a promoter. Isobutane (2774 g/h), ethylene (1245 g/h), hydrogen (1.78 g/h),
  • TEB 25 g/h of 200 ppm solution
  • 1 -butene 28.6 g/h
  • the catalyst feed to the reactor was controlled in order to maintain a constant ethylene concentration in the reactor of 13.2 mol%.
  • the polymer yield was 1036 g/h.
  • the catalyst activity (determined by XRF analysis of the polymer) was 2850 grams of polyethylene powder per gram of catalyst.
  • the polyethylene powder was stabilized with 1500 ppm Irganox B225 and 500 ppm PEG 9000 and pelletized in a twin-screw extruder at 245°C.
  • the polyethylene pellets had the following characteristics: density : 952.2 kg/m 3 ESCR : 144 hours high-load melt index: 9.0 g/10 min die swell 1600 s "1 : 3.20 M w / M n : 35

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un copolymère d'éthylène ayant: une densité supérieure à 940 kg/m3 (selon ISO1183), un ESCR supérieur à 100 heures (selon méthode DSM STAC 100-1106), un indice de fluidité en charge élevée (HLMI) inférieur à 30 g/10 min (selon ISO 1133), un gonflement à la filière à 1600 s-1 inférieur à 4 (selon ISO 11443) et MW / Mn d'au moins 28 (selon la chromatographie par filtration sur gel). L'invention porte également sur un procédé de polymérisation d'oléfines permettant la préparation des copolymères d'éthylène par polymérisation de l'éthylène et d'au moins un comonomère oléfinique possédant entre trois et dix atomes de carbone par molécule dans un réacteur unique en présence d'un catalyseur de chrome non modifié supporté par la silice don't le diamètre de pore moyen est supérieur à 15 nanomètres et ayant une superficie spécifique d'au moins 550 m2/gramme.
PCT/EP2004/012484 2003-11-28 2004-11-01 Copolymere d'ethylene WO2005054315A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP03078768.3 2003-11-28
EP03078768.3A EP1535937A1 (fr) 2003-11-28 Copolymère d' éthyléne

Publications (1)

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WO2005054315A1 true WO2005054315A1 (fr) 2005-06-16

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007088000A1 (fr) * 2006-01-31 2007-08-09 Basell Polyolefine Gmbh Procede de preparation de polymeres d'ethylene pour films souffles
EP1992658A1 (fr) * 2006-02-15 2008-11-19 Mitsui Chemicals, Inc. Agent modificateur de resistance a la rupture sous contrainte environnementale et composition de resine modifiee en resistance a la rupture sous contrainte environnementale le contenant
WO2010063444A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de fûts avec couvercle amovible
WO2010063443A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de fûts avec couvercle hermétique
WO2010063445A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de gros contenants intermédiaires
US8039564B2 (en) 2007-10-26 2011-10-18 Pq Silicas Uk Limited Catalyst precursor particles, their preparation and use
CN108610440A (zh) * 2016-12-13 2018-10-02 中国石油天然气股份有限公司 烯烃聚合催化剂及其制备方法
CN112679641A (zh) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 中空制品用聚乙烯树脂及其组合物和制备方法
WO2023056208A1 (fr) * 2021-09-30 2023-04-06 Exxonmobil Chemical Patents Inc. Auxiliaires de transformation de polymère sans fluor comprenant des polyéthylènes glycols

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174981B1 (en) * 1998-12-17 2001-01-16 Phillips Petroleum Company Polymerization process
US6465586B2 (en) * 1999-11-12 2002-10-15 Mcdaniel Max P. Polymerization catalyst and process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174981B1 (en) * 1998-12-17 2001-01-16 Phillips Petroleum Company Polymerization process
US6465586B2 (en) * 1999-11-12 2002-10-15 Mcdaniel Max P. Polymerization catalyst and process

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101384626A (zh) * 2006-01-31 2009-03-11 巴塞尔聚烯烃股份有限公司 制备用于吹塑薄膜的乙烯聚合物的方法
WO2007088000A1 (fr) * 2006-01-31 2007-08-09 Basell Polyolefine Gmbh Procede de preparation de polymeres d'ethylene pour films souffles
US8022124B2 (en) 2006-01-31 2011-09-20 Basell Polyolefine Gmbh Process for preparation of ethylene polymers for blown films
EP1992658A4 (fr) * 2006-02-15 2011-04-06 Mitsui Chemicals Inc Agent modificateur de resistance a la rupture sous contrainte environnementale et composition de resine modifiee en resistance a la rupture sous contrainte environnementale le contenant
EP1992658A1 (fr) * 2006-02-15 2008-11-19 Mitsui Chemicals, Inc. Agent modificateur de resistance a la rupture sous contrainte environnementale et composition de resine modifiee en resistance a la rupture sous contrainte environnementale le contenant
US8039564B2 (en) 2007-10-26 2011-10-18 Pq Silicas Uk Limited Catalyst precursor particles, their preparation and use
WO2010063443A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de fûts avec couvercle hermétique
WO2010063445A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de gros contenants intermédiaires
WO2010063444A1 (fr) * 2008-12-04 2010-06-10 Saudi Basic Industries Corporation Polyéthylène pour la fabrication de fûts avec couvercle amovible
EA019273B1 (ru) * 2008-12-04 2014-02-28 Сауди Бейсик Индастриз Корпорейшн Полиэтилен для изготовления герметичных барабанов
EA019272B1 (ru) * 2008-12-04 2014-02-28 Сауди Бейсик Индастриз Корпорейшн Полиэтилен для изготовления бочек с открытым верхом
EA023829B1 (ru) * 2008-12-04 2016-07-29 Сауди Бейсик Индастриз Корпорейшн Полиэтилен для изготовления контейнеров средней грузоподъемности для массовых грузов
CN108610440A (zh) * 2016-12-13 2018-10-02 中国石油天然气股份有限公司 烯烃聚合催化剂及其制备方法
CN112679641A (zh) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 中空制品用聚乙烯树脂及其组合物和制备方法
CN112679641B (zh) * 2019-10-18 2023-01-20 中国石油化工股份有限公司 中空制品用聚乙烯树脂及其组合物和制备方法
WO2023056208A1 (fr) * 2021-09-30 2023-04-06 Exxonmobil Chemical Patents Inc. Auxiliaires de transformation de polymère sans fluor comprenant des polyéthylènes glycols
US12018142B2 (en) 2021-09-30 2024-06-25 Exxonmobil Chemical Patents Inc. Fluorine-free polymer processing aids including polyethylene glycols

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