AR111560A1 - Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones mixtas de catalizadores homogéneos - Google Patents

Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones mixtas de catalizadores homogéneos

Info

Publication number
AR111560A1
AR111560A1 ARP180100977A ARP180100977A AR111560A1 AR 111560 A1 AR111560 A1 AR 111560A1 AR P180100977 A ARP180100977 A AR P180100977A AR P180100977 A ARP180100977 A AR P180100977A AR 111560 A1 AR111560 A1 AR 111560A1
Authority
AR
Argentina
Prior art keywords
reactor
ethylene interpolymer
density
molecular weight
homogenal
Prior art date
Application number
ARP180100977A
Other languages
English (en)
Inventor
Hamidreza Khakdaman
Kenneth Taylor
Fazle Sibtain
Christopher Dobbin
Xiaochuan Wang
Charles Carter
Peter Zoricak
Qinyan Wang
Brian Molloy
Mehdi Keshtkar
Monika Kleczek
Niousha Kazemi
Zengrong Zhang
Stephen Salomons
Lawrence Vanasseldonk
Original Assignee
Nova Chem Int Sa
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
Application filed by Nova Chem Int Sa filed Critical Nova Chem Int Sa
Publication of AR111560A1 publication Critical patent/AR111560A1/es

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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
    • 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
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
    • 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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/05—Transitioning, i.e. transition from one catalyst to another with use of a deactivating agent
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/02—Low molecular weight, e.g. <100,000 Da.
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/05—Bimodal or multimodal molecular weight distribution
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/06—Comonomer distribution, e.g. normal, reverse or narrow
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/09—Long chain branches
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/10—Short chain branches
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/17—Viscosity
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • 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
    • C08F4/65927—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 two cyclopentadienyl rings being mutually bridged
    • 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
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/07—Long chain branching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Un proceso continuo de polimerización en solución en el que se emplean por lo menos dos formulaciones de catalizadores. Se emplea una primera formulación de catalizador homogéneo en un primer reactor para producir un primer interpolímero de etileno y se emplea una primera formulación de catalizador heterogéneo en un segundo reactor para producir un segundo interpolímero de etileno. Opcionalmente, en un tercer reactor se forma un tercer interpolímero de etileno. Los productos de interpolímeros de etileno que se obtienen como resultado poseen propiedades deseables en una variedad de aplicaciones de uso final, por ejemplo en aplicaciones en películas. Se divulga un medio para incrementar el peso molecular del primer interpolímero de etileno y/o un medio para incrementar la temperatura del primer reactor, con relación a una tercera formulación de catalizador homogéneo. Se divulga un medio para reducir la proporción en peso de (a-olefina / etileno) en el primer reactor y/o reducir la densidad del primer interpolímero de etileno, con relación a una tercera formulación de catalizador homogéneo.
ARP180100977A 2017-04-19 2018-04-17 Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones mixtas de catalizadores homogéneos AR111560A1 (es)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15/491,330 US10442921B2 (en) 2017-04-19 2017-04-19 Means for increasing the molecular weight and decreasing the density employing mixed homogeneous catalyst formulations

Publications (1)

Publication Number Publication Date
AR111560A1 true AR111560A1 (es) 2019-07-24

Family

ID=62089796

Family Applications (1)

Application Number Title Priority Date Filing Date
ARP180100977A AR111560A1 (es) 2017-04-19 2018-04-17 Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones mixtas de catalizadores homogéneos

Country Status (11)

Country Link
US (2) US10442921B2 (es)
EP (1) EP3612574A1 (es)
JP (1) JP6913762B2 (es)
KR (1) KR102259584B1 (es)
CN (1) CN110831986A (es)
AR (1) AR111560A1 (es)
AU (1) AU2018254206A1 (es)
BR (1) BR112019021958B1 (es)
CL (1) CL2019002997A1 (es)
PE (1) PE20200030A1 (es)
WO (1) WO2018193331A1 (es)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10538654B2 (en) * 2017-04-19 2020-01-21 Nova Chemicals (International) S.A. Multi reactor solution polymerization, polyethylene and polyethylene film
US20190135960A1 (en) * 2017-11-07 2019-05-09 Nova Chemicals (International) S.A. Process to manufacture ethylene interpolymer products
US10995166B2 (en) * 2017-11-07 2021-05-04 Nova Chemicals (International) S.A. Ethylene interpolymer products and films
US10683376B2 (en) * 2017-11-07 2020-06-16 Nova Chemicals (International) S.A. Manufacturing ethylene interpolymer products at higher production rate
KR102133030B1 (ko) * 2017-12-18 2020-07-10 주식회사 엘지화학 올레핀 중합체, 이의 제조 방법, 그리고 이를 이용한 필름
US11555084B2 (en) * 2017-12-26 2023-01-17 Dow Global Technologies Llc Multimodal ethylene-based polymer processing systems and methods
US11603452B2 (en) * 2017-12-26 2023-03-14 Dow Global Technologies Llc Multimodal ethylene-based polymer compositions having improved toughness
JP7326283B2 (ja) 2017-12-26 2023-08-15 ダウ グローバル テクノロジーズ エルエルシー マルチモーダルエチレン系ポリマーの製造のための二重反応器溶液プロセス
EP3732216B1 (en) * 2017-12-26 2023-04-19 Dow Global Technologies LLC Process for the production of multimodal ethylene-based polymers
SG11202005779SA (en) * 2017-12-26 2020-07-29 Dow Global Technologies Llc Compositions comprising multimodal ethylene based polymers and low density polyethylene (ldpe)
US10654949B2 (en) * 2018-02-22 2020-05-19 Exxonmobil Chemical Patents Inc. High molecular weight functionalized olefin copolymer quenching agent
US11198747B2 (en) 2018-06-04 2021-12-14 Exxonmobil Chemical Patents Inc. Catalyst systems including two hafnocene catalyst compounds
MX2021006758A (es) * 2018-12-18 2021-07-15 Nova Chem Int Sa Peliculas de multiples capas.
US11987655B2 (en) * 2018-12-21 2024-05-21 Lg Chem, Ltd. Polyolefin
KR102394383B1 (ko) 2018-12-21 2022-05-04 주식회사 엘지화학 폴리올레핀
US11046843B2 (en) 2019-07-29 2021-06-29 Nova Chemicals (International) S.A. Ethylene copolymers and films with excellent sealing properties
US11667777B2 (en) 2019-10-04 2023-06-06 Chevron Phillips Chemical Company Lp Bimodal polyethylene copolymers
KR20220165756A (ko) * 2020-05-08 2022-12-15 노바 케미컬즈 (인터내셔널) 소시에테 아노님 독특한 용융 흐름 고유 점도 지수(mfivi) 및 낮은 불포화도를 갖는 에틸렌 혼성중합체 생성물
CN116234871A (zh) * 2020-09-30 2023-06-06 博里利斯股份公司 用于生产在线混合的聚合物的设备和方法
KR20230130025A (ko) * 2021-01-28 2023-09-11 셰브론 필립스 케미컬 컴퍼니 엘피 이봉 폴리에틸렌 공중합체
CN116917404A (zh) 2021-02-24 2023-10-20 诺瓦化学品(国际)股份有限公司 双峰聚乙烯组合物
BR112023017190A2 (pt) 2021-03-08 2023-09-26 Nova Chem Int Sa Plastômeros com rápidas taxas de cristalização
BR112023017679A2 (pt) 2021-03-19 2023-09-26 Nova Chem Int Sa Composição de polietileno para orientação biaxial
CN117015463A (zh) 2021-03-19 2023-11-07 诺瓦化学品(国际)股份有限公司 高密度聚乙烯组合物
CN117222523A (zh) 2021-04-14 2023-12-12 诺瓦化学品(国际)股份有限公司 双轴取向的膜

Family Cites Families (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2302305A1 (fr) 1975-02-28 1976-09-24 Charbonnages Ste Chimique Procede perfectionne de polymerisation et de copolyme
JPS5783538A (en) 1980-11-12 1982-05-25 Kyowa Chem Ind Co Ltd Polyolefin composition and agent thereof
GB8610126D0 (en) 1986-04-25 1986-05-29 Du Pont Canada Isopropanolamines
US4731438A (en) 1986-12-30 1988-03-15 Union Carbide Corporation Water treatment method for resin in a purge vessel
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5382630A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution
US5382631A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions
US5571880A (en) 1991-05-09 1996-11-05 Phillips Petroleum Company Organometallic fluorenyl compounds and use thereof in an alpha-olefin polymerization process
US5525695A (en) 1991-10-15 1996-06-11 The Dow Chemical Company Elastic linear interpolymers
US5278272A (en) 1991-10-15 1994-01-11 The Dow Chemical Company Elastic substantialy linear olefin polymers
US5206075A (en) 1991-12-19 1993-04-27 Exxon Chemical Patents Inc. Sealable polyolefin films containing very low density ethylene copolymers
CA2125780C (en) 1991-12-30 2004-07-06 Deepak R. Parikh Ethylene interpolymer polymerizations
ATE148905T1 (de) 1992-09-16 1997-02-15 Exxon Chemical Patents Inc Weiche filme mit verbesserten physikalischen eigenschaften
US6313240B1 (en) 1993-02-22 2001-11-06 Tosoh Corporation Process for producing ethylene/α-olefin copolymer
US5408004A (en) 1993-08-17 1995-04-18 The Dow Chemical Company Polyolefin blends and their solid state processing
US5773106A (en) 1994-10-21 1998-06-30 The Dow Chemical Company Polyolefin compositions exhibiting heat resistivity, low hexane-extractives and controlled modulus
US7153909B2 (en) 1994-11-17 2006-12-26 Dow Global Technologies Inc. High density ethylene homopolymers and blend compositions
US5767208A (en) 1995-10-20 1998-06-16 Exxon Chemical Patents Inc. High temperature olefin polymerization process
EP0889912B1 (en) 1996-03-27 2000-07-12 The Dow Chemical Company Highly soluble olefin polymerization catalyst activator
JPH09309926A (ja) 1996-05-17 1997-12-02 Dow Chem Co:The エチレン共重合体の製造方法
CN1076731C (zh) * 1996-08-12 2001-12-26 中国石油化工集团公司 复合型限定几何构型金属茂催化剂、其制备及应用
BR9713050A (pt) 1996-11-13 2000-04-04 Dow Chemical Co Filme contrátil e método para fazer um filme contrátil.
GB9712663D0 (en) 1997-06-16 1997-08-20 Borealis As Process
ES2236921T3 (es) 1997-08-15 2005-07-16 Dow Global Technologies, Inc. Peliculas producidas a partir de composiciones de polimeros de olefina homogeneas, esencialmente lineales.
US6441116B1 (en) 1997-09-03 2002-08-27 Idemitsu Kosan Co., Ltd. Ethylenic copolymer, composition containing said copolymer, and ethylenic copolymer film
ATE258958T1 (de) 1997-09-19 2004-02-15 Dow Chemical Co Ethylen-kopolymer-mischungen mit enger molekulargewichtsverteilung und optimierter zusammensetzung, verfahren zu ihrer herstellung und ihre verwendung
US6242545B1 (en) 1997-12-08 2001-06-05 Univation Technologies Polymerization catalyst systems comprising substituted hafinocenes
GB9800245D0 (en) 1998-01-07 1998-03-04 Bp Chem Int Ltd Novel polymers
CA2227674C (en) 1998-01-21 2007-04-24 Stephen John Brown Catalyst deactivation
ES2198098T3 (es) 1998-03-09 2004-01-16 Basell Poliolefine Italia S.P.A. Procedimiento multietapas para la polimerizacion de olefinas.
CA2586497A1 (en) 1998-03-12 1999-09-16 Ineos Europe Limited Polymerisation catalysts comprising a pyridine-bis(imine) complex
GB9806407D0 (en) 1998-03-25 1998-05-20 Bp Chem Int Ltd Novel polymer compositions
CA2247703C (en) 1998-09-22 2007-04-17 Nova Chemicals Ltd. Dual reactor ethylene polymerization process
EP0989140A1 (en) * 1998-09-25 2000-03-29 Fina Research S.A. Production of multimodal polyethylene
US6300433B1 (en) 1998-10-23 2001-10-09 Exxonmobil Chemical Patents Inc. Olefin copolymerization process with bridged hafnocenes
US6486088B1 (en) 1998-10-23 2002-11-26 Exxonmobil Chemical Patents Inc. High activity carbenium-activated polymerization catalysts
WO2000024822A1 (fr) 1998-10-23 2000-05-04 Mitsui Chemicals, Inc. Copolymere d'ethylene et son procede de production, composition de resine comprenant ledit copolymere et utilisations dudit copolymere d'ethylene et de ladite composition de resine
US6392076B1 (en) 1999-03-10 2002-05-21 Colorado State University Research Foundation Weakly coordinating anions containing polyfluoroalkoxide ligands
EP1041113A1 (en) 1999-03-30 2000-10-04 Fina Research S.A. Polyolefins and uses thereof
DE60041397D1 (de) 1999-05-05 2009-03-05 Ineos Europe Ltd Ethylencopolymere und daraus hergestellte filme
TW495527B (en) 1999-07-30 2002-07-21 Sumitomo Chemical Co Ethylene polymer and resin composition for producing cast film, and process for producing cast film
CA2379607A1 (en) 1999-09-29 2001-04-05 E.I. Du Pont De Nemours And Company Manufacture of polyethylenes
CN100434433C (zh) * 1999-10-08 2008-11-19 三井化学株式会社 茂金属化合物及制备方法、烯烃聚合催化剂、聚烯烃及制备方法
US7041617B2 (en) 2004-01-09 2006-05-09 Chevron Phillips Chemical Company, L.P. Catalyst compositions and polyolefins for extrusion coating applications
US7125933B2 (en) 2000-06-22 2006-10-24 Univation Technologies, Llc Very low density polyethylene blends
MY137183A (en) * 2001-03-16 2009-01-30 Dow Global Technologies Inc Method of making interpolymers and products made therefrom
CA2343662C (en) * 2001-04-11 2010-01-05 Nova Chemicals Corporation Plastic films
KR100895729B1 (ko) 2001-08-31 2009-04-30 다우 글로벌 테크놀로지스 인크. 다봉 분자량 분포를 갖는 폴리에틸렌 물질
EP1546252B1 (en) 2002-10-01 2010-03-03 ExxonMobil Chemical Patents, Inc. a Corporation of the State of Delaware Polyethylene compositions for injection molding
US7396881B2 (en) 2002-10-01 2008-07-08 Exxonmobil Chemical Patents Inc. Polyethylene compositions for rotational molding
CN101372520B (zh) * 2003-11-20 2010-12-08 联合碳化化学及塑料技术有限责任公司 喷雾干燥的混合金属齐格勒催化剂组合物
US6870010B1 (en) 2003-12-01 2005-03-22 Univation Technologies, Llc Low haze high strength polyethylene compositions
US7193017B2 (en) 2004-08-13 2007-03-20 Univation Technologies, Llc High strength biomodal polyethylene compositions
US7868092B2 (en) 2005-06-14 2011-01-11 Univation Technologies, Llc Bimodal polyethylene compositions for blow molding applications
US7439306B2 (en) 2004-11-23 2008-10-21 Exxonmobil Chemical Patents Inc. Polyethylene blends with improved Vicat softening point
CN101155841B (zh) 2005-02-09 2011-06-08 英尼奥斯欧洲有限公司 共聚物及其薄膜
BRPI0609825B1 (pt) * 2005-03-17 2023-05-16 Dow Global Technologies Inc Composição e artigo
US7858702B2 (en) 2005-06-14 2010-12-28 Univation Technologies, Llc Enhanced ESCR bimodal HDPE for blow molding applications
CN101316889B (zh) 2005-11-28 2012-09-05 巴塞尔聚烯烃股份有限公司 适用于制备膜的聚乙烯组合物及其制备方法
JP2009001780A (ja) 2007-05-18 2009-01-08 Sumitomo Chemical Co Ltd エチレン系重合体組成物およびフィルム
US8475898B2 (en) 2007-08-29 2013-07-02 Equistar Chemicals, Lp Polyolefin resin blends for crack-resistant pipe
US8101685B2 (en) 2008-12-15 2012-01-24 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom
US8410217B2 (en) 2008-12-15 2013-04-02 Exxonmobil Chemical Patents Inc. Thermoplastic polyolefin blends
US20120028866A1 (en) * 2010-07-28 2012-02-02 Sudhin Datta Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers
EP2387590B2 (en) 2009-12-18 2019-12-25 Total Research & Technology Feluy Method for replacing compatible ethylene polymerization catalysts
US9085650B2 (en) 2009-12-18 2015-07-21 Total Research & Technology Feluy Method for replacing incompatible ethylene polymerization catalysts
JP2013523974A (ja) * 2010-04-05 2013-06-17 ダウ グローバル テクノロジーズ エルエルシー 高分子量画分を含むオレフィン系ポリマーを凝縮及び超凝縮モードで重合するための方法
CA2846637C (en) 2011-08-30 2020-08-04 Chevron Phillips Chemical Company Lp Hyperbranched polymers and methods of making and using same
US9266977B2 (en) 2012-12-21 2016-02-23 Exxonmobil Chemical Patents Inc. Bridged metallocene compounds, catalyst systems and processes for polymerization therewith
US9751998B2 (en) 2012-12-27 2017-09-05 Dow Global Technologies Llc Catalyst systems for olefin polymerization
US9540459B2 (en) 2013-03-12 2017-01-10 Mitsui Chemicals, Inc. Production method of olefin polymer and olefin polymerization catalyst
US9181370B2 (en) * 2013-11-06 2015-11-10 Chevron Phillips Chemical Company Lp Low density polyolefin resins with low molecular weight and high molecular weight components, and films made therefrom
US9217049B2 (en) 2013-11-19 2015-12-22 Chevron Phillips Chemical Company Lp Dual catalyst systems for producing polymers with a broad molecular weight distribution and a uniform short chain branch distribution
US10167355B2 (en) * 2014-04-17 2019-01-01 Borealis Ag Catalyst system for producing polyethylene copolymers in a high temperature solution polymerization process
EP3209721B1 (en) * 2014-10-21 2021-09-22 Nova Chemicals (International) S.A. Continuous solution polymerization process
CA2868640C (en) * 2014-10-21 2021-10-26 Nova Chemicals Corporation Solution polymerization process
WO2016063205A2 (en) * 2014-10-21 2016-04-28 Nova Chemicals (International) S.A. Dilution index
US10442920B2 (en) 2017-04-19 2019-10-15 Nova Chemicals (International) S.A. Means for increasing the molecular weight and decreasing the density of ethylene interpolymers employing homogeneous and heterogeneous catalyst formulations

Also Published As

Publication number Publication date
CN110831986A (zh) 2020-02-21
BR112019021958B1 (pt) 2022-12-13
US10442921B2 (en) 2019-10-15
KR102259584B1 (ko) 2021-06-03
EP3612574A1 (en) 2020-02-26
WO2018193331A1 (en) 2018-10-25
CL2019002997A1 (es) 2020-02-14
US20200056024A1 (en) 2020-02-20
JP6913762B2 (ja) 2021-08-04
BR112019021958A2 (pt) 2020-05-05
KR20190137156A (ko) 2019-12-10
AU2018254206A1 (en) 2019-10-31
US11015044B2 (en) 2021-05-25
US20180305532A1 (en) 2018-10-25
JP2020517770A (ja) 2020-06-18
PE20200030A1 (es) 2020-01-09

Similar Documents

Publication Publication Date Title
AR111560A1 (es) Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones mixtas de catalizadores homogéneos
AR111477A1 (es) Medios para incrementar el peso molecular y reducir la densidad de los interpolímeros de etileno mediante el empleo de formulaciones de catalizadores homogéneos y heterogéneos
AR111607A1 (es) Polimerización en solución en reactor múltiple
AR111605A1 (es) Polimerización en solución en múltiples reactores, polietileno y películas de polietileno
BR112016019327A2 (pt) Método para polimerizar olefinas para produzir um polímero de poliolefina com uma distribuição de composição multimodal
MX2017008336A (es) Polietileno para tuberias.
BR112013022111A2 (pt) Processo para preparar homopolímero ou copolímero de etileno na presença de iniciador de polimerização de radical livre e pelo menos um agente de transferência de cadeia em reator tubular, homopolímero ou copolímero de etileno obtenível por tal processo, seu uso e processo para revestimento por extrusão de substrato
CO6620039A2 (es) Composiciones de catalizador para producir poliolefinas de alt mz/mw
BR112018009278A2 (pt) polimerizações de radicais livres de alta pressão
EA201700261A1 (ru) Полимерные композиции и изделия с экструзионным покрытием
BR112013030650A2 (pt) processo para preparar um pró-catalisador multimetálico, pró-catalisador, catalisador de polimerização, polímero de polietileno, composição e artigo
BR112018009036A2 (pt) polimerizações via radicais livres a alta pressão para produzir polímeros à base de etileno
CL2020001200A1 (es) Un proceso mejorado para fabricar productos de interpolímero de etileno.
CL2020001204A1 (es) Fabricación de productos de interpolímero de etileno a una mayor tasa de producción.
BR112014002692A8 (pt) catalisadores para a preparação de polietileno de ultra-alto peso molecular (uhmwpe)
AR101445A1 (es) Procesos para preparar polímeros basados en etileno que utilizan una distribución de monóxido de carbono
AR116141A1 (es) CATALIZADOR QUE CONTIENE Ni PARA LA OLIGOMERIZACIÓN DE OLEFINAS
BR112017011278A2 (pt) polímero multifásico como um espessante e agente de suspensão
CL2018001658A1 (es) Formulaciones de polietileno parcialmente reticulado y métodos para obtenerlas.
AR104981A1 (es) Proceso continuo para producir polioles de poliéter que tienen un elevado contenido de óxido de etileno polimerizado, mediante el uso de un complejo catalizador de cianuro de metal doble y un compuesto metálico de la serie de lantanida o metal del grupo 3 - grupo 15, magnesio
BR112019015629B8 (pt) Composição de copolímero de etileno curável por peróxido, método para produzir uma composição de copolímero de etileno curável por peróxido, produto de copolímero de etileno/alfa-olefina reticulado, artigo fabricado, condutor revestido e método de conduzir eletricidade
BR112015026427A2 (pt) polímeros à base de etileno e artigos feitos do mesmo
BR112018014896A2 (pt) catalisadores e métodos para produzir propileno a partir de etileno e buteno
CO2017011814A2 (es) Composición de resina para recubrimiento por extrusión
AR102954A1 (es) Una estructura de capa múltiple, un método para producir la misma, y un envasado que comprende la misma

Legal Events

Date Code Title Description
FB Suspension of granting procedure