ES2529033T3 - Uso de polietileno para preparación de artículos rotomoldeados - Google Patents

Uso de polietileno para preparación de artículos rotomoldeados Download PDF

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Publication number
ES2529033T3
ES2529033T3 ES03729978.1T ES03729978T ES2529033T3 ES 2529033 T3 ES2529033 T3 ES 2529033T3 ES 03729978 T ES03729978 T ES 03729978T ES 2529033 T3 ES2529033 T3 ES 2529033T3
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Prior art keywords
ind
substituted
system based
articles
polyethylene resin
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Expired - Lifetime
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ES03729978.1T
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English (en)
Inventor
Eric Maziers
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TotalEnergies Onetech Belgium SA
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Total Research and Technology Feluy SA
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Priority claimed from EP02076658A external-priority patent/EP1357135A1/en
Priority claimed from EP02027878A external-priority patent/EP1428841A1/en
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • 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
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • 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
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Moulding By Coating Moulds (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Uso de una resina de polietileno polimerizada con un sistema catalítico basado en un componente de bistetrahidroindenil- metaloceno de fórmula R"(Ind)2MQ2, en la que (Ind) es un indenilo hidrogenado, sustituido o no sustituido, R" es un puente estructural entre los dos indenilos para impartir estereorrigidez que comprende un radical alquileno C1-C4, un dialquilgermanio o silicio o siloxano, o un radical alquilfosfina o amina, estando el puente sustituido o no sustituido, Q es un radical hidrocarbilo que tiene de 1 a 20 átomos de carbono o un halógeno, y M es un metal de transición del grupo IVb o vanadio, para producir artículos rotomoldeados que tienen al menos una de las propiedades siguientes: - deformación reducida - mejor dispersión de burbujas en artículos rotomoldeados espumados - microestructura muy fina - brillo mejorado - impermeabilidad mejorada a disolventes en comparación con artículos rotomoldeados que consisten esencialmente en resina de polietileno polimerizada con un sistema catalítico basado en Ziegler-Natta u otros componentes catalíticos de metaloceno.

Description

imagen1
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imagen10
E03729978
28-01-2015
-muestras 3 y 4: máquina Wedco con diferentes granulometrías
-muestras 5 y 6: máquina Palman HI con diferentes granulometrías.
Todos los molidos se llevaron a cabo con el rendimiento más alto para cada máquina con producciones en el intervalo de 800 a 1200 kg/h. La resina R9 fue fácil de moler y el molido alcanzó el estado estacionario después de
5 aproximadamente 30 minutos en vez de las dos a tres horas necesarias para resinas convencionales. No se observaron problemas de electricidad estática. El análisis de granulometría para estas 6 muestras se representa en la figura 9, que representa la fracción másica del polvo expresada en porcentaje en función del tamaño de partícula expresada en micrómetros.
La influencia de la granulometría de los polvos en la procesabilidad se estudió después para estas mismas 6
10 muestras, siendo el factor más importante el proceso de densificación resultante de la eliminación de las burbujas. Los resultados se representan en la figura 10, que representa el número de burbujas por mm2 remanentes en la resina fundida en función de la temperatura expresada en °C para las seis muestras. De forma bastante sorprendente, las resinas que tenían el tamaño de partícula más grande representaron la tasa más alta de eliminación de burbujas en función del aumento de la temperatura.
15 Las resinas R1, R7, R9, R11 y R12 se sometieron a ensayo para la producción de microgránulos. Se usaron tres tipos de máquinas (Gala, BKG, Black Clawson) y las condiciones de granulación para cada máquina se resumen en la Tabla VII.
TABLA VII
Máquina 1
Máquina 2 Máquina 3
Resina
R9 R1 R12 R9 R1 R11 R9 R7
Microgránulos
<Deq> (μm)
700 600 650 525 525 470 600 550
Producción (kg/h)
60 80 60 100 100 100 3 4
Rendimiento (%)
65 95 95 95 95 95 <50 <50
Agua residual
no no no sí sí sí ní sí
Granulación
Tipo de extrusora
Tornillos gemelos: 60 mm Tornillos gemelos: 75 mm Tornillos gemelos: 50,8 mm
Bomba de fusión
sí sí sí sí sí sí no no
Número de agujeros
300 300 300 2200 2200 2200 520 520
Diámetro de los agujeros (μm)
400 400 400 300 300 300 350 350
Longitud de los agujeros
3 3 3 - - - 1.5 1.5
Número de cuchillas
18 18 18 6 6 6 6 6
Resina
R9 R1 R12 R9 R1 R11 R9 R7
Configuración
DA1 DA DA DA DA DA AA2 AA
Condiciones
T del molde de fusión (ºC)
228 236 242 240 249 240 250 250
Presión en el molde (MPa)
13 14,9 17,4 16,3 18,6 19,8 110 130
Velocidad de las cuchillas (rpm)
3590 3595 3585 3600 3600 3600 3400 3400
T del agua (ºC)
75 74 79 73 71 66 18 18
Caudal del agua (m3/h)
20 20 20 10 10 10 - -
Presión del agua (kPa)
- - - - - - 68 68
Rendimiento/agujero (kg/h)
0,2 0,267 0,2 0,045 0,045 0,045 0,006 0,006
Velocidad de cizallamiento/agujero (s-1)
12000 15900 12000 6450 6450 6450 470 700
Fractura de fusión
no sí sí no sí sí no sí
DA1: debajo del agua AA2: anillo de agua
20
A partir de la Tabla VII puede concluirse que, en todos los tipos de máquinas, la resina R9 se convirtió en microgránulos a una presión del molde inferior y a una temperatura del molde de fusión inferior que otras resinas sometidas a ensayo y las operaciones de estado estacionario se establecieron después de 30 minutos. Además, R9 no mostró ninguna fractura de fusión incluso a una velocidad de cizallamiento alta de 12000 s-1.
25 Debe indicarse también que las resinas de alta viscosidad R11 y R12 se convirtieron fácilmente en microgránulos incluso aunque tenían un índice de fluidez muy bajo. Las distribuciones de tamaño para varias resinas y máquinas se representan en la figura 11, que representa la fracción másica de los microgránulos expresada en porcentaje en función del tamaño de partícula expresada en micrómetros. Las muestras de microgránulos se representan en la
12
imagen11

Claims (1)

  1. imagen1
ES03729978.1T 2002-04-26 2003-04-23 Uso de polietileno para preparación de artículos rotomoldeados Expired - Lifetime ES2529033T3 (es)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
EP02076658A EP1357135A1 (en) 2002-04-26 2002-04-26 Rotomoulded articles with dimensional stability
EP02076658 2002-04-26
EP02079264 2002-10-15
EP02079264 2002-10-15
EP02027878 2002-12-12
EP02027878A EP1428841A1 (en) 2002-12-12 2002-12-12 Rotomoulded articles with dimensional stability
PCT/EP2003/004698 WO2003091294A1 (en) 2002-04-26 2003-04-23 Rotomoulded articles prepared with polyethylene

Publications (1)

Publication Number Publication Date
ES2529033T3 true ES2529033T3 (es) 2015-02-16

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ES03729978.1T Expired - Lifetime ES2529033T3 (es) 2002-04-26 2003-04-23 Uso de polietileno para preparación de artículos rotomoldeados

Country Status (10)

Country Link
US (2) US20050255264A1 (es)
EP (1) EP1499648B1 (es)
JP (1) JP2005523954A (es)
KR (1) KR101011168B1 (es)
CN (2) CN102443209B (es)
AU (1) AU2003240600A1 (es)
DK (1) DK1499648T3 (es)
ES (1) ES2529033T3 (es)
SI (1) SI1499648T1 (es)
WO (1) WO2003091294A1 (es)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005077994A1 (en) * 2004-02-13 2005-08-25 Total Petrochemicals Research Feluy Process for improving the co-polymerization of ethylene and an olefin co-monomer in a polymerization loop reactor.
EP1659136A1 (en) * 2004-11-19 2006-05-24 Total Petrochemicals Research Feluy Solid state properties of polyethylene prepared with tetrahydroindenyl-based catalyst system
EP1721931A1 (en) * 2005-05-09 2006-11-15 Total Petrochemicals Research Feluy mono-layer rotomoulded articles prepared from blends comprising polyethylene
EP1721739A1 (en) * 2005-05-09 2006-11-15 Total Petrochemicals Research Feluy Bi-layer rotomoulding applications
EP1854609A1 (en) * 2006-05-09 2007-11-14 Total Petrochemicals Research Feluy Coloured rotomoulded articles
EP1862288A1 (en) * 2006-05-29 2007-12-05 Total Petrochemicals Research Feluy Optimisation in rotomoulded applications.
HU226837B1 (hu) 2006-05-31 2009-12-28 Semmelweis Egyetem Folyadéksugárral mûködõ deszorpciós ionizációs eljárás és eszköz
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EP2199078A1 (en) * 2008-12-22 2010-06-23 Total Petrochemicals Research Feluy Polyethylene and poly(hydroxy carboxylic acid) multilayer films
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KR101309389B1 (ko) * 2011-06-28 2013-09-17 삼성토탈 주식회사 열수축 필름용 폴리에틸렌 수지 조성물 및 열수축 필름
CN104105722B (zh) * 2011-12-14 2016-11-09 英尼奥斯欧洲股份公司 聚合物
EP3699950A1 (en) 2011-12-28 2020-08-26 Micromass UK Limited Collision ion generator and separator
US10995203B2 (en) * 2016-07-21 2021-05-04 Exxonmobil Chemical Patents Inc. Rotomolded compositions, articles, and processes for making the same
KR101862928B1 (ko) 2016-09-05 2018-05-30 한화토탈 주식회사 선형 중밀도 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품
CN114729080A (zh) * 2019-11-14 2022-07-08 埃克森美孚化学专利公司 气相聚乙烯共聚物
US11746220B2 (en) 2020-06-12 2023-09-05 Braskem S.A. High flow rotomolding compositions, processes thereof, and articles therefrom

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Also Published As

Publication number Publication date
WO2003091294A1 (en) 2003-11-06
EP1499648B1 (en) 2014-11-05
KR20040106400A (ko) 2004-12-17
SI1499648T1 (sl) 2015-02-27
JP2005523954A (ja) 2005-08-11
CN1649912A (zh) 2005-08-03
CN102443209A (zh) 2012-05-09
EP1499648A1 (en) 2005-01-26
CN102443209B (zh) 2017-04-12
US20050255264A1 (en) 2005-11-17
US20120128908A1 (en) 2012-05-24
AU2003240600A1 (en) 2003-11-10
US8420194B2 (en) 2013-04-16
DK1499648T3 (en) 2015-02-09
KR101011168B1 (ko) 2011-01-26

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