[go: up one dir, main page]

WO1998033842A1 - Procede de reaction de polyolefines avec des hydrosilanes - Google Patents

Procede de reaction de polyolefines avec des hydrosilanes Download PDF

Info

Publication number
WO1998033842A1
WO1998033842A1 PCT/NL1998/000058 NL9800058W WO9833842A1 WO 1998033842 A1 WO1998033842 A1 WO 1998033842A1 NL 9800058 W NL9800058 W NL 9800058W WO 9833842 A1 WO9833842 A1 WO 9833842A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyolefin
reaction
prearm
group
polyhydrosilane
Prior art date
Application number
PCT/NL1998/000058
Other languages
English (en)
Inventor
Koen Jan Gerarda Janssen
Wilhelmus Gerardus Marie Bruls
Theodoor Wilhelm Leonard Rauch
Michel Paul Van Boggelen
Gerardus Arnoldus Rademarkers
Original Assignee
Dsm N.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
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to AU58841/98A priority Critical patent/AU5884198A/en
Publication of WO1998033842A1 publication Critical patent/WO1998033842A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G

Definitions

  • This invention relates to branched polyolefin polymers, and more specifically to a process for use in the production of branched polyolefin polymers compri- sing a silicon containing polymeric backbone with branches extending therefrom in which the branches are formed of polyolefins wherein the branched polymers are produced by a hydrosilation reaction between polyolefin prearms with a hydrosilane containing compound.
  • X is a heteroatom, such as O, P, S, N, Si or one or more carbon atoms either as part of an aliphatic or aromatic group and R is hydrogen or an organic group .
  • polyhydro-siloxanes derived from an alkylhydrosiloxane end-capped with either a hydrosilane functionality or an alkylsilane functionality.
  • Such compounds have the general formula:
  • R x to R 7 is each independently hydrogen or an organic group; preferably, R x and R 2 can be either alkyl, aryl or cycloalkyl; R 3 can be either hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; R 4 is hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; R 5 and R 6 are alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy and R 7 is hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; n is an integer having a minimum value of about 10, and preferably 25 or higher.
  • Such polyhydrosiloxanes are commonly available from a number of companies including Dow Corning and Rhone Poulenc.
  • the branched polymers utilizing a hydrosilane- containing backbone are prepared by reacting one or more of the hydrosilanes with a polyolefin prearm preferably containing terminal unsaturation, either in the form of vinyl, vinylidene, vinylene groups and mixtures thereof, in the presence of a suitable catalyst wherein the silicon-hydrogen bond adds across the double bond of the prearm. That reaction can be illustrated for those prearms containing terminal vinylidene unsaturation according to the following equation:
  • EP represents the remainder of the polyolefin pre-arm.
  • hydrosilation reaction can be carried out in the presence of a solvent along with a catalyst to promote the reaction.
  • Suitable hydrosilation catalysts to effect that addition reaction are known in the art and include compounds of metals from Groups 8 to 10 of the Periodic Table, typically catalysts based on palladium, platinum or nickel.
  • the concepts of the present invention reside in a method for carrying out in dilute solution or in bulk the reaction of a hydrosilane-containing silicon polymer with a polyolefin prearm containing ethylenic unsaturation in the presence or absence of an acce- lerator for the preparation of branched polyolefin polymers, wherein the polyolefin arms become attached to a silicon polymer as the backbone to form a highly branched polymer in the form of a star, comb, nanogel and structural combinations thereof.
  • the polyolefin prearms containing ethylenic unsaturation are reacted with a compound containing a plurality of hydrosilane groups in the presence of a catalyst to promote the addition of the Si-H groups across the ethylenic unsaturation of the polyolefin and optionally in the presence of an accelerator for that reaction. It has been found that, reaction times can be significantly reduced for both the dilute solution reaction and the bulk reaction provided the catalyst is dosed to, that is, it is mixed with, the reaction mixture containing polyolefin prearms and polyhydrosilane at elevated temperatures.
  • the reaction can be carried out efficiently and at significantly reduced reaction times under both dilute solution or bulk reaction conditions.
  • the term "bulk reaction conditions” refers to and includes a reaction of either a solid or a liquid polyolefin prearm polymer either in the absence of a solvent or in the presence of limited quantities of solvent.
  • concentration of polyolefin prearm in the solvent is at least 10% by weight, preferably at least 50% by weight, and most preferably 75% by weight or higher.
  • the reaction is carried out in the presence of a hydrosilation catalyst, and preferably a catalyst containing a metal from Groups 8 to 10 of the Periodic Table.
  • Typical catalysts are based on palladium, platinum, nickel, rhodium or cobalt.
  • Accelerators used in the practice of this invention are preferably halogenated organic compounds including trichloroacetic acid esters, hexachloro- acetone, hexachloropropylene, trichlorotoluene or perchlorocrotonic acid esters. Such compounds promote or accelerate the reaction between the ethylenic unsaturation in the prearm and the Si-H group in the silicon containing polymeric backbone in the preparation of branched polymers.
  • the accelerators effectively increase the coupling efficiency of both the bulk reaction and the conventional more diluted reaction in solvent.
  • the reaction can be carried out as desired in high intensity mixing devices such as melt processing equipment like a Banbury mixer or an extruder or reactors such as a Haake high intensity mixer or like equipment for blending solid and semi-solid reactants.
  • high intensity mixing devices such as melt processing equipment like a Banbury mixer or an extruder or reactors such as a Haake high intensity mixer or like equipment for blending solid and semi-solid reactants.
  • the polyolefin prearms can be efficiently reacted with a polyhydrosilane containing silicon polymer to produce a branched polyolefin polymer to form a star, comb, nanogel and structural combinations thereof with an increased reaction rate when the catalyst or a combination of catalyst and accelerator are added to the mixture of polymers at elevated temperatures, in the range of 80 to 350 °C.
  • reaction in accordance with the practice of this invention is far more efficient as compared to prior art processes.
  • polyolefin prearms containing ethylenic unsaturation are reacted with a polymeric backbone polymer containing Si-H groups whereby the Si-H groups add across the ethylenic unsaturation to form a branched polyolefin polymer in the form of a comb, star, nanogel or structural combinations thereof as described in the foregoing co-pending applications Serial No. 08/511,402 filed August 4, 1995 and Serial No. 08/683,518 filed July 12, 1996.
  • polyolefin prearm refers to a polyolefin polymer containing ethylenic unsaturation, preferably at its terminus or within the terminating monomeric unit, so that it can react with the Si-H bond of the silicon- containing backbone. That ethylenic unsaturation is preferably one of vinyl, vinylidene or vinylene unsaturation. Terminal ethylenic unsaturation is preferred to reduce steric effects resulting from reaction between two polymeric molecules.
  • polyolefin prearms which can be used in the practice of the present invention depend in large measure on the properties desired in the branched polyolefin polymer. In most embodiments, it is generally preferred, that the polyolefin prearm be formed of a polyolefin containing terminal unsaturation in the form of either vinyl, vinylidene, vinylene, or mixtures thereof. Use can be made of polyolefin homopolymers, such as polyethylene and polypropylene, but it is also possible, and sometimes preferred, to employ copolymers of one or more 1- alkenes or to employ copolymers of one or more 1-alkenes with other unsaturated monomers copolymerizable therewith.
  • polyolefin prearms formed by copolymerization of ethylene and propylene or ethylene and/or propylene with at least one other 1-alkene.
  • polyenes which either may or may not be functionalized.
  • comonomers in the formation of the polyolefin prearms are functionalized ethylenically unsaturated monomers in which the functional group may be one or more polar groups capable of undergoing metallocene catalyzed polymerization.
  • the polyolefin prearms used in the practice of the present invention refer to and include polymers of l-alkenes generally, and preferably ethylene/ propylene copolymers or copolymers of ethylene and propylene with other 1-alkenes, as well as copolymers formed by the interpoly erization of ethylene, 1-alkenes and at least one other polyene monomer.
  • Such polymers are themselves well known to those skilled in the art and are typically prepared by using conventional Ziegler or metallocene polymeriza- tion techniques well known to those skilled in the art . Both types of polymers hereinafter collectively are referred to as EP(D)M.
  • propylene is a preferred monomer for copolymerization with ethylene and optionally a diene monomer
  • the use of such higher 1-alkenes together with or in place of propylene are well known to those skilled in the art and include, particularly, 1-butene, 1-hexene and 1-octene.
  • polyene monomers When using an interpolymer of ethylene, 1-alkene and a polyene monomer, use can be made of a variety of polyene monomers known to those skilled in the art containing two or more carbon-to-carbon double bonds containing 4 to 20 carbon atoms, including non-cyclic polyene monomers, monocyclic polyene monomers and polycyclic polyene monomers.
  • Representative of such compounds include 1, 4-hexadiene, dicyclopentadiene, bicyclo (2, 2, l)hepta-2 , 5-diene, commonly known as norbornadiene, as well as the alkenyl norbornenes wherein the alkenyl group contains 1 to 20 carbon atoms and preferably 1 to 12 carbon atoms . Examples of some of the latter compounds includes 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, vinyl norbornene as well as alkyl norbornadienes .
  • a functional ethylenically unsatura- ted monomer typically contain 2 to 20 carbon atoms and contain an ethylenically unsaturated group.
  • Preferred functional ethylenically unsaturated monomers include acrylate and methacrylate esters wherein the ester group is Cj . to C 20 alkyl or C 6 to C 25 aryl including substituted aryl, vinyl amines, vinyl- cyano compounds and vinyl esters.
  • suitable functional monomers which can be used in the practice of the present invention include methylmeth- acrylate, methylacrylate, N-vinylamine, N-vinylpyri- dine, acrylonitrile, vinylacetate, etc.
  • the polyolefin prearm is produced using metallocene catalysts.
  • metallocene catalyst system refers to and includes the use of a transition metal compound comprising a metal from Groups 3 to 6 of the Periodic Table such as titanium, zirconium, chromium, hafnium, yttrium containing at least one coordinating ligand that is a highly conjugated organic compound (e.g., cyclopenta- dienyl or indenyl) .
  • Phillips catalyst systems One such example is titanium chloride supported on magnesium chloride and used in high temperature (above 100°C) polymerization systems. Another example is the copolymerization of ethylene with higher 1-alkenes using V0C1 3 and diethylaluminum chloride.
  • the choice of catalyst system and polymerization conditions will depend on the specific type of polyolefin prearm desired, as known to those skilled in the art of Ziegler-Natta polymerization technology.
  • the composition of the arms are dependent on the limits of Ziegler-Natta polymerization technology and can be controlled independent of the composition of the backbone.
  • the concepts of the present invention also may employ polyolefins derived from conjugated dienes which contain ethylenic unsaturation.
  • polyolefins can be described as homopolymers of conjugated dienes containing 4-8 carbon atoms (such as butadiene, isoprene and chloroprene) , and copolymers of those monomers with one or more vinyl monomers copolymerizable therewith.
  • polyolefin prearms which can be reacted in accordance with the concepts of the present invention are polybutadiene polymers .
  • the properties of the polyolefin arms linked to the polymeric backbone dominate the properties of the resulting branched polymer.
  • the molecular weight of the polyolefin prearms can be varied to control the properties desired in the overall branched polymer.
  • the method of preparation of the prearms can be used to, in part, control over the properties of the arms.
  • the lengths of the arms expressed as the number-average molecular weight, M n , can be varied within broad limits, depending on the properties desired.
  • M n number-average molecular weight
  • the molecular weight distribution (MWD) referring to the ratio between the weight-average molecular weight (M w ) and the number-average molecular weight (M n ) as determined by size exclusion chromatograph-differential viscometry (SEC-DV) , of the arms be relatively narrow, that is in the range of at least 1.2 ranging up to 3.5 to improve efficiency of the coupling reaction.
  • SEC-DV size exclusion chromatograph-differential viscometry
  • broader MWD polyolefin prearms can be used and are often desired in the practice of this invention.
  • the number of double bonds in the polyolefin prearm decreases on a weight basis . That in turn results in a reduction of the coupling efficiency generally expressed as the percent of polyolefin prearms actually bonded to the polymeric backbone .
  • the number of repeating units with Si-H functionality capable of being coupled to a plurality of polyolefin prearms depends, to some degree, also on the intended application of the polymer.
  • the hydrosilane-containing polymeric backbone contains at least 4 functional Si-H groups through which polyolefin arms can be linked to form a branched structure.
  • a reactive polymeric backbone having the capability of forming at least 3 to 300 polyolefin arms linked to the polymeric backbone .
  • One suitable class of polymeric backbones used in the practice of the present invention are polyhydrosilane polymers and copolymers containing a large number of repeating units containing a silicon-hydrogen bond.
  • R wherein X is a group containing a heteroatom, such as 0, P, S, N, Si and/or one or more carbon atoms either as part of an aliphatic or aromatic group, and R is hydrogen or an organic group, and preferably hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy.
  • siloxanes derived from an alkylhydrosiloxane end-capped with either a hydrosilane functionality or an alkylsilane functionality.
  • Such siloxanes have the general formula:
  • R x to R 7 is each independently hydrogen or an organic group; preferably, R x , R 2 and R 3 can be either hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; R 4 is hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; R 5 and R 6 are alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy and R 7 is hydrogen, alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy; n is an integer having a minimum value of 4, preferably of 10 and more preferably 25 or higher.
  • Such polyhydrosiloxanes are commonly available from a number of companies including Dow Corning and Rhone Poulenc .
  • siloxane copolymers containing 10 or more and typically 10 to 80 silicon-hydrogen groups as repeating units.
  • suitable polyhydrosilane polymers are polymethylhydrosilane, polymethylhydro- siloxane, methylhydrodimethyl-siloxane copolymer, methylhydrophenylmethylsiloxane copolymer, methyl- hydrocyanopropylsiloxane copolymer, methylhydromethyl- octylsiloxane copolymer, poly (1, 2-dimethylsilazane) , (1-methylsilazane) (1, 2-dimethylsilazane) copolymer and methylhydrocyclosiloxane polymer.
  • silicon-containing polymer backbone having a number average molecular weight of 300 or higher, and preferably 300 to 10,000.
  • the reaction between the polyolefin prearm and the silicon-containing polymeric backbone is carried out under conditions of heat and a suitable catalyst to effect addition of the silicon hydride across the terminal unsaturation of the polyolefin prearm to link the arm to the silicon-containing polymeric backbone.
  • Suitable hydrosilation catalysts to effect that reaction are known in the art and contain metals from Groups 8 to 10 of the Periodic Table of the Elements. Such catalysts are described in Lukevics et al . in J. Organomet . Chem. Lib. 1977, 5, pages 1-80 and include compounds based on palladium, platinum, nickel, rhodium and cobalt. Hydrosilation catalysts which have been found to be particularly effective are
  • the hydrosilation catalyst may be dissolved in a suitable solvent to facilitate handling and measuring of the small amounts of metal catalyst usually employed.
  • suitable solvents include aromatic hydrocarbons (such as benzene, toluene, xylene) and/or polar solvents (such as alcohols, ketones, glycols and esters) . While the hydrosilation catalyst can be handled in suitable solvents, storage in those solvents, particularly at temperatures above ambient, results in deactivation of the metal catalyst.
  • D 4- Struktur C X n wherein X is a halogen atom, and preferably chlorine and bromine; D is a substituent which is hydrogen, halogen as described above, a halogenated alkyl, alkenyl, aryl, aralkyl or cycloalkyl group or a carboxy, carbonyl, oxycarbonyl or alkoxy containing group; and n is an integer from 1-4.
  • the accelerators have the general formula:
  • A is a phenyl group which may contain 1 or 2 halogen atoms or alkyl groups substituted thereon, or a thienyl, furyl pyrollyl, N-alkyl pyrollyl or a pyridyl group. Those groups are either bonded directly to the carbon atom or indirectly through a carbonyl group .
  • A can be a phenyl or benzyl group substituted with 1 or 2 nitro groups .
  • X is halogen and preferably chlorine or bromine and Y is halogen as described above, hydrogen or a ⁇ to C 8 hydrocarbon group.
  • Z is selected from any one of the following in which R' and R" are a hydrogen atom or a carbon group containing 1-8 carbon atoms :
  • m 1-8 and p is 0-8.
  • Preferred accelerators are those having the structure : Cl 0
  • the amount of accelerator employed in the practice of this invention depends on the quantity of hydrosilation catalyst employed and is generally ratioed in terms of moles of accelerator to moles of metal component in the hydrosilation catalyst. For reactions at 80 to 350 °C, generally it is convenient to employ molar ratios of accelerator to metal component of 0.01/1 to 100/1.
  • the accelerator is used in the practice of this invention, it is preferred to prepare, in a suitable solvent, a stock solution of the metal catalyst component and the accelerator for addition to the reaction vessel. It has been found that storage of the accelerator and catalyst in aromatic hydrocarbon solvents or aliphatic alcohol even at temperatures above ambient does not result in deactivation of the catalyst. Suitable solvents for preparation of the stock solution are aliphatic alcohols, aromatic alcohols, aliphatic ketones, esters or glycols.
  • the reaction between the polyolefin prearms and the hydrosilane-containing polymeric backbone can be carried out with far greater efficiency and shorter reaction times as compared to the prior art when the reaction is carried out as a bulk reaction and/or in the presence of the accelerator.
  • the term "bulk reaction” refers to a process in which the solid or liquid polyolefin prearms are reacted with the hydrosilane-containing polymer backbone in the presence of a minimum amount of solvent. It has been found that the reaction rate can be increased markedly when the concentration of polyolefin prearm in any solvent is at least 50%, and preferably at least 75%.
  • the reaction between the polyolefin prearms and the hydrosilane-containing polymeric backbone can be carried out in a batch or continuous high intensity mixing device such as various types of melt processing equipment including a Haake mixer, Banbury mixer, Brabender plasticord, an extruder or like blending equipment with little to no solvent employed.
  • the solvent can be a solvent for the polyolefin prearm such as aliphatic hydrocarbons (including pentane, hexane, heptane, pentamethylheptane or distillation fractions) ; aromatic hydrocarbons (such as benzene or toluene) ; halogenated derivatives of aliphatic or aromatic hydrocarbons (such as tetrachloroethylene) , or ethers (such as tetrahydrofuran or dioxane) .
  • aliphatic hydrocarbons including pentane, hexane, heptane, pentamethylheptane or distillation fractions
  • aromatic hydrocarbons such as benzene or toluene
  • halogenated derivatives of aliphatic or aromatic hydrocarbons such as tetrachloroethylene
  • ethers such as tetrahydrofuran or dioxane
  • the relative proportions of the polyolefin prearm and the polyhydrosilane are controlled to ensure that the desired number of polyolefin prearms become linked by the addition reaction to the polymeric backbone.
  • reaction temperature employed in the bulk reaction is generally higher than that frequently used in dilute solution reactions or prior art addition reactions of this type.
  • the use of generally higher temperatures is yet another factor which promotes the efficiency in the reaction.
  • temperatures ranging from about 100 to 350 °C can be used, and preferably 120 to 300 °C.
  • reaction time afforded by the process of the present invention is generally less than that required in prior processes.
  • reaction times are generally less than 10 hours, and preferably less than 4 hours.
  • the reaction time can be controlled within the range of 10 seconds to 240 minutes and preferably 10 seconds to 60 minutes.
  • A, B, C, E, F, G and I are ethylene/propylene copolymers prepared by solution polymerization with a metallocene type catalyst; D is Stamylan 7625 (registered trademark of DSM N.V. , the Netherlands) ; H is a low density polyethylene with a density of .966 g/cm 3 .
  • SEC-DV Size Exclusion Chromatography-Differential Viscometry
  • TSK Toyo Soda
  • M w weight average molecular weight
  • MWD M W /M n
  • the number of arms on the branched polyolefin polymers was defined as the ratio of the molecular weight at the top of the SEC-DV chromatogram of the branched polymer to the molecular weight at the top of the SEC-DV chromatogram of the original polyolefin prearm (the polyolefin before the coupling reaction) . Therefore, the number of arms as defined herein was the mean number of arms on the backbone for that experiment.
  • the coupling efficiency was determined from the SEC-DV chromatograms as the ratio of the molar mass distribution calculated for the branched polyolefin (in some cases after correction for residual prearm) to the molar mass distribution calculated for the polyolefin prearms, using curve fitting techniques known in the art for measuring molar mass distribution.
  • DCPAE dichlorophenylacetic acid ethylester
  • MCDPAE monochlorodiphenylacetic acid ethyl ester
  • IPA isopropylalcohol
  • SNO130 a paraffinic petroleum oil
  • Polymer I 10 gm ⁇ , dissolved in 100 ml PMH was mixed with HPCH dissolved in tetrahydrofuran at a molar ratio of 1000/1.
  • the reaction mixture was stirred at 140 °C for 14 days.
  • the branched polyolefin collected after evaporation of the solvent mixture at 80 °C under vacuum was analyzed by SEC-DV to contain 5 arms .
  • Comparative Experiment B The procedure of Comparative Experiment A was repeated except that the reaction mixture was stirred at 90 °C for 3 days.
  • the recovered branched polyolefin was analyzed by SEC-DV to contain 4 arms. The coupling efficiency was 85%.
  • Example I-IX demonstrate the use of an accelerator.
  • the accelerator and Pt catalyst were predissolved in IPA and charged as a stock solution.
  • Polymer A 10 gms, was dissolved in 100 ml of toluene in an agitated flask.
  • This reaction mixture was agitated at 130 °C for 24 hours, then blocked with an excess of 1-decene.
  • the branched polyolefin was recovered after evaporation of the solvent under vacuum at 80 °C and was analyzed by SEC-DV to contain 3 arms. The coupling efficiency was 82%.
  • Polymer F was dissolved in PMH at a concentration of 10 wt%.
  • Example III-IX were carried out in bulk, that is, as concentrated solutions or in the melt with an accelerator in the form of DCPAE.
  • Polymer C 70 gms, was dissolved in 100 ml of PMH.
  • the reaction mixture was stirred maintaining
  • Polymer F was dissolved in SNO-130 oil with PMHS and reacted according to the procedure of Example III. After addition of the catalyst at 130 °C, the reaction mixture was stirred an additional 20 minutes before blocking. Analysis of the oil solution by SEC-DV showed a polymer with M w of 210 kg/mol . The coupling efficiency was 83%.
  • Example III The procedure of Example III was repeated with the following exceptions: 40 gms of Polymer C were dissolved in 20 ml of PMH, the reaction mixture was heated to 150 °C prior to addition of the catalyst and accelerator. The molar ratio of DCPAE to Pt in the HPCH was 16. After addition of the DCPAE and HPCH solutions, the reaction mixture was stirred for an additional 5 minutes at 150 °C, then blocked with an excess of 1-decene. The branched polymer recovered after evaporation of the PMH under vacuum at 80 °C was analyzed by SEC-DV to contain 5 arms. The coupling efficiency was 96%.
  • This mixture was heated and agitated at 150 °C for 5.5 minutes, then blocked with an excess of 1-decene.
  • the branched polymer was analyzed by SEC-DV to contain 5 arms. The coupling efficiency was 90%.
  • Polymer B 10 gms, was heated and agitated in a flask like Example 1, but without solvent to 130 °C.
  • This mixture was stirred, maintaining 130 °C for 45 minutes.
  • the reaction was blocked with an excess 1-decene.
  • the branched polymer recovered from the reactor was analyzed by SEC-DV and contained 5 arms. The coupling efficiency was 86%.
  • Example IX - Coupling of Polymer D in an extruder Polymer D (melt index of 0.97 dg/min. @ 190 °C, 15) was treated with an IPA solution of PMHS in a Diosna mixing unit to provide a mixture containing 0.1 wt% PMHS in Polymer D.
  • This mixture was fed to a ZSK 30 mn/42F extruder at a speed of 4 kg/hr, simultaneously with an IPA solution of HPCH and DCPAE (4.3 mol/1 HPCH in IPA with a DCPAE to Pt ratio of 10/1) fed at 5 ml/min through a liquid injection port.
  • the temperature in the extruder was maintained at 180 °C and the screw speed was 100 rpm.
  • the branched polymer leaving the extruder was analyzed to have a melt index (190°C, 15) of 0.41 dg/min. and by SEC-DV to contain 4 arms.
  • the mixture was agitated at 150 °C for 6 minutes before blocking with decene.
  • the recovered branched polyolefin was analyzed by SEC-DV to have a M w of 720 kg/mol and to contain 7 arms. The coupling efficiency was 93%.
  • Example XI - Coupling of Polymer C at 50 wt% Solution The procedure of Example III was repeated with Polymer C and PMHS with the exception that no
  • DCPAE accelerator was added.
  • the HPCH in IPA was dosed to the reaction solution at 130 °C and the temperature held for 60 minutes before blocking.
  • the branched polyolefin recovered by evaporation of the solvent under vacuum at 80 °C was analyzed by SEC-DV to have 4 arms and a M w of 225 kg/mol. The coupling efficiency was 96%.
  • Example XII Coupling of Polymer A at 10 wt% Solution The procedure of Example I was repeated with
  • the temperature was maintained at 90°C with agitation for 23 hours, then the reaction was blocked.
  • the branched polyolefin recovered after evaporation of the solvent was analyzed by SEC-DV to contain 3 arms and to have a M w of 180 kg/mol.
  • the coupling efficiency was
  • Polymer G was l/l, the reaction temperature was 150 °C, and no DCPAE was used. The reaction mixture was maintained at 150 °C after charging the HPCH/IPA solution for 60 minutes before blocking. The branched polyolefin recovered from the reaction was analyzed by SEC-DV to have 6 arms. The coupling efficiency was 65%.
  • the reaction mixture was maintained at 150 °C with agitation for 3 minutes after charging the HPCH/IPA at 150 °C.
  • the coupling efficiency was 100%.
  • the branched polyolefin was analyzed by SEC-DV to have a M w of 160 kg/mole and was a mixture of branched and linear polyethylene because only 40% of Polymer H molecules had terminal ethylenic unsaturation.

Landscapes

  • 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)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Silicon Polymers (AREA)

Abstract

Ce procédé de préparation de polyoléfines à ramifications en forme de peigne, d'étoile, de nanogel ou de combinaisons de ces structures, consiste à faire réagir les pré-segments polyoléfiniques avec un polyhydrosilane, en présence d'un catalyseur d'hydrosilation que l'on ajoute en quantité mesurée et à une température élevée au mélange de réaction, afin de promouvoir l'addition de groupes Si-H dans l'insaturation éthylénique du pré-segment polyoléfinique. Le cas échéant, on peut exécuter le procédé de l'invention en présence d'un promoteur de réaction, afin de promouvoir la réaction d'hydrosilation.
PCT/NL1998/000058 1997-01-31 1998-01-28 Procede de reaction de polyolefines avec des hydrosilanes WO1998033842A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58841/98A AU5884198A (en) 1997-01-31 1998-01-28 Process for the reaction of polyolefins with hydrosilanes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79764797A 1997-01-31 1997-01-31
US08/797,647 1997-01-31

Publications (1)

Publication Number Publication Date
WO1998033842A1 true WO1998033842A1 (fr) 1998-08-06

Family

ID=25171430

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1998/000058 WO1998033842A1 (fr) 1997-01-31 1998-01-28 Procede de reaction de polyolefines avec des hydrosilanes

Country Status (2)

Country Link
AU (1) AU5884198A (fr)
WO (1) WO1998033842A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376512B2 (en) 2012-09-24 2016-06-28 Exxonmobil Chemical Patents Inc. Production of vinyl terminated polyethylene
US9434795B2 (en) 2012-09-24 2016-09-06 Exxonmobil Chemical Patents Inc. Production of vinyl terminated polyethylene using supported catalyst system
US9527933B2 (en) 2012-09-24 2016-12-27 Exxonmobil Chemical Patents Inc. Branched polyethylenes by hydrosilation grafting to improve processability of polyethylene
US11078335B2 (en) 2017-07-25 2021-08-03 Dow Silicones Corporation Method for preparing a graft copolymer with a polyolefin backbone and polyorganosiloxane pendant groups
US11193051B2 (en) 2018-03-19 2021-12-07 Dow Silicones Corporation Hot melt adhesive composition containing a polyolefin-polydiorganosiloxane copolymer and methods for the preparation and use thereof
US11332583B2 (en) 2018-03-19 2022-05-17 Dow Silicones Corporation Polyolefin-polydiorganosiloxane block copolymer and hydrosilylation reaction method for the synthesis thereof
US11702512B2 (en) 2018-07-17 2023-07-18 Dow Silicones Corporation Polysiloxane resin-polyolefin copolymer and methods for the preparation and use thereof
US11814555B2 (en) 2018-03-19 2023-11-14 Dow Silicones Corporation Hot melt adhesive compositions containing polyolefin-polydiorganosiloxane copolymers and methods for the preparation and use thereof
US12037462B2 (en) 2018-03-19 2024-07-16 Dow Global Technologies Llc Polyolefin-polydiorganosiloxane block copolymer and method for the synthesis thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451637A (en) * 1994-05-10 1995-09-19 Hercules Incorporated Organosilicon compositions prepared from unsaturated elastomeric polymers
WO1996020964A1 (fr) * 1994-12-30 1996-07-11 Novartis Ag Reseaux contenant du siloxane
WO1997006201A1 (fr) * 1995-08-04 1997-02-20 Dsm N.V. Polymeres ramifies avec branches polyolefiniques
EP0802216A1 (fr) * 1996-04-15 1997-10-22 DOW CORNING ASIA, Ltd. Copolymère de polypropylène et d'organopolysiloxane et procédé de sa préparation
EP0818525A2 (fr) * 1996-07-12 1998-01-14 DSM Copolymer, Inc. Polymères polyoléfiniques ramifiés, comme additifs dans des compositions d'huile lubrifiante et combustible

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5451637A (en) * 1994-05-10 1995-09-19 Hercules Incorporated Organosilicon compositions prepared from unsaturated elastomeric polymers
WO1996020964A1 (fr) * 1994-12-30 1996-07-11 Novartis Ag Reseaux contenant du siloxane
WO1997006201A1 (fr) * 1995-08-04 1997-02-20 Dsm N.V. Polymeres ramifies avec branches polyolefiniques
EP0802216A1 (fr) * 1996-04-15 1997-10-22 DOW CORNING ASIA, Ltd. Copolymère de polypropylène et d'organopolysiloxane et procédé de sa préparation
EP0818525A2 (fr) * 1996-07-12 1998-01-14 DSM Copolymer, Inc. Polymères polyoléfiniques ramifiés, comme additifs dans des compositions d'huile lubrifiante et combustible

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376512B2 (en) 2012-09-24 2016-06-28 Exxonmobil Chemical Patents Inc. Production of vinyl terminated polyethylene
US9434795B2 (en) 2012-09-24 2016-09-06 Exxonmobil Chemical Patents Inc. Production of vinyl terminated polyethylene using supported catalyst system
US9527933B2 (en) 2012-09-24 2016-12-27 Exxonmobil Chemical Patents Inc. Branched polyethylenes by hydrosilation grafting to improve processability of polyethylene
US11078335B2 (en) 2017-07-25 2021-08-03 Dow Silicones Corporation Method for preparing a graft copolymer with a polyolefin backbone and polyorganosiloxane pendant groups
US11193051B2 (en) 2018-03-19 2021-12-07 Dow Silicones Corporation Hot melt adhesive composition containing a polyolefin-polydiorganosiloxane copolymer and methods for the preparation and use thereof
US11332583B2 (en) 2018-03-19 2022-05-17 Dow Silicones Corporation Polyolefin-polydiorganosiloxane block copolymer and hydrosilylation reaction method for the synthesis thereof
US11814555B2 (en) 2018-03-19 2023-11-14 Dow Silicones Corporation Hot melt adhesive compositions containing polyolefin-polydiorganosiloxane copolymers and methods for the preparation and use thereof
US12037462B2 (en) 2018-03-19 2024-07-16 Dow Global Technologies Llc Polyolefin-polydiorganosiloxane block copolymer and method for the synthesis thereof
US11702512B2 (en) 2018-07-17 2023-07-18 Dow Silicones Corporation Polysiloxane resin-polyolefin copolymer and methods for the preparation and use thereof

Also Published As

Publication number Publication date
AU5884198A (en) 1998-08-25

Similar Documents

Publication Publication Date Title
EP0842213B1 (fr) Polymeres ramifies avec branches polyolefiniques
JP5276757B2 (ja) 剪断減粘性エチレン／α−オレフィンインターポリマーおよびそれらの製造法
JP4418107B2 (ja) 生成物及びポリオレフィンポリマー分散体を製造するための方法
EP1113028B1 (fr) Procédé pour la préparation de polymères d'oléfines ayant des ramifications à longues chaînes
CN1042160A (zh) 用金属茂铝烷催化剂制备高分子量乙烯α-烯烃弹性体的方法
CA2000655A1 (fr) Polymeres de greffe renfermant un copolymere ethylene alpha-olefinieque avec du propylene; methodes de preparation et utilisation dans des compositions a base de polypropylene
CN1121930A (zh) 环状烯烃聚合物
WO1997022639A1 (fr) Procede de polymerisation en solution a haute temperature
RU2192426C2 (ru) Каталитический компонент, способ его получения, способ гомо- и сополимеризации альфа-олефинов и способ суспензионной полимеризации
US5578690A (en) Silyl-terminated interpolymer of ethylene and method for preparing silyl-terminated polyolefins
US6258904B1 (en) Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production
WO1998033842A1 (fr) Procede de reaction de polyolefines avec des hydrosilanes
CN111741997A (zh) 聚烯烃-聚二有机硅氧烷嵌段共聚物及用于其合成的氢化硅烷化反应方法
HUT58354A (en) Process for producing copolymere products consisting of ethylene and 1,5-hexadiene-containing other components
US5693713A (en) Process for making block graft copolymers by grafting halosilanes onto polyolefin/diene polymers
EP0146507B1 (fr) Procédé pour la polymérisation de l'ethylène et pour la copolymerisation de l'ethylène avec des alpha-olefines et catalyseurs utilisés dans ce procédé
CN108864348A (zh) 一种乙烯-α烯烃-非共轭二烯烃聚合物及其制备方法
EP0856517A1 (fr) Procédé d'hydrosilylation
Kateb et al. Synthesis of 1‐hexene/1, 7‐octadiene copolymers using coordination polymerization and postfunctionalization with triethoxysilane
JP2503527B2 (ja) ポリシロキサン含有共重合体の製造方法
KR20000023043A (ko) 관능기를 갖는 미립 고체와의 반응에 의한 올레핀 중합용비다리화된 모노시클로펜타디에닐 금속 착물 촉매
EP0361598A2 (fr) Procédé d'homopolymérisation d'éthylène et de copolymérisation d'éthylène avec des alpha-oléfines et catalyseur
WO2021099947A1 (fr) Composition de catalyseur et son procédé de préparation
JP3181704B2 (ja) ポリオレフィンの架橋成形物の製造方法
WO1998033838A1 (fr) Polyolefines ramifiees

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE GE HU ID IL IS JP KP KR LC LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK SL TR TT UA US UZ VN YU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1998532750

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase