WO2012103080A1 - Procédé de fabrication d'un copolymère séquencé à base de polyoléfine-polysiloxane - Google Patents

Procédé de fabrication d'un copolymère séquencé à base de polyoléfine-polysiloxane Download PDF

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Publication number
WO2012103080A1
WO2012103080A1 PCT/US2012/022348 US2012022348W WO2012103080A1 WO 2012103080 A1 WO2012103080 A1 WO 2012103080A1 US 2012022348 W US2012022348 W US 2012022348W WO 2012103080 A1 WO2012103080 A1 WO 2012103080A1
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polyolefin
polysiloxane
polyolefinyl
olefin
block
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PCT/US2012/022348
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English (en)
Inventor
Daniel J. Arriola
Thomas P. Clark
Thomas H. Peterson
Curt N. Theriault
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Dow Global Technologies Llc
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Publication of WO2012103080A1 publication Critical patent/WO2012103080A1/fr

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    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the invention generally relates to a process for making a polyolefin-polysiloxane block copolymer, a polyolefin-polysiloxane block copolymer made by the process, and an article comprising the polyolefin-polysiloxane block copolymer.
  • organopolysiloxane -containing materials have been known for more than 50 years.
  • US 2,853,504 mentions, among other things, a specific alkylation of a higher molecular weight organopolysiloxane using a hydrocarbon aluminum compound to yield a lower molecular weight organopolysiloxane containing alkyl group(s).
  • US 2,853,504 does not describe a polyolefinyl-aluminum compound or a use for the alkylation products.
  • specific subtypes of polyolefin-polysiloxane block copolymers have been known and found use in applications such as release coating, film, or sheet compositions. These compositions can be used in adhesive applications.
  • polyolefin-polysiloxane block copolymers have been limited to those types that can be prepared by known methods of coupling a polyolefin to a polysiloxane such as mentioned in Block Copolymers by Noshay and McGrath, Academic Press, New York, 1977, pages 156-162; and US 5,169,900; US 5,229,179; and US 5,728,469. Noshay and McGrath and US 5,169,900; US 5,229,179; and US 5,728,469 do not mention any aluminum-containing compound.
  • Other sub-types of polyolefin-polysiloxane block copolymers are not known or synthetically accessible using prior art methods.
  • WO 2005/073283 Al; WO 2005/090425 Al; WO 2005/090426 Al; WO 2005/090427 A2; WO 2006/101595 Al; WO 2007/035485 Al; WO 2007/035492 Al; and WO 2007/035493 A2 mention, among other things, certain chain shuttling agents (e.g., trialkyl aluminum compounds), catalyst systems, and olefin polymer compositions prepared therewith.
  • chain shuttling agents e.g., trialkyl aluminum compounds
  • the present inventors have recognized numerous problems with the prior art polyolefin- polysiloxane block copolymers and preparation methods and provide here a solution to at least one such problem.
  • the inventors recognized that prior art polyolefin-polydimethylsiloxane block copolymers and polyolefin-polysiloxane block copolymers are undesirably limited in composition.
  • the present invention provides a method and polyolefin-poly siloxane block copolymer that advantageously employs coordination catalysis for preparing higher M n polyolefin blocks (M n > 10,000 g/mol) and a polyolefinyl-aluminum compound for enabling coupling of the polyolefinyl directly to an acyclic polysiloxane or cyclic siloxane monomer, without employing a connecting segment or linker compound to connect the instant polyolefin block to the instant polysiloxane block.
  • the present invention provides a process for preparing a polyolefin- polysiloxane block copolymer, the process comprising contacting under coupling effective conditions a polyolefinyl-aluminum compound with an acyclic polysiloxane or cyclic siloxane monomer in such a way so as to give a polyolefin-polysiloxane block copolymer comprising a polyolefin block directly covalently bonded to a polysiloxane block (i.e., lacking a residual of a linker compound therebetween), wherein the polyolefin block comprises the polyolefinyl portion of the polyolefinyl-aluminum compound and the polysiloxane block comprises at least a portion of the acyclic polysiloxane.
  • the present invention provides the polyolefin-polysiloxane block copolymer that is prepared according to the process of the first embodiment, wherein the process of the first embodiment further comprises a preliminary step of preparing the polyolefinyl-aluminum compound, the preliminary step comprising contacting a catalyst comprising, or prepared from, a metal-ligand complex effective for polymerizing olefin monomers by coordination catalysis and at least one activating co-catalyst therefor, with a mixture comprising at least one olefin monomer and an aluminum coupling agent in a solvent under olefin polymerizing conditions so as to give the polyolefinyl-aluminum compound, wherein the metal of the metal-ligand complex is a metal of Group 4 of the Periodic Table of the Elements and the aluminum coupling agent is a compound of formula (K): A1(R K ) 3 (K), or a (C 4 -C 6 o)etherate thereof,
  • the polyolefin- polysiloxane block copolymer comprises a first polyoleiin block and a first polysiloxane block, wherein the first polyoleiin block has a number average molecular weight greater than 10,000 g/mol by gel permeation chromatography (GPC) and is directly covalently bonded to the first polysiloxane block polyoleiin block of the polyolefin-polysiloxane block copolymer.
  • GPC gel permeation chromatography
  • the GPC is GPC Method 1 described later.
  • the present invention provides a manufactured article comprising the polyolefin-polysiloxane block copolymer of the second embodiment.
  • the polyolefinyl-aluminum compound and invention process are useful with either the acyclic polysiloxane or cyclic siloxane monomer, or a mixture thereof for preparing the invention polyolefin-polysiloxane block copolymer.
  • the polyolefin-polysiloxane block copolymer is useful for preparing manufactured articles.
  • the manufactured article are useful in applications such as adhesives, release coating, film, or sheet compositions; peelable coatings, films, or sheet compositions; and slip coating compositions.
  • the polyolefin-polysiloxane block copolymer and manufactured article can be used in adhesive applications that include pressure-sensitive adhesive applications. Examples of such adhesive applications are tapes and labels, including peelable tapes and labels and two-sided tapes; backing material for carpet, especially for squares of carpet having adhesive backings; adhesive strips for medical and sanitary articles containing adhesive strips; and adhesive gaskets.
  • the invention process employs coordination catalysis chemistry, which enables advantageous preparation of the polyoleiin block from an olefin monomer that cannot be polymerized by anionic polymerization to a polyoleiin block having a number average molecular weight greater than 10,000 g/mol.
  • the aluminum-alkyl agent enables advantageous coupling (covalent bonding) oi the polyoleiin block to the polysiloxane block by a process that desirably avoids use oi a free radical grafting method.
  • the advantages of the present invention are not limited to the foregoing ones.
  • Figure (Fig.) 1 shows a reaction scheme for the reaction of Example 1.
  • Figs. 2a and 2b respectively show black-and-white photographs of transmission electron microscopy images of the polyolefin-polysiloxane block copolymer of Example 1 before and after exposure thereof to Ru0 4 vapors.
  • acyclic polysiloxane i.e., distinct from the polysiloxane block
  • coordination catalysis means employing a catalytically effective amount of an olefin polymerizing catalyst comprising or prepared from a mixture of at least one metal-ligand complex and at least one activating co-catalyst or activating condition, wherein each metal-ligand complex independently is an overall neutral molecule.
  • catalytically effective amount means a quantity (of the ad rem catalyst) that is sufficient to increase rate of reaction to a measurable extent under the circumstances.
  • Coupled conditions means circumstances comprising temperature and pressure of a reaction mixture comprising the contacted polyolefinyl-aluminum compound and acyclic polysiloxane or cyclic siloxane monomer, or combination thereof, and preferably a solvent, wherein the circumstances facilitate covalent bonding of the polyolefinyl-aluminum compound to the cyclic siloxane monomer or acyclic polysiloxane.
  • copolymer means a material comprising at least 6 repeat units prepared from at least two monomers.
  • cyclic siloxane monomer means a compound of formula (O): [(R x ) 2 SiO] c (0), wherein each R x independently is (Ci-Cio)alkyl; vinyl; allyl; phenyl; or benzyl; c is an integer from 3 to 20; and the O and Si atoms in formula (O) are located in a ring consisting thereof.
  • the phrase “directly covalently bonded” means lacking or omitting an intermediary connecting segment, which is a residual of a linker compound.
  • manufactured article means a member of a class of things, wherein the member is not found in nature.
  • polyolefin-polysiloxane block copolymer means a material comprising at least two chemically different oligomeric or polymeric segments, wherein at least one of the at least two oligomeric or polymeric segments is referred to herein as the "polyolefin block” or “first polyolefin block” and at least another one of the at least two oligomeric or polymeric segments is referred to herein as the "polysiloxane block” or "first polysiloxane block,” and the (first) polyolefin block is directly covalently bonded to the (first) polysiloxane block.
  • polyolefinyl means a radical of an oligomeric or polymeric polymeryl chain that is straight or branched and has been prepared by a process comprising polymerizing at least one olefin monomer, preferably wherein the
  • polyolefinyl-aluminum compound preferably means a metal-ligand complex of formula (L): [polyolefinyl] m Al(R L ) n (L), wherein m is an integer of 1 , 2, or 3; n is an integer of 2, 1 , or 0, respectively; the sum of (m + n) is 3; each R L independently is a (Ci-C 30 )hydrocarbyl, (Ci-C 30 )heterohydrocarbyl, halo, -NH 2 , or -OH; and polyolefinyl is as defined previously.
  • Numerical ranges any lower limit of a range of numbers, or any preferred lower limit of the range, may be combined with any upper limit of the range, or any preferred upper limit of the range, to define a preferred aspect or embodiment of the range (e.g., "from 1 to 5" includes, for example, 1, 1.5, 2, 2.75, 3, 3.81, 4, and 5).
  • (Ci-C 3 o)hydrocarbyl means a hydrocarbon radical of from 1 to 30 carbon atoms wherein each hydrocarbon radical independently is aromatic (i.e., (C6-C 30 )aryl, e.g., phenyl) or non-aromatic (i.e., (Ci-C 30 )aliphatic radical); saturated (i.e., (Ci-C 30 )alkyl or (C 3 -C 30 )cycloalkyl) or unsaturated (i.e., (C 2 -C 30 )alkenyl, (C 2 -C 30 )alkynyl, or (C 3 -C 30 )cycloalkenyl); straight chain (i.e., normal-(d- C 30 )alkyl) or branched chain (e.g., secondary-, iso-, or tertiary-(C 3 -C 30 )alkyl); cyclic (at least 3 carbon atoms, (C
  • radicals of the hydrocarbon radical can be on same or, preferably, different carbon atoms.
  • Other hydrocarbyl groups e.g.,
  • (Ci-Cio)hydrocarbyl, (Ci-C 20 )hydrocarbyl, and (C 2 -C 20 )hydrocarbyl)) are defined in an analogous manner.
  • a (Ci-C 30 )hydrocarbyl independently is an unsubstituted or substituted
  • the (Ci-C 30 )hydrocarbyl is a (Ci-C 20 )alkyl, more preferably (Ci-Cio)alkyl, and still more preferably (Ci-C6)alkyl.
  • (C 2 -C 30 )hydrocarbylene is as defined for (Ci-C 30 )hydrocarbyl except
  • (C 2 -C 30 )hydrocarbylene is a diradical and contains from 2 to 30 carbon.
  • (C 2 -C 30 )hydrocarbylene is a (C 2 -C 20 )alkylene, and more preferably a (C 2 -Ci 0 )alkylene (e.g., -CH 2 CH 2 -, -CH 2 C(H)(CH 3 )-, CH 2 CH 2 CH 2 -, or -( CH 2 ) 4 -).
  • (Ci-C 30 )heterohydrocarbyl means a heterohydrocarbon radical of from 1 to 30 carbon atoms and from 1 to 6 heteroatoms; wherein each heterohydrocarbon radical independently is aromatic (i.e., (Ci-C 30 )heteroaryl, e.g., tetrazol-5-yl, l,3,4-oxadiazol-2-yl, imidazol-l-yl, pyrrol-l-yl, pyridine-2-yl, and indol-5-yl) or non-aromatic (i.e., (Ci-C 30 )heteroaliphatic radical); saturated (i.e., (Ci-C 30 )heteroalkyl or (C 2 -C 30 )heterocycloalkyl) or unsaturated (i.e., (C 2 -C 30 )heteroalkenyl, (C 2 - C 30 )heteroalkynyl
  • the radical of the heterohydrocarbon radical can be on a carbon (e.g., CH 3 CH 2 CH 2 OCH 2 -), oxygen (e.g., CH 3 CH 2 CH 2 -0-), nitrogen (e.g., CH 3 CH 2 -N(R N )-), or sulfur (e.g., CH 3 CH 2 -S-, CH 3 CH 2 CH 2 -S(0)-, or CH 3 CH 2 -S(0) 2 -).
  • Other heterohydrocarbyl groups e.g., (C 2 -Ci 0 )heterohydrocarbyl) are defined in an analogous manner.
  • each hydrocarbon radical and heterohydrocarbon radical independently is unsubstituted or, in other embodiments, at least one is substituted by at least 1 , preferably 1 to 6, substituents, R s .
  • each R s independently is selected from the group consisting of a halogen atom (halo); any one of polyfluoro and perfluoro substitution, unsubstituted (Ci-Cig)alkyl; F 3 C-; FCH 2 0-; F 2 HCO-; F 3 CO-; R v 3 Si-; R G 0-; R G S-; R G S(0)-;
  • halo means fluoro, chloro, bromo, or iodo; or in some embodiments in order of increasing preference chloro; bromo or iodo; chloro or bromo; or chloro.
  • each unsubstituted chemical group and each substituted chemical group has a maximum of 15; 12; 6; or 4 carbon atoms.
  • the manufactured article can entirely consist essentially of the polyolefin-polysiloxane block copolymer or the polyolefin-polysiloxane block copolymer can comprise a portion of the manufactured article.
  • the portion of the manufactured article comprising the polyolefin- polysiloxane block copolymer can be prepared from the polyolefin-polysiloxane block copolymer alone or in a blend with at least one other polymer (e.g., a polyolefin or polysiloxane).
  • the invention process further comprises subsequent steps of preparing the
  • the subsequent steps comprise shaping a melt (optionally containing a liquid plasticizer) of the polyolefin-polysiloxane block copolymer or shaping a solution of the polyolefin- polysiloxane block copolymer dissolved in a solvent (e.g., chloroform, acetonitrile, or
  • tetrahydrofuran to respectively give a shaped melt or shaped solution of the polyolefin-polysiloxane block copolymer, and allowing the shaped melt to solidify or the liquid plasticizer or solvent to separate out so as to prepare the manufactured article.
  • Shaped solutions typically employ a support until enough of the solvent can be removed therefrom so as to form a self-supporting shaped manufactured article.
  • An example of a shaped solution is a cast film (on a support). Solution casting is useful for preparing the manufactured article as a film, coating or sheet.
  • melt when referring to the polyolefin-polysiloxane block copolymer means a ductile phase that can be plastically deformed without fracture, wherein the ductile phase comprises at least most, and preferably consists essentially of all, of the polyolefin-polysiloxane block copolymer as a liquid phase.
  • solidify means completely or almost completely (e.g., at least 95 wt ) changing phase into a mass having a definite shape and volume (as opposed to being "fluid”). In some embodiments the mass can be characterized as being amorphous, partially crystalline, or crystalline.
  • the separating out is evaporating; blotting; wiping; phase separating; centrifuging; or a combination thereof.
  • the optional liquid plasticizer e.g., chloroform or acetonitrile
  • the solvent comprises from 50 wt to 99 wt of the solution.
  • the solvent and liquid plasticizer can be the same or different.
  • the (portion of) manufactured article can comprise insubstantial residual amounts (typically ⁇ 5 wt ) of the liquid plasticizer or solvent.
  • Examples of suitable shaping processes for forming the manufactured article, or portion thereof, comprising the polyolefin-polysiloxane block copolymer are calendaring, coating, casting, extruding, flaking, flattening, granulating, grinding, inflating, molding, pelletizing, pressing, rolling, and spraying.
  • Examples of useful three-dimensional configurations are bowls, coatings, cylinders, die casts, extruded shapes, films (having a length, width, and thickness), flakes, granules, molded shapes, pellets, powders, sheets (having a length, width, and thickness, which is greater than the thickness of the film), and trays.
  • Examples of the sheets are flat sheets and pleated sheets.
  • the manufactured article is a particulate packing material; plaque; film; rolled sheet (e.g., a hollow cylinder); or container.
  • the polyolefin-polysiloxane block copolymer can be prepared under coupling effective conditions as described previously.
  • the coupling effective conditions comprise a coupling pressure of from 100 kilopascals (kPa) to 200 kPa, and more preferably ambient pressure (e.g., 101 kPa).
  • the coupling effective conditions also comprise a coupling temperature of from 120 degrees Celsius (°C) to 250 °C, more preferably from 140 °C to 200 °C, and still more preferably from 150 °C to 190 °C.
  • the coupling effective conditions further comprise a solvent ("coupling solvent”), which preferably is an aprotic solvent, more preferably a hydrocarbon solvent such as that described later for olefin polymerizing conditions (e.g., toluene).
  • a solvent e.g., an aprotic solvent, more preferably a hydrocarbon solvent such as that described later for olefin polymerizing conditions (e.g., toluene).
  • the polyolefinyl-aluminum compound is contacted with the acyclic polysiloxane or cyclic siloxane monomer, or a combination thereof, in the solvent (e.g., about 1 milliliter (mL)) of solvent per gram of polyolefinyl-aluminum compound), and the resulting reaction mixture is heated.
  • the solvent has a boiling point approximately the same as the desired coupling temperature and the reaction mixture is heated at reflux to facilitate coupling. If the boiling point of the solvent is lower than the desired coupling temperature, the reaction mixture can be sealed in a reactor (i.e., a pressure vessel), and contents of the sealed reactor can be heated to the desired reaction temperature therein.
  • a reactor i.e., a pressure vessel
  • Progress of the reaction can be monitored by periodically removing aliquots of the reaction mixture, cooling them to ambient temperature, and quenching them if desired (e.g., by addition of a quenching agent such as an alcohol (e.g., methanol) to give a mixture comprising the polyolefin-polysiloxane block copolymer product and, optionally from any unreacted polyolefinyl-aluminum compound, free polyolefin.
  • a quenching agent such as an alcohol (e.g., methanol)
  • the product mixture can be characterized by l H- NMR or 13 C-NMR spectroscopy, gel permeation chromatography (GPC), or transmission electron microscopy (TEM).
  • Characterization of the product can include detection and integration of a multiplet centered at about ⁇ 0.67 in ⁇ -NMR that is due to a linking methylene proton resonance of the linking methylene shown in the formula: polysiloxane block-Si-CH 2 -polyolefin block.
  • the linking methylene is a part of the polyolefin block and is derived from the polyolefinyl.
  • the methylene protons i.e., the Si-CH 2 CH 3
  • the Si-CH 2 CH 3 can be detected as a multiplet centered at about ⁇ 0.60 in ⁇ -NMR, and thus can be distinguished from the aforementioned linking methylene.
  • acyclic polysiloxane R x e.g., CH 3 in a polydimethylsiloxane
  • M n number average molecular weight of the polysiloxane
  • a coupling temperature of 150 °C typically enables a sufficient degree of coupling reaction to occur and a desirable product to form within 24 hours.
  • the reaction mixture can be cooled to ambient temperature, quenched with a quenching agent, and purified by removing volatiles therefrom in vacuo, optionally with heating, to give the polyolefin-polysiloxane block copolymer.
  • the polyolefin-polysiloxane block copolymer product prepared in this way is sufficiently pure for use in the manufactured article.
  • the coupling effective conditions and polyolefin-polysiloxane block copolymer can also comprise residual olefin polymerization catalyst, olefin monomers, olefin oligomers, olefin polymerization solvent and the like that in some embodiments are carried through from the preliminary olefin polymerization reaction to the coupling reaction in such a way that the coupling reaction is not prevented thereby.
  • the product can be further purified by, for example, differential crystallization or differential extraction of any olefin monomers, free polysiloxanes or polyolefins therefrom with an extracting solvent such as additional coupling solvent.
  • Each molecule of the polyolefin-polysiloxane block copolymer contains two end polymer blocks and, optionally, one or more internal polymer block.
  • Each of the at least one polyolefin block of the polyolefin-polysiloxane block copolymer can independently comprise an end polyolefin block or internal polyolefin block therein.
  • the polyolefin block is represented in some embodiments by letter "A" and, when there are additional polyolefin blocks prepared from different monomers, by letters "B” or "C.” That is, where the polyolefin block comprises a multiblock polyolefin, combinations of letters A, B and C for describing the different polyolefin blocks are contemplated also.
  • Numerical superscripts can be employed with the block letters to distinguish between two different polyolefin blocks prepared from the same olefin monomer(s) (e.g., A 1 and A 2 polyethylene blocks) and hyphens can be optionally employed between block letters for readability.
  • Each polyolefin block can be prepared by, and in some embodiments the process further comprises the aforementioned preliminary step of preparing the polyolefinyl-aluminum compound.
  • Each of the at least one polysiloxane block of the polyolefin-polysiloxane block copolymer can comprise an end polysiloxane block or an internal polysiloxane block therein.
  • each end polysiloxane block independently is a material of formula (S): -Si(R x ) 2 -[OSi(R x ) 2 ]y-R T (S), wherein y is a number representing an average value of the number of the repeat units of formula OSi(R x ) 2 shown in the ad rem brackets; and each R T and R x independently is (Ci-Cio)alkyl; vinyl; allyl; phenyl; or benzyl.
  • each internal polysiloxane block independently is a material of formula (T): -Si(R x ) 2 -[OSi(R x ) 2 ]y-0- (T), wherein y is a number representing an average value of the number of the repeat units of formula OSi(R x ) 2 shown in the ad rem brackets; and each R x independently is (Ci-Cio)alkyl; vinyl; allyl; phenyl; or benzyl.
  • the polysiloxane blocks are represented in some embodiments by the letter "S.” Numerical superscripts can be employed with the polysiloxane block letters to distinguish between two different polysiloxane blocks prepared from the same cyclic polysiloxane monomer or acyclic polysiloxane (e.g., S 1 and S 2 polysiloxane blocks) and hyphens can be optionally employed between block letters for readability.
  • the process further comprises a preliminary step of preparing the acyclic polysiloxane or cyclic siloxane monomer as described later.
  • the polyolefin-polysiloxane block copolymer comprises a polyolefin- polysiloxane diblock copolymer.
  • the diblock copolymer consists essentially of A-S.
  • the polyolefin-polysiloxane block copolymer comprises a first triblock copolymer consisting essentially of A ⁇ S-A 2 , wherein A 1 and A 2 can be the same or different.
  • the polyolefin-polysiloxane block copolymer comprises a mixture having statistical distribution of A-S and A ⁇ S-A 2 .
  • the polyolefin-polysiloxane block copolymer comprises a first mixture or blend of the diblock and first triblock copolymers, or a second mixture or blend of the diblock and first triblock copolymers and free polysiloxane.
  • the polyolefin- polysiloxane block copolymer comprises a second triblock copolymer consisting essentially of A 2 - A l -S (e.g., wherein A 2 is a homopolyethylene and A 1 is a polyethylene having a low mol of alpha- olefin residuals, or vice versa).
  • the polyolefinyl portion of the polyolefinyl-aluminum compound is a radical of an olefin block copolymer (OBC, described later) such as a radical of an olefin diblock copolymer represented as B-A- (e.g., a polyethylene block A and a poly(l-octene) block B, or vice versa) or olefin triblock copolymer represented as C-B-A-.
  • OBC olefin block copolymer
  • free polysiloxane refers to at least one of unreacted cyclic siloxane monomer, unreacted acyclic polysiloxane, or a siloxane by-product or side product of any one or more thereof.
  • An example of the siloxane side product is two acyclic polysiloxanes produced by degradative cleavage of a larger acyclic polysiloxane.
  • An example of the siloxane by-product is an acyclic polysiloxane by-product cleaved from the material of formula (P) as a result of the reaction of the material of formula (P) with the polyolefinyl-aluminum compound in the invention process.
  • cleaved acyclic polysiloxane by-product is an acyclic polysiloxane of formula R T -[Si(R x ) 2 0] x -Si(R x ) 2 OH, wherein x, R x , and R T are as defined previously for the material of formula (P).
  • the polyolefin-polysiloxane block copolymer comprises another triblock copolymer consisting essentially of S ⁇ A-S 2 .
  • the polyolefin-polysiloxane block copolymer is a third triblock copolymer consisting essentially of A-S ⁇ (multifunctional coupling agent residual)-S 2 .
  • the third triblock copolymer can be prepared by preparing the first diblock copolymer A-S wherein block S is block S 1 , contacting A-S 1 with a multifunctional coupling agent to prepare intermediate
  • multifunctional coupling agent means a silane having a silicon atom (Si) bonded to four groups comprising at least two leaving groups (e.g., halo or
  • (Ci-Cio)carboxy e.g., dichlorodimethylsilane, diacetoxydimethylsilane, or trichloroethylsilane
  • R x groups e.g., (Ci-Cio)alkyl
  • the polyolefin-polysiloxane block copolymer is a first tetrablock copolymer consisting essentially of A 2 -A 1 -S 1 -(multifunctional coupling agent residual)-S 2 or B -A-S ⁇ (multifunctional coupling agent residual)-S 2 .
  • the polyolefin- polysiloxane block copolymer is a second tetrablock copolymer consisting essentially of A ⁇ S 1 - (multifunctional coupling agent residual)-S 2 -A 2 or A-S ⁇ (multifunctional coupling agent residual)- S 2 -B.
  • the first tetrablock copolymer can be prepared as described above for the third triblock copolymer except using the polyolefinyl-aluminum compound wherein the polyolefinyl portion is the radical of the olefin diblock copolymer represented as A 2 -A l - or B-A- in place of the polyolefinyl-aluminum compound wherein the polyolefinyl portion is the radical of block A.
  • the second tetrablock copolymer can be prepared by preparing two diblock copolymers consisting essentially A ⁇ S 1 and S 2 -A 2 or A-S 1 and S 2 -B, respectively, and then contacting the two diblock copolymers together with the multifunctional coupling agent in a manner similar to that described previously for preparing the third triblock copolymer so as to give the second tetrablock copolymer.
  • the present invention contemplates still other embodiments of the polyolefin-polysiloxane block copolymer, including embodiments of other triblock or tetrablock copolymers and embodiments of pentablock and higher copolymers.
  • Such other multiblock copolymers can be prepared by employing, for example, the dual-functional aluminum coupling agent so as to prepare an aluminum-polyolefinyl-aluminum compound, which is then reacted with two, three or more acyclic polysiloxane materials of formula (P), or the cyclic siloxane monomer, in a manner similar to that already described.
  • the term "dual-functional aluminum coupling agent” preferably means the compound of formula (K) that is a compound of formula (K-l): (R D ) 2 A1-(C 2 - C 30 )hydrocarbylene-Al-(R K1 ) 2 (K-l), or a (C 4 -C6o)etherate thereof, wherein at least one R K1 and at least one R D independently is a (Ci-C 30 )hydrocarbyl and each of the other R K1 and R D independently is (Ci-C 30 )hydrocarbyl; (Ci-C 30 )heterohydrocarbyl; halo; -NH 2 ; or -OH; and the (C 4 -C 6 o)etherate is as described before.
  • the invention process can employ a vinyl-polyolefinyl- aluminum compound in place of the polyolefinyl-aluminum compound, and, using any one of the aforementioned preparations, further employ a free radical grafting of a free vinyl-polyolefin thereto so as to prepare, for example, a C-B— A-S, C-B-S ⁇ multifunctional coupling agent residual)-S 2 , or C-A ⁇ S-A 2 , wherein blocks A and A 1 is derived from the vinyl-polyolefinyl-aluminum compound; block C is derived from the free vinyl-polyolefin; block S is derived from the acyclic polysiloxane material of formula (P); blocks B and the multifunctional coupling agent residual are derived according to the aforementioned method for preparing the third triblock copolymer; and block A 2 is derived according to
  • each R x is the same as another, and in other embodiments at least one R x is different than another R x .
  • each R T is the same as R x and in other embodiments at least one R T is different than at least one R x .
  • (C C 30 )hydrocarbyl groups of R x and R T independently are (Ci-C 20 )alkyl groups, and more preferably linear or branched, (Ci-C 3 )alkyl groups.
  • each R x and R T independently is a methyl, ethyl, a propyl (e.g., 1-propyl or 2-propyl), a butyl (e.g., 1-butyl; 2-butyl; or 1,1-dimethylethyl), a pentyl (e.g., 1-pentyl); a hexyl; a heptyl; or an octyl.
  • the polyolefinyl is a radical of a homopoly olefin; or a radical of a poly(olefin-co-olefin) copolymer.
  • the polyolefinyl is the radical of the homopolyolefinyl.
  • the homopolyolefin are polyethylene and polypropylene.
  • the polyolefinyl is the radical of the poly(olefin 1 -co-olefin) copolymer.
  • the poly(olefin-co-olefin) copolymer contains residuals from 2 to 4 different olefin monomers.
  • An example of the poly(olefin-co-olefin) copolymer containing residuals from 2 different olefin monomers is a poly(ethylene-co-(l-octene)); from 3 different olefin monomers is poly(ethylene-co-(l-octene)-(l,3-butadiene)); and from 4 different olefin monomers is poly(ethylene-co-(propylene-(l-octene)-(l,3-butadiene)).
  • (Ci-C 30 )hydrocarbyl groups of R L independently are (d- C 2 o)alkyl groups, and more preferably linear or branched, (Ci-C 8 )alkyl groups.
  • each R L independently is a (C r C 8 )alkyl, (C C 8 )alkylO-, (Ci-C 8 )alkylC0 2 -, or halo.
  • halo is CI or Br, and more preferably CI.
  • each (Ci-C 8 )alkyl is a methyl, ethyl, a propyl (e.g., 1-propyl or 2-propyl), a butyl (e.g., 1-butyl; 2-butyl; or 1,1-dimethylethyl), a pentyl (e.g., 1-pentyl); a hexyl; a heptyl; or an octyl.
  • the aluminum coupling agent is the (C 4 -C6o)etherate of the compound of formula (K).
  • the (C 4 -C 6 o)etherate is diethyl ether, tetrahydrofuran, or 1,4-dioxane.
  • the (C 4 -C 6 o)etherate is absent and the aluminum coupling agent is the compound of formula (K).
  • at least one R K is the (Ci- C 2 o)alkyl and at least one of the other R K is: (Ci-C 2 o)hydrocarbyl; in other embodiments
  • (Ci-C 20 )heterohydrocarbyl in other embodiments (C 2 -C 20 )hydrocarbylene-Al-(R K1 ) 2 ; in other embodiments -0-Al-(R K2 ) 2 ; in other embodiments halo; in other embodiments -NH 2 ; or in other embodiments -OH.
  • (Ci-C 30 )hydrocarbyl groups of R K independently are (Ci-C 20 )alkyl groups, and more preferably linear or branched, (Ci-C 8 )alkyl groups.
  • each R K and R K1 and R K2 independently is a (Ci-C 20 )alkyl.
  • each R K and R K1 and R K2 independently is a (C C C 8 )alkyl, (C C 8 )alkylO-, (C C 8 )alkylC0 2 -, or halo.
  • halo is CI or Br, and more preferably CI.
  • each (Ci-C 8 )alkyl is a methyl, ethyl, a propyl (e.g., 1-propyl or 2-propyl), a butyl (e.g., 1-butyl; 2-butyl; or 1,1-dimethylethyl), a pentyl (e.g., 1-pentyl); a hexyl; a heptyl; or an octyl.
  • the aluminum coupling agent i.e., the compound of formula (K), or the (C 4 -C6o)etherate thereof
  • the aluminum coupling agent for use in the present invention is a trialkyl aluminum compound, and still more preferably triethylaluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n-hexyl) aluminum, or tri(n-octyl)aluminum.
  • the aluminum coupling agent is a primary reaction product or mixture formed by contacting any one of the immediately foregoing a trialkyl aluminum compounds with less than a stoichiometric amount of a (Ci-C 30 )heterohydrocarbon ligand, wherein the stoichiometric amount is equal to the number of moles of alkyl groups in the immediately foregoing a trialkyl aluminum compounds.
  • Each mole of the trialkyl aluminum compound has 3 moles of alkyl groups, and so the less than stoichiometric amount is less than 3 mole equivalents, and preferably is 1 mole equivalent, and more preferably 2 mole equivalents of the (Ci-C 30 )heterohydrocarbon ligand.
  • the less than stoichiometric amount is less than 3 mole equivalents, and preferably is 1 mole equivalent, and more preferably 2 mole equivalents of the (Ci-C 30 )heterohydrocarbon ligand.
  • (Ci-C 30 )heterohydrocarbon ligand is a primary or secondary (Ci-C 30 )hydrocarbylamine (e.g., butylamine or dibutylamine), primary or secondary (Ci-C 30 )hydrocarbylsilylamine (e.g., butyldimethylsilylamine or bis(trimethylsilyl)amine), primary or secondary
  • hydrocarbylphosphine e.g., phenylphosphine or diphenylphosphine
  • (Ci-C 30 )hydrocarbylthiol e.g., thiophenol
  • a (Ci-C 30 )hydrocarbylhydroxyl compound e.g., 1,1- dimethylethanol or phenol.
  • the (Ci-C 30 )heterohydrocarbon ligand is
  • the primary reaction product that is obtained from reaction of any one of the foregoing trialkyl aluminum compounds with any one of the foregoing (Ci-C 30 )heterohydrocarbon ligands preferably is n-octylaluminum
  • the aluminum coupling agent is a (C 4 -C 6 o)etherate of any one of the foregoing named compounds of formula (K) or (K-l).
  • the aluminum coupling agent means the aforementioned dual- functional aluminum coupling agent.
  • Other compounds that can be used as dual-functional aluminum coupling agent are the multicentered (chain) shuttling agents of formula (M') m A described in US 2008/0275189 Al, wherein m is 2, each M' is aluminum, and A is the linking group as defined therein (e.g., A is (C 2 -C 2 o)hydrocarbylene).
  • M' multicentered (chain) shuttling agents of formula (M') m A described in US 2008/0275189 Al, wherein m is 2, each M' is aluminum, and A is the linking group as defined therein (e.g., A is (C 2 -C 2 o)hydrocarbylene).
  • A is (C 2 -C 2 o)hydrocarbylene).
  • a tri-functional aluminum coupling agent wherein m is 3, each M' is aluminum, and A is the linking group.
  • the preliminary step of preparing the polyolefinyl-aluminum compound employs only one metal-ligand complex effective for polymerizing olefin monomers by coordination catalysis and at least one activating co-catalyst therefor in a reactor, and so in that reactor the aluminum coupling agent functions as an aluminum-containing chain transfer agent.
  • the aluminum-containing chain transfer agent can be generally characterized as a molecule lacking an acidic hydrogen atom (e.g., lacking H-O, H-N, or H-S moiety) that contains an aluminum-based moiety effective for causing irreversible movement of the polymeryl chain from the active site of the catalyst to the aluminum of the aluminum-containing chain transfer agent (e.g., a preferred embodiment of the aluminum coupling agent) or to a second or third site on the aluminum- containing chain transfer agent having an available second or third site (e.g., the compound of formula (K) or (L) respectively having two or one R K or R L , or a combination thereof). Where there is only one coordination catalyst in a reactor, any of the aluminum coupling agents and
  • the preliminary step of preparing the polyolefinyl-aluminum compound employs at least two different metal-ligand complexes independently effective for polymerizing olefin monomers by coordination catalysis and at least one activating co-catalyst therefor in a reactor, and so in that reactor the aluminum coupling agent functions as a chain shuttling agent.
  • chain shuttling agent generally refers to a compound or mixture of such compounds that is capable of causing polymeryl (i.e., polymer chain) exchange between at least two active catalyst sites of a same olefin polymerization catalyst or between at least two active catalyst sites of at least two different olefin polymerization catalysts under the olefin polymerization conditions. That is, transfer of a polymer fragment occurs both to and from one or more of active sites of the olefin polymerization catalysts.
  • a chain transfer agent causes termination of polymer chain growth and amounts to a one-time transfer of polymer from a catalyst to the chain transfer agent.
  • polyolefinyl of the polyolefinyl-aluminum compound and the polyolefin block of the polyolefin-polysiloxane block copolymer are the same as each other; and in other embodiments they are different than each other.
  • the olefin monomers i.e., polymerizable olefins, including olefin comonomers are (C 2 -C 40 )hydrocarbons consisting of carbon and hydrogen atoms and containing at least 1 and preferably no more than 3, and more preferably no more than 2 carbon- carbon double bonds, where the carbon-carbon double bonds do not include aromatic carbon-carbon bonds (e.g., as in phenyl).
  • C 40 )hydrocarbons are replaced, each by a halogen atom, preferably fluoro or chloro to give halo- substituted (C 2 -C 4 o)hydrocarbons.
  • the unsubstituted (C 2 -C 4 o)hydrocarbons are preferred over the substituted (C 2 -C 0 )hydrocarbons (i.e., halo-substituted).
  • Preferred olefin monomers useful for making the polyolefinyls are ethylene and polymerizable (C 3 -C 0 )olefins.
  • the (C 3 -C 0 )olefins include an alpha-olefin, a cyclic olefin, styrene, and a cyclic or acyclic diene.
  • Another preferred polyolefin is a (C 8 -C 40 )olefin that is non- aromatic or aromatic, the aromatic (C 8 -C 40 )olefin containing at least one derivative of benzene (e.g., styrene, alpha-methylstyrene or divinylbenzene) or naphthalene (e.g., vinyl-naphthalene).
  • the (C 8 -C 40 )olefin can be optionally substituted to give a halo-substituted (C 8 - C 40 )olefin (e.g., 4-fluorostyrene).
  • the cyclic olefin is a (C 3 -C 40 )cyclic olefin.
  • the cyclic or acyclic diene is a (C -C 0 )diene, preferably an acyclic diene, more preferably an acyclic conjugated (C -C 0 )diene, more preferably an acyclic 1,3-conjugated (C -C 0 )diene, and still more preferably 1,3-butadiene.
  • the polyolefin block is prepared from at least one of the foregoing olefin monomers.
  • the polyolefin block is prepared from the at least one olefin monomer, at least one of which (i.e., at least one of the olefin monomer(s)) is ethylene, in other embodiments an alpha-olefin, and in other embodiments a cyclic olefin (e.g., cyclopentene or norbornene).
  • the at least one olefin monomer consists of carbon, hydrogen, and, optionally, halo (preferably, fluoro or chloro).
  • the at least one olefin monomer contains a single carbon-carbon double bond, and more preferably contains a single carbon-carbon double bond that is not conjugated with an aromatic ring or carbonyl group.
  • the polyolefin block lacks a residual of styrene.
  • the polyolefin block is prepared from the at least one olefin monomer, at least one of which (i.e., at least one of the olefin monomer(s)) is characterizable as not being polymerizable to a polyolefin of high molecular weight (e.g., high number average molecular weight, e.g., M n of equal to or, preferably, greater than 5,000 g/mol) by anionic polymerization.
  • a polyolefin of high molecular weight e.g., high number average molecular weight, e.g., M n of equal to or, preferably, greater than 5,000 g/mol
  • olefin monomers examples include: alpha-olefins (e.g., propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and (Cn-C 30 )-alpha-olefin) cyclic olefins (e.g., cyclopentene and norbornene), and non-conjugated substituted olefins.
  • alpha-olefins e.g., propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and (Cn-C 30 )-alpha-olefin
  • cyclic olefins e.g., cyclopentene and norbornene
  • At least one polyolefinyl of the polyolefinyl-aluminum compound comprises a residual of an olefin monomer that cannot be polymerized to the polyolefin of the high molecular weight (e.g., M n > 5,000 g/mol) by anionic polymerization or the polyolefinyl is a polyolefinyl characterizable in that it cannot be coupled to a free radical coupling agent (e.g., a vinyl-silane or an iniferter) via a free radical grafting method without the aforementioned polyolefinyl chain scission and degradation of molecular weight and physical properties.
  • a free radical coupling agent e.g., a vinyl-silane or an iniferter
  • Examples of such polyolefinyls are: homopolyolefins prepared from any one olefin monomer named in the immediately foregoing list of olefin monomers (e
  • polyethylenyl or polypropylenyl a polyethylene-based interpolymer prepared from ethylene and at least one olefin monomer named in the immediately foregoing list of olefin monomers (e.g., poly(ethylene-co- 1-octene) or poly(ethylene-co-(l-octene)-norbornadiene)); or a non-poly ethylene - based polyolefin interpolymer prepared from at least two different olefin monomers named in the immediately foregoing list of olefin monomers (e.g., poly(propylene-co- 1-octene) or poly(propylene-co-(l-octene)-norbornadiene).
  • olefin monomers e.g., poly(ethylene-co- 1-octene) or poly(ethylene-co-(l-octene)-norbornadiene
  • such polyolefinyls and polyolefinyl- aluminums can be prepared to the high molecular weight (e.g., M n > 5,000 g/mol) by coordination catalysis without the aforementioned polyolefinyl chain scission and degradation of molecular weight and physical properties.
  • the polyolefin block(s) include olefin homopolymers comprising residuals of one of the olefin monomers described in the two immediately preceding paragraphs.
  • the olefin homopolymers are radicals of polyethylene, polypropylene, poly(C 3 - C 40 )alpha-olefins, and polystyrene.
  • Other polyolefins include, for example, olefin interpolymers, including olefin copolymers, especially olefin block copolymers, more preferably olefin
  • interpolymers that comprise residuals of ethylene and one or more polymerizable (C 3 -C 4 o)olefins such as, for example, a poly(olefin monomer-olefin comonomer) block copolymer.
  • polymerizable (C 3 -C 4 o)olefins such as, for example, a poly(olefin monomer-olefin comonomer) block copolymer.
  • Other preferred olefin interpolymers are those prepared by co-polymerizing a mixture of two or more olefin monomers such as, for example, ethylene/propylene, ethylene/1 -butene, ethylene/ 1-pentene, ethylene/1 -hexene, ethylene/4-methyl-l-pentene, ethylene/1 -octene, ethylene/styrene,
  • the polyolefins include non-block poly(olefin monomer-olefin comonomer) copolymers.
  • the polyolefin comprises a blend of at least two different polyolefins, at least one of which can be made by the invention process. Examples of such blends include a blend of a polypropylene homopolymer and a poly(olefin monomer-olefin comonomer) block copolymer.
  • a polyolefin block (e.g., OBC block) of the polyolefin-polysiloxane block copolymer can be characterized as being a hard or soft block.
  • Hard blocks or segments refer to crystalline or semi-crystalline blocks of polymerized units in which in some embodiments contain ethylene, preferably ethylene is present in an amount greater than about 80 mole percent, and preferably greater than 88 mole percent. In other words, the comonomer content in the hard segments is less than 20 mole percent, and preferably less than 12 weight percent. In some embodiments, the hard segments comprise all or substantially all ethylene. Such hard blocks are sometimes referred to herein as "rich polyethylene" blocks or segments.
  • Soft blocks or segments refer to blocks of polymerized units in which the comonomer content is greater than 20 mole percent, preferably greater than 25 mole percent, up to 100 mole percent. In some embodiments, the comonomer content in the soft segments can be greater than 20 mole percent, greater than 25 mole percent, greater than 30 mole percent, greater than 35 mole percent, greater than 40 mole percent, greater than 45 mole percent, greater than 50 mole percent, or greater than 60 mole percent. "Soft” blocks or segments may refer to amorphous blocks or segments or with levels of crystallinity lower than that of the "hard” blocks or segments.
  • Preferred polyolefinyls include radicals of copolymers (e.g., ethylene/octene copolymers) having trade names ATTANETM and AFFINITYTM, and ENGAGETM polyolefin elastomers, each available from The Dow Chemical Company, Michigan, USA; and olefin copolymers (e.g., ethylene/ 1-butene copolymers) made using INSITE® technology of The Dow Chemical Company.
  • copolymers e.g., ethylene/octene copolymers
  • ATTANETM and AFFINITYTM trade names ATTANETM and AFFINITYTM
  • ENGAGETM polyolefin elastomers each available from The Dow Chemical Company, Michigan, USA
  • olefin copolymers e.g., ethylene/ 1-butene copolymers
  • a preferred poly(olefin monomer-olefin comonomer) block copolymer is a poly(olefin monomer-olefin comonomer) that is characterizable as being a multiblock interpolymer having blocks or segments of two or more polymerized monomer units differing in chemical or physical properties, and characterizable as being mesophase separated.
  • Such copolymers are sometimes referred to herein as "mesophase-separated olefin multiblock interpolymer s.”
  • each poly(olefin monomer-olefin comonomer) independently is characterizable as being mesophase separated and having a PDI of 1.4 or greater.
  • the poly(olefin monomer-olefin comonomer) block copolymer is an ethylene/alpha-olefin interpolymer, such as those described in US 2010/0298515 Al, preferably a block copolymer, which comprises a hard segment and a soft segment, and is characterized by a M /M in the range of from about 1.4 to about 2.8 and (a), (b), (c), (d), (e), (f), or (g): (a) paragraph
  • the poly(olefin monomer-olefin comonomer) block copolymer is an ethylene/alpha-olefin interpolymer, such as that described in US 7,355,089 and US 2006/0199930 Al, wherein the interpolymer is preferably a block copolymer, and comprises a hard segment and a soft segment, and the ethylene/alpha-olefin interpolymer (a), (b), (c), (d), (e), (f), (g), or (h): (a) paragraph [0049] of US 2006/0199930 Al; or (b) paragraphs [0049] and [0051] of US
  • polyolefins and processes such as those described in US 2007/0167315 Al, US 2008/0311812 Al, and US 2007/0167578 Al; and WO 2009/097565.
  • the polyoleiinyl of the polyolefinyl-aluminum compound and the polyolefin block of the polyolefin-polysiloxane block copolymer can be readily characterized directly by nuclear magnetic resonance (NMR) including proton-NMR ( ⁇ H-NMR). Such characterization can be based on its monomer and comonomer content.
  • Characterization of the polyoleiinyl can include detection and integration of a multiplet centered at about ⁇ 0.28 in ⁇ -NMR that is due to a linking methylene proton resonance of the linking methylene shown in the formula: >Al-CH 2 -polyolefinyl. An aliquot can be removed from a reaction mixture and polymerization terminated with a chain transfer agent as described later before doing the ⁇ -NMR.
  • the polyoleiinyl of the polyolefinyl-aluminum compound can be readily characterized by quenching the polyoleiinyl so as to give a characterizable amount free polyolefin.
  • the polyolefin is thereby released from the polyolefinyl-aluminum compound while leaving terminal functional groups attached to the free polyolefin.
  • quenching comprises, for example, contacting the polyolefinyl-aluminum compound to a proton source (e.g., water, aqueous acid, or an alcohol such as 2-propanol).
  • the chain transfer or quenching agent further comprises a stabilizing agent such as, for example, an antioxidant (e.g., a hindered phenol antioxidant (IRGANOXTM 1010 from Ciba Geigy Corporation)), a phosphorous stabilizer (e.g., IRGAFOSTM 168 from Ciba Geigy Corporation), or both.
  • a stabilizing agent such as, for example, an antioxidant (e.g., a hindered phenol antioxidant (IRGANOXTM 1010 from Ciba Geigy Corporation)), a phosphorous stabilizer (e.g., IRGAFOSTM 168 from Ciba Geigy Corporation), or both.
  • an antioxidant e.g., a hindered phenol antioxidant (IRGANOXTM 1010 from Ciba Geigy Corporation)
  • a phosphorous stabilizer e.g., IRGAFOSTM 168 from Ciba Geigy Corporation
  • the monomer and comonomer content of the polyoleiinyl of the polyolefinyl-aluminum compound and the polyolefin block of the polyolefin-polysiloxane block copolymer can also be measured using another technique such as, for example, Fourier Transform infrared (FT-IR) spectroscopy or 13 C NMR spectroscopy, with the aforementioned techniques based on H-NMR spectroscopy being more preferred.
  • FT-IR Fourier Transform infrared
  • the spectral width is 25,000 Hz with a minimum file size of 32,000 data points.
  • the amount of olefin comonomer incorporated into the polyoleiinyl or the polyolefin block oi the polyolefin-polysiloxane block copolymer is characterized by a comonomer incorporation index.
  • comonomer incorporation index reiers to the mole percent of residuals of olefin comonomer incorporated into olefin monomer/comonomer copolymer, or segment thereof, prepared under representative olefin polymerization conditions.
  • the olefin monomer is ethylene or propylene and the comonomer respectively is an (C 3 -C 40 )alpha-olefin or (C 4 -C 40 )alpha-olefin.
  • the olefin polymerization conditions are described fully later but are ideally under steady-state, continuous solution polymerization conditions in a hydrocarbon diluent at 100 °C, 4.5 megapascals (MPa) ethylene (or propylene) pressure (reactor pressure), greater than 92 percent (more preferably greater than 95 percent) olefin monomer conversion, and greater than 0.01 percent olefin comonomer conversion.
  • catalyst compositions having the greatest difference in olefin comonomer incorporation indices results in poly(olefin monomer-olefin comonomer) block copolymers from two or more olefin monomers having the largest difference in block or segment properties, such as density.
  • the olefin comonomer incorporation index may be determined directly, for example by the use of NMR spectroscopic techniques described previously or by IR spectroscopy. If NMR or IR cannot be used, then any difference in comonomer incorporation is indirectly determined. For polyolefins formed from multiple olefin monomers this indirect determination may be accomplished by various techniques based on monomer reactivities.
  • the relative amounts of olefin comonomer and monomer in the polyolefin copolymer and hence the polyolefin copolymer composition is determined by relative rates of reaction of olefin comonomer and monomer, expressed as reactivity ratios.
  • the molar ratio of olefin comonomer to monomer is given by the equations described in US 2007/0167578 Al, in paragraphs numbered [0081] to
  • the polyolefin composition is a function only of temperature dependent reactivity ratios and olefin comonomer mole fraction in the reactor. The same is also true when reverse olefin comonomer or monomer insertion may occur or in the case of the
  • the polyolefinyl of the polyolefinyl-aluminum compound is prepared by the coordination catalysis chemistry comprising contacting at least one olefin monomer with the metal- ligand complex effective for polymerizing olefin monomers by coordination catalysis, preferably wherein the metal of the metal-ligand complex is a metal of Group 4 of the Periodic Table, and at least one activating co-catalyst therefor and an aluminum coupling agent in a solvent under olefin polymerizing conditions (described previously) so as to as give the polyolefinyl-aluminum compound, all as described later herein.
  • the Group 4 metal is titanium, in other embodiments hafnium, and in other embodiments zirconium; preferably it is hafnium.
  • the preliminary step of preparing the polyolefinyl-aluminum compound employs a catalyst as mentioned previously.
  • a catalyst as mentioned previously.
  • at least two olefin monomers are employed in a same reactor for preparing a multiblock (e.g., diblock) polyolefin wherein at least one block is
  • two catalysts can be employed in the preliminary step as a catalyst system comprising a mixture or reaction product of: (A) a first olefin polymerization catalyst, the first olefin polymerization catalyst being characterized as having a high comonomer incorporation index (e.g., a comonomer incorporation index of 15 mole percent of comonomer or higher); (B) a second olefin polymerization catalyst, the second olefin polymerization catalyst being characterized as having a comonomer incorporation index that is less than 90 percent of the comonomer incorporation index of the first olefin polymerization catalyst; and (C) the aluminum coupling agent.
  • A a first olefin polymerization catalyst
  • the first olefin polymerization catalyst being characterized as having a high comonomer incorporation index (e.g., a comonomer incorporation index of 15 mole percent of comonomer or higher);
  • organic polymerization catalyst may refer to an unactivated form of a metal-ligand complex (i.e., precursor) or, preferably, the activated form thereof (e.g., after contact of the unactivated form with an activating cocatalyst to give a catalytically active mixture or product thereof).
  • the metal of the metal-ligand complex can be a metal of any one of Groups 3 to 15, preferably any one of Groups 3 to 6 or Groups 7 to 9, and more preferably Group 4, of the Periodic Table of the Elements.
  • metal-ligand complexes examples include metallocene, half-metallocene, constrained geometry, and polyvalent pyridylamine-, polyether-, or other polychelating base complexes.
  • metal-ligand complexes are described in the WO 2008/027283 and corresponding US 2010/0069573 Al.
  • first olefin polymerization catalyst is interchangeably referred to herein as “Catalyst (1st).”
  • second olefin polymerization catalyst is interchangeably referred to herein as “Catalyst (2nd).”
  • the first and second olefin polymerization catalysts preferably have different ethylene and (C 3 -C 4 o)alpha-olefin selectivities.
  • the comonomer incorporation index of Catalyst (2nd) is less than 50 percent and more preferably less than 5 percent of the comonomer incorporation index of Catalyst (1st).
  • the comonomer incorporation index for Catalyst (1st) is greater than 20 mol , more preferably greater than 30 mol , and still more preferably greater than 40 mol incorporation of comonomer.
  • each Catalyst (1st) and Catalyst (2 nd ) independently is a catalyst described in US 2004/0220050 Al; US 2006/0199930 Al ; US 2007/0167578 Al ; US 2008/0275189 Al ; US 2008/0311812 Al; US 7,355,089 B2; or WO 2009/012215 A2. More preferred are the catalysts described in US 2007/0167578 Al, paragraphs numbered [0138] to [0476].
  • Catalyst (B2) l,2-bis-(3,5-di-t-butylphenylene)(l-(N-(2- methylcyclohexyl)-imino)methyl)(2-oxoyl) zirconium dibenzyl (US 2008/0275189 Al), and having the structure:
  • the each olefin polymerization catalyst is rendered catalytically active by contacting it to, or reacting it with, a cocatalyst or by using an activating technique such as those that are known in the art for use with metal (e.g., Group 4) olefin polymerization reactions. Where there are two or more such catalysts, they can be activated by the same or different cocatalyst or same or different activating technique.
  • Many cocatalysts and activating techniques have been previously taught with respect to different metal-ligand complexes in the following USPNs: US 5,064,802; US 5,153,157; US 5,296,433; US 5,321,106; US 5,350,723; US 5,425,872; US
  • cocatalysts activating co-catalysts
  • alkyl aluminums include alkyl aluminums; polymeric or oligomeric alumoxanes (also known as aluminoxanes); neutral Lewis acids; and non- polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions).
  • a suitable activating technique is bulk electrolysis (explained in more detail hereinafter). Combinations of one or more of the foregoing cocatalysts and techniques are also contemplated.
  • alkyl aluminum means a monoalkyl aluminum dihydride or
  • alkyl of the foregoing alkyl-aluminums is from 1 to 10 carbon atoms. Triethylaluminum is more preferred.
  • Aluminoxanes and their preparations are known at, for example, United States Patent Number (USPN) US 6,103,657. Examples of preferred polymeric or oligomeric alumoxanes are methylalumoxane, triisobutylaluminum-modified methylalumoxane, and isobutylalumoxane.
  • cocatalysts are tri((C 6 -Ci 8 )aryl)boron compounds and halogenated (including perhalogenated) derivatives thereof, (e.g., tris(pentafluorophenyl)borane, trityl tetrafluoroborate, or, more preferably bis(octadecyl)methylammonium
  • the ratio of total number of moles of the olefin polymerization catalysts to total number of moles of one or more of the cocatalysts is from 1 : 10,000 to 100: 1. Preferably, the ratio is at least 1 :5000, more preferably at least 1: 1000; and 10: 1 or less, more preferably 1 : 1 or less.
  • the number of moles of the alumoxane that are employed is at least 100 times the number of moles of olefin polymerization catalysts.
  • the number of moles of the tris(pentafluorophenyl)borane that are employed to the total number of moles of one or more olefin polymerization catalysts form 0.5: 1 to 10: 1, more preferably from 1 : 1 to 6: 1, still more preferably from 1 : 1 to 5: 1.
  • the remaining cocatalysts are generally employed in approximately mole quantities equal to the total mole quantities of one or more olefin polymerization catalysts.
  • the olefin polymerization catalysts can be prepared under catalyst preparing conditions.
  • catalyst preparing conditions independently refers to reaction conditions such as solvent(s), atmosphere(s), temperature(s), pressure(s), time(s), and the like that are preferred for giving at least a 10 percent (%), more preferably at least 20%, and still more preferably at least 30% reaction yield of the catalyst from the relevant invention process of after 2 hours reaction time.
  • the relevant invention process independently is run under an inert atmosphere (e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof).
  • the relevant invention process is run with an aprotic solvent or mixture of two or more aprotic solvents, e.g., toluene.
  • the reaction mixture may comprise additional ingredients such as those described previously herein.
  • the relevant invention process is run at a temperature of the reaction mixture of from -20 °C to about 200 °C. In some embodiments, the temperature is at least 0 °C, and more preferably at least 20 °C. In other embodiments, the temperature is 100 °C or lower, more preferably 50 °C or lower, and still more preferably 40 °C or lower. A convenient temperature is about ambient temperature, i.e., from about 20 °C to about 30 °C.
  • the relevant invention process independently is run at ambient pressure, i.e., at about 1 atm (e.g., from about 95 kPa to about 107 kPa, such as 101 kPa).
  • a preferred catalytically effective amount means mole percent (mol%) of the catalyst for a catalyzed reaction that is less than 100 mol% of a number of moles of a product-limiting stoichiometric reactant employed in the catalyzed reaction and equal to or greater than a minimum mol value that is necessary for at least some product of the catalyzed reaction to be formed and detected (e.g., by mass spectrometry), wherein 100 mol is equal to the number of moles of the product-limiting stoichiometric reactant employed in the catalyzed reaction.
  • the minimum catalytic amount preferably is 0.000001 mol , and may be 0.00001 mol , 0.0001 mol , 0.001 mol , or even 0.01 mol .
  • the catalytic amount of each of the olefin polymerization catalysts independently is from 0.00001 mol % to 50 mol % of the moles of olefin monomer or comonomer, whichever is lower.
  • the polyolefinyl-aluminum compound can be prepared by contacting the olefin-terminated polyolefin (e.g., a vinyl-terminated polyethylene) with the aluminum coupling agent in a solvent under conditions that are the same as the olefin polymerizing conditions so as to as give the polyolefinyl-aluminum compound.
  • olefin-terminated polyolefin e.g., a vinyl-terminated polyethylene
  • the olefin-terminated polyolefin can be obtained from a commercial source or prepared by dehydrogenation (i.e., beta-hydride elimination) of a polyolefinyl chain (which can be bonded to an aluminum or boron) prepared in an olefin polymerization method described later or by quenching the polyolefinyl chain with a vinyl- containing end-capping agent such as a allyl bromide.
  • dehydrogenation i.e., beta-hydride elimination
  • a polyolefinyl chain which can be bonded to an aluminum or boron
  • a vinyl- containing end-capping agent such as a allyl bromide.
  • the beta-hydride elimination method is preferred.
  • the olefin-terminated polyolefin is prepared in a first reactor, transferred to a second reactor, where it is contacted as described with the aluminum coupling agent so as to prepare the polyolefinyl-aluminum compound.
  • the polyolefinyl-aluminum compound can be prepared by adapting any one of the following olefin polymerization methods so that the aluminum coupling agent is added to the olefin polymerization reaction mixture prior to adding the catalyst so that polyolefinyl chains produced therein do not experience a chain quenching (that undesirably would give free polyolefin), but instead are preserved as the polyolefinyl-aluminum compound for use in the invention coupling process with the acyclic polysiloxane or cyclic siloxane monomer.
  • a general process for making polyolefins that can be adapted for making the polyolefinyls of the present invention has been disclosed in US 2008/0269412 Al.
  • the olefin polymerization process that can be adapted for making the polyolefinyl- aluminum compound can comprise a continuous, batch or semi-batch preparation method and run in gas phase or liquid (preferably solution) phase.
  • a continuous process is preferred, in which continuous process, for example, catalyst, ethylene, a co-monomer olefin other than ethylene, and optionally a solvent, diluent, dispersant, or combination thereof are essentially continuously supplied to the reaction zone, and resulting polyolefin product is essentially continuously removed therefrom.
  • the olefin polymerization process can be carried out in a same reactor or in separate reactors (e.g., to make an OBC), preferably connected in series or in parallel, to prepare polymer blends having desirable properties.
  • a general description of such a process is disclosed in WO 94/00500.
  • the olefin polymerization is carried out according to the batch solution polymerization described later or by adapting the high throughput parallel polymerization conditions described in paragraph [0338] or the continuous solution polymerization conditions described in paragraph
  • the polyolefinyl-aluminum compound is produced in a solution process, more preferably an essentially continuous solution process, especially where the polyolefinyl is a radical of an OBC as in US 2008/0269412 Al.
  • An illustrative means for carrying out an essentially continuous polymerization process using at least two olefin monomers is as follows.
  • a stream of at least one olefin monomer and a stream of one of the aforementioned aluminum coupling compounds are introduced continuously, optionally with solvent (e.g., isoparaffinic alkanes) or diluent.
  • the reactor contains a liquid phase composed substantially of olefin monomer(s), together with any solvent, diluent and dissolved polymer.
  • a small amount of a "H" -branch-inducing diene such as norbornadiene, 1,7-octadiene, or 1 ,9-decadiene is also added. Then a solution of at least one metal- ligand complex and at least one activating co-catalyst therefor in a relatively small amount of solvent (e.g., toluene) are continuously introduced into the reactor liquid phase.
  • solvent e.g., toluene
  • control reactor temperature and pressure by, for example, adjusting solvent/olefin monomer ratio, adjusting olefin monomer/comonomer ratio (e.g., by manipulating the respective feed rates of the olefin monomers into the reactor) adjusting ingredient addition rates (e.g., adjusting rate of addition of catalyst), cooling or heating the reactor liquid phase (e.g., using coils, jackets or both), or a combination thereof.
  • control molecular weight (e.g., M n ) of polyolefinyl (co)polymer product by, for example, adjusting polymerization temperature, olefin monomer(s) concentration, or adjusting composition or concentration of the aluminum-containing chain transfer agent.
  • Discharge effluent containing the polyolefinyl-aluminum compound from the reactor and preferably contact the discharged effluent with a catalyst poisoning agent such as the 1,3,7-octatriene, which
  • molecular weight of the polyolefinyl of the resulting polyolefinyl-aluminum compound can be prevented from increasing in the effluent and, if desired, the polyolefinyl-aluminum compound can be directly contacted to the acyclic polysiloxane or cyclic siloxane monomer in the presence of any excess olefin monomer(s) under the coupling effective conditions so as to give the polyolefin-polysiloxane block copolymer in the effluent, i.e., without needing to remove any excess olefin monomer(s) from the reactor before performing the invention coupling step.
  • the effluent can be heated, and if desired a concentrated composition of the polyolefinyl-aluminum compound can be recovered by devolatilizing, e.g., flashing off volatiles such as gaseous olefin monomers, residual solvent, and diluents at reduced pressure under an inert gas atmosphere (inert gas bleed).
  • devolatilizing e.g., flashing off volatiles such as gaseous olefin monomers, residual solvent, and diluents at reduced pressure under an inert gas atmosphere (inert gas bleed).
  • devolatilization is conducted in equipment such as a devolatilizing extruder.
  • mean residence time of the catalyst and polyolefinyl-aluminum compound product in the reactor preferably is from about 5 minutes to about 8 hours, and more preferably 10 minutes to 6 hours.
  • the aluminum coupling compound can function as a chain shuttling agent in the reactor as a way to prolong the lifetime of (i.e., safekeep) a polyolefinyl chain such that a substantial fraction of the polyolefinyl chains exit at least a first reactor of a multiple reactor series or a first reactor zone in a multiple zoned reactor operating substantially under plug flow conditions in the form of the polyolefinyl- aluminum compound, and the polyolefinyl chains experience different polymerization conditions in the next reactor or polymerization zone.
  • Different polymerization conditions in the respective reactors or zones include the use of different olefin monomers, comonomers, or
  • the polyolefinyls resulting from the present process comprises two, three, or more, preferably two or three, differentiated polyolefinyl segments arranged intramolecularly.
  • the resulting polyolefinyl block of the polyolefin-polysiloxane block copolymer has improved properties over a random copolymer or monodisperse block copolymer.
  • the process can employ other (non-aluminum based) chain shuttling agents (preferably (Ci-Ci 2 )hydrocarbyl substituted gallium or zinc compounds) as described in US 2008/0269412 Al.
  • olefin polymerizing conditions independently refer to reaction conditions such as solvent(s), atmosphere(s), temper ature(s), pressure(s), time(s), and the like that are preferred for giving at least a 10 percent (%), more preferably at least 20%, and still more preferably at least 30% reaction yield of the polyolefin or poly(olefin monomer-olefin comonomer) block copolymer after 15 minutes reaction time.
  • the polymerization processes independently are run under an inert atmosphere (e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof).
  • inert atmosphere e.g., under an inert gas consisting essentially of, for example, nitrogen gas, argon gas, helium gas, or a mixture of any two or more thereof.
  • Other atmospheres are examples of gases, for example, nitrogen gas, argon gas, helium gas, or a mixture of any
  • the polymerization processes independently are run without any solvent, i.e., is a neat polymerization process that is run in a neat mixture of aforementioned ingredients.
  • the neat mixture further contains additional ingredients (e.g., catalyst stabilizer such as triphenylphosphine) other than solvent(s).
  • the polymerization processes independently are run with a solvent or mixture of two or more solvents, i.e., is a solvent-based process that is run as a solvent-containing mixture of aforementioned ingredients, and at least one solvent, e.g., an aprotic solvent, more preferably a hydrocarbon solvent (e.g., isoparaffinic hydrocarbons, toluene, dodecane, mesitylene, or a mixture thereof).
  • the polymerization process is run at a temperature of the reaction ingredients of from 0 °C to about 200 °C, and more preferably from 20 °C to about 190 °C.
  • the temperature is at least 30 °C, and more preferably at least 40 °C. In other embodiments, the temperature is 175 °C or lower, more preferably 150 °C or lower, and still more preferably 140 °C or lower.
  • a convenient temperature is about from 60 °C to 100 °C, and more preferably from 80 °C to 90 °C.
  • the polymerization processes independently run under a pressure of about 1000 pounds per square inch (psi) or less, i.e., about 70 atmospheres (atm) or 7000 kilopascals (kPa), or less.
  • the polymerization processes independently run under a pressure of from about about 91 kiloPascals (kPa) to about 5000 kPa.
  • a convenient pressure is from 3000 kPa to 4900 kPa.
  • the olefin polymerization can be substantially slowed, halted or stopped without quenching the polyolefinyl-aluminum compound once a desired composition or average molecular weight of the polyolefinyl portion thereof is reached (e.g., as determined based on past experience such as reaction time and temperature and catalyst or by characterization of an aliquot removed therefrom).
  • the stopping without quenching comprises adding a poisoning effective amount of a catalyst poisoning agent to the olefin polymerization reaction mixture.
  • the catalyst poisoning agent is molecule lacking an acidic hydrogen atom (e.g., lacking H-O, H-N, or H-S moiety) that contains a functional moiety effective for causing a substantial slowing or stopping of rate of polymerization.
  • the catalyst poisoning agent is 1,3,7-octatriene, which can react with the coordination catalyst without disrupting the polyolefinyl-aluminum bond.
  • the poisoning effective amount is a quantity sufficient to slow or stop the polymerization.
  • any polyolefinyl of the polyolefinyl-aluminum compound and the polyolefin block used herein can be obtained from a commercial source or readily prepared using at least one of the aforementioned ad rem methods.
  • the polyolefinyl-aluminum compound can be contacted with the acyclic polysiloxane or cyclic siloxane monomer under the coupling effective conditions and in such a way so as to give the polyolefin-polysiloxane block copolymer according to the invention process.
  • the polyolefinyl-aluminum compound can be prepared in situ, and then the acyclic polysiloxane or cyclic siloxane monomer can be contacted therewith.
  • the reaction between the polyolefinyl-aluminum compound and the acyclic polysiloxane or cyclic siloxane monomer is believed to be a thermal reaction that is facilitated by heating.
  • the acyclic polysiloxane (i.e., material of formula (P)) is a discrete molecule having a formula weight of from >230 g/mol to 2,000 g/mol. In other embodiments, it is a mixture of molecules and has a weight average molecular weight (M w ) of >2,000 g/mol, >5,000 g/mol, >10,000 g/mol, or >50,000 g/mol; and ⁇ 10,000,000 g/mol, ⁇ 5,000,000 g/mol, or ⁇ 2,000,000 g/mol. More preferably, the acyclic polysiloxane is the mixture of molecules having M w of from 100,000 g/mol to 1,000,000 g/mol.
  • the M w of the acyclic polysiloxane is determined according to the procedure described later.
  • a preferred acyclic polysiloxane is polydimethylsiloxane (also referred to as dimethylpolysiloxane or dimethicone), still more preferably a polydimethylsiloxane that has a weight average molecular weight of from 100,000 g/mol to 1,000,000 g/mol.
  • the polydimethylsiloxane is end-capped.
  • the acyclic polysiloxane is a linear polysiloxane and in other embodiments a branched polysiloxane.
  • the acyclic polysiloxane is an end-capped acyclic polysiloxane, which is end- capped with a functional group that does not react with an alkylaluminum during the invention process.
  • end-capped acyclic polysiloxane means that at least two, and preferably each, of the terminal silicon atoms of the acyclic polysiloxane are bonded to 1 oxygen atom and 3 carbon atoms. (The linear end-capped acyclic polysiloxane has only 2 terminal silicon atoms.) Examples of such end-cap functional groups are methyl, ethyl, trimethylsilyl and vinyl.
  • Examples of such end-capped acyclic polysiloxanes are ethyl-polysiloxane -ethyl, trimethylsilyl- polysiloxane-methyl, trimethylsilyl-polysiloxane-trimethylsilyl, and vinyl-polysiloxane -vinyl.
  • the end-cap functional groups of the end-capped acyclic polysiloxane can be directly covalently bonded to a terminating silicon atom (not counting any silicon atom in the end-cap functional group) in the acyclic polysiloxane or bonded to the terminating silicon atom via a linking moiety (e.g., -O- or -O- C(O)-O).
  • the cyclic siloxane monomer comprises the compound of formula (O) wherein in some embodiments the ring is monocyclic and in other embodiments the ring is polycyclic (e.g., bicyclic, fused bicyclic, or tricyclic).
  • c is 3, 4, or 5, and more preferably 3.
  • the coupling process advantageously enables building M w of the polysiloxane block by growing a polysiloxane chain off of the polyolefinyl of the polyolefinyl-aluminum compound, typically under coupling effective conditions comprising a coupling temperature of from 100 °C to 200 °C.
  • the acyclic polysiloxane and cyclic siloxane monomer can be prepared or obtained from a commercial supplier.
  • the acyclic polysiloxane and cyclic siloxane monomer can be readily prepared by chemistry long known in the art.
  • linear acyclic polysiloxanes can be prepared from dichlorodi(R x )silanes (or diacetoxydi(R x )silanes) and branched acyclic polysiloxanes can be prepared from trichloro(R x )silanes following a procedure analogous to the procedure using dichlorodi(R x )silanes.
  • the linear acyclic polysiloxane material of formula (P) can be prepared by reacting x+y+2 moles of a
  • a diacetoxydi(R x )silane of formula Si(R x )2(0 2 CCH 3 )2 can be used in place of the dichlorodi(R x )silane.
  • the reactions generate HC1 or acetic acid as by-products, which along with unreacted starting materials and volatile Si-containing intermediates can be removed from the linear acyclic polysiloxane product by a method known in the art such as aqueous base extraction (e.g., washing with aqueous sodium hydroxide) or evaporation of the HC1 or acetic acid in vacuo.
  • the dichlorodi(R x )silane or diacetoxydi(R x )silane can be obtained from a commercial source or prepared from a suitable starting material (e.g., silicon tetrachloride or silicon tetraacetate, respectively, which are commercially available from the Sigma-Aldrich Company) by a method known in the art.
  • a suitable starting material e.g., silicon tetrachloride or silicon tetraacetate, respectively, which are commercially available from the Sigma-Aldrich Company
  • dichlorodi(R x )silanes that include dichlorodimethylsilane, dichloro(methyl)phenylsilane, dichloro(methyl)propylsilane, dichloro-methyl-octadecylsilane, and bis(pentachlorophenyl)dichlorosilane can be obtained from the Sigma-Aldrich Company.
  • dichlorodi(R x )silanes can be prepared by contacting silicon tetrachloride with 2 mole equivalents of a suitable organolithium (e.g., phenyl lithium, vinyl lithium, allyl lithium, benzyl lithium, or ethyl lithium) in an anhydrous solvent (e.g., tetrahydrofuran or toluene) under an inert gas atmosphere (e.g., atmosphere of nitrogen or argon gas) at a temperature of from -78 °C to 25 °C to give dichlorosilane, which can be purified if desired by distillation in vacuo.
  • a suitable organolithium e.g., phenyl lithium, vinyl lithium, allyl lithium, benzyl lithium, or ethyl lithium
  • anhydrous solvent e.g., tetrahydrofuran or toluene
  • an inert gas atmosphere e.g., atmosphere of nitrogen or
  • the dichlorodi(R x )silane is also useful for preparing the cyclic siloxane monomers according to the method described in US 3,110,720.
  • the trichloro(R x )silanes can be used in place of the aforementioned
  • the diacetoxydi(R x )silane can be prepared from the corresponding dichlorodi(R x )silane by contacting the dichlorodi(R x )silane with 2 mole equivalents of a Group 1 metal acetate (e.g., lithium acetate) in an anhydrous solvent under an inert gas atmosphere at a temperature of from -78 °C to 100 °C to give the diacetoxydi(R x )silane, which can be purified if desired by distillation in vacuo.
  • a Group 1 metal acetate e.g., lithium acetate
  • the M w of the acyclic polysiloxane (linear or branched) product can be controlled by adjusting reaction time and temperature so as to give linear acyclic polysiloxanes of formula (P) wherein the sum of x + y is a low number (e.g., the sum of x + y is an average number of from 3 to 30); wherein the sum of x + y is a high number (e.g., the sum of x + y is an average of from 1,000 to 150,000); or wherein the sum of x + y is an intermediate number (e.g., the sum of x + y is an average of from 100 to 1,000).
  • P linear acyclic polysiloxanes of formula (P) wherein the sum of x + y is a low number (e.g., the sum of x + y is an average number of from 3 to 30); wherein the sum of x + y is a high number (e.g., the sum of
  • any acyclic polysiloxane or cyclic siloxane monomer used herein can be obtained from a commercial source or readily prepared using at least one of the aforementioned ad rem methods.
  • the end-capped acyclic polysiloxanes comprising the end-cap functional groups that are directly covalently bonded to the terminating silicon atom can be prepared, for example, by polymerizing the aforementioned dichlorosilane with water as described previously for the preparation of the acyclic polysiloxane, wherein in addition the polymerization reaction further employs an end-capping amount of a monochlorosilane such as, for example, chlorotrimethylsilane, chlorotriethylsilane, chlorodimethylvinylsilane.
  • the end-capped acyclic polysiloxanes comprising the end-cap functional groups that are bonded to the terminating silicon atom via a linking moiety can be prepared from, for example, hydroxy terminated acyclic polysiloxanes.
  • the terminal hydroxyl groups of the hydroxy terminated acyclic polysiloxanes can be end capped by reaction with a suitable end capping reactant such as, for example, methyl iodide, ethyl iodide,
  • hydroxy terminated acyclic polysiloxanes can be prepared as described previously (e.g., see US 4,990,555).
  • the polydimethylsiloxane has CAS number 68083-19-2 and a M n 72,800 g/mol or has CAS number 9016-00-6 and M w 300,000 g/mol to 350,000 g/mol.
  • Catalyst (Al) was prepared as described in Example 1 of US 2004/0220050 Al.
  • DSC Differential scanning calorimetry
  • BHT butylated hydroxytoluene
  • GPC Method 2 In a capped vial with a stir bar, stir and dissolve samples for 90 minutes at 160 °C at a concentration of 30 mg/mL in 1 ,2,4-trichlorobenzene (TCB) stabilized by 300 ppm BHT. Then dilute solutions to Img/mL concentration, and then immediately remove and inject a 400 aliquot of the sample into the GPC instrument. Use two (2) Polymer Labs PLgel 10 ⁇ MIXED- B columns (300 mm x 10 mm) at a flow rate of 2.0 mL/minute at 150 °C. Detect sample using a
  • PolyChar IR4 detector in concentration mode Use a conventional calibration of narrow Polystyrene (PS) standards with apparent units adjusted to homopolyethylene (PE) using known Mark-Houwink coefficients for polystyrene and polyethylene in TCB at this temperature. Calculate absolute M w using a PDI static low-angle light scatter detector.
  • PS Polystyrene
  • PE homopolyethylene
  • Spectroscopy FT-IR
  • Polymer density Dissolve samples to at a concentration of 30 mg/mL in 1 ,2,4-trichlorobenzene at 160 °C for 1 hour while shaking. Deposit the 160 °C solution into individual cells on a silicon wafer, and evaporate the solution. Cool the residual polymer to room temperature. Analyze the wafer using a Nicolet Nexus 670 FT-IR ESP infrared spectrometer to determine mol octene within each sample.
  • FT-IR Spectroscopy
  • TEM Transmission electron microscopy: Place sample (typically a white paste) on a glass slide to form a film, and heat film in vacuum oven at 80 °C to remove any excess solvent and to allow the polymeric material of the sample to anneal to form an equilibrium structure. After 24 hours of heating, lower temperature to 35 °C, and maintain vacuum for 2 to 3 days. The sample remains a paste. Place a portion of the paste on a cryo-pin, and section the paste to 100 nanometer (nm) thickness using a Lecia Ultracryomicrotome at -120 °C. Place the resulting thin sections of unexposed paste onto a TEM carbon support grid, and characterize it using a JEOL 1230 transmission electron microscope.
  • TEM Transmission electron microscopy
  • Example 1 polyoctene-polydimethylsiloxane block copolymer.
  • Triethylaluminum 140 mg
  • a glass jar 120 mL
  • a poly(tetrafluoroethylene) (PTFE) coated stir bar then toluene (20 mL) followed by 1-octene (3 mL).
  • PTFE poly(tetrafluoroethylene)
  • Examples 2 and 3 polyethylene-polydimethylsiloxane block copolymers.
  • TAA triethylaluminum
  • Catalyst Efficiency catalyst efficiency calculated by dividing weight of high density polyethylene (HDPE) product by weight of the hafnium metal of Catalyst (Al).
  • Step (b) Dilute polydimethylsiloxane (PDMS, CAS number 9016-00-6, and M w 300,000 g/mol to 350,000 g/mol) in toluene (to ease handling), then add the diluted PDMS via the catalyst shot tank to the reactor, seal, and stir the resulting reaction mixture in the sealed reactor for 17 hours at 180 °C. Cool reactor contents, and empty reactor contents to the dump pot. Pour contents of the dump pot into trays placed in a lab hood, and allow the solvent to evaporate off overnight. Dry in a vacuum oven, and heat them under vacuum to remove any remaining solvent. Cool and weigh the final product for determining reaction yield and catalyst efficiency.
  • PDMS polydimethylsiloxane
  • the present invention has the uses and advantages described previously herein, especially those listed in the Brief Summary of the Present Invention.
  • the polyolefinyl-aluminum compound and invention process are useful with either the acyclic polysiloxane or cyclic siloxane monomer, or a mixture thereof for preparing the invention polyolefin-polysiloxane block copolymer.
  • the polyolefin-polysiloxane block copolymer can be used, for example, as an adhesive and can, if desired, be prepared as a manufactured article or as a portion thereof.

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Abstract

La présente invention concerne de façon générale un procédé de fabrication d'un copolymère séquencé à base de polyoléfine-polysiloxane, un copolymère séquencé à base de polyoléfine-polysiloxane fabriqué par le procédé, et un article comprenant le copolymère séquencé à base de polyoléfine-polysiloxane. Le procédé consiste de façon générale à coupler un composé polyoléfinyl-aluminium avec un monomère polysiloxane acyclique ou un monomère siloxane cyclique pour donner un copolymère séquencé à base de polyoléfine-polysiloxane.
PCT/US2012/022348 2011-01-26 2012-01-24 Procédé de fabrication d'un copolymère séquencé à base de polyoléfine-polysiloxane WO2012103080A1 (fr)

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Citations (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2571884A (en) 1950-07-19 1951-10-16 Dow Corning Method of preparing chlorosiloxanes
US2580852A (en) 1946-01-11 1952-01-01 Shaw Clifford Preparation of siloxanes by reacting dialkyldichlorosilanes with cupric oxide
US2629726A (en) 1950-07-19 1953-02-24 Dow Corning Method of preparing halosiloxanes
US2853504A (en) 1955-05-05 1958-09-23 Kali Chemie Ag Alkylation of organopolysiloxanes using a hydrocarbon aluminum compound
US3110720A (en) 1960-11-01 1963-11-12 Union Carbide Corp Process for producing cyclic diorganosiloxanes from diorganodihalosilanes and alkaliand alkali earth metal oxides and carbonates
DD152136A1 (de) * 1980-07-14 1981-11-18 Klaus Prof Dr Rer Na Ruehlmann Verfahren zur stabilisierung von polymeren durch zumischen von polymeren antioxydanzien
US4578494A (en) 1985-06-14 1986-03-25 Dow Corning Corporation Preparation of polysiloxanes from halosilanes
US4990555A (en) 1987-10-24 1991-02-05 Dow Corning S.A. Preparation of hydroxy terminated polysiloxanes
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5169900A (en) 1988-08-05 1992-12-08 Du Pont Canada Inc. Polyolefin coatings and films having release characteristics
US5229179A (en) 1989-08-14 1993-07-20 Minnesota Mining And Manufacturing Company General purpose siloxane release coatings
WO1994000500A1 (fr) 1992-06-26 1994-01-06 Exxon Chemical Patents Inc. Procede de polymerisation en solution utilisant un catalyseur metallocene pour la production de polymeres olefiniques
US5296433A (en) 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
US5321106A (en) 1990-07-03 1994-06-14 The Dow Chemical Company Addition polymerization catalyst with oxidative activation
US5350723A (en) 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5425872A (en) 1993-06-24 1995-06-20 The Dow Chemical Company Electrochemical preparation of addition polymerization catalysts
US5470993A (en) 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
US5625087A (en) 1994-09-12 1997-04-29 The Dow Chemical Company Silylium cationic polymerization activators for metallocene complexes
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5728469A (en) 1995-06-06 1998-03-17 Avery Dennison Corporation Block copolymer release surface for pressure sensitive adhesives
US5783512A (en) 1996-12-18 1998-07-21 The Dow Chemical Company Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same
US5866704A (en) 1996-12-19 1999-02-02 The Dow Chemical Company 3-aryl substituted indenyl containing metal complexes and polymerization process
US5883204A (en) 1996-03-27 1999-03-16 The Dow Chemical Company Solution polymerization process with dispersed catalyst activator
US5919983A (en) 1996-03-27 1999-07-06 The Dow Chemical Company Highly soluble olefin polymerization catalyst activator
US6015868A (en) 1996-10-03 2000-01-18 The Dow Chemical Company Substituted indenyl containing metal complexes and olefin polymerization process
US6034022A (en) 1996-12-19 2000-03-07 The Dow Chemical Company Fused ring substituted indenyl metal complexes and polymerization
US6103657A (en) 1997-07-02 2000-08-15 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6150297A (en) 1997-09-15 2000-11-21 The Dow Chemical Company Cyclopentaphenanthrenyl metal complexes and polymerization process
US6268444B1 (en) 1996-08-08 2001-07-31 Dow Chemical Company 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
WO2002002577A1 (fr) 2000-06-30 2002-01-10 Dow Global Technology Inc. Composes polycycliques a cycles accoles, complexes metalliques et procede de polymerisation
WO2002038628A2 (fr) 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
WO2002092610A1 (fr) 2001-05-14 2002-11-21 Dow Global Technologies Inc. Complexes metalliques a substitution aryle en 3, et processus de polymerisation
US20030004286A1 (en) 1999-12-10 2003-01-02 Jerzy Klosin Alkaryl-substituted Group 4 metal complexes, catalysts and olefin polymerization process
US6515155B1 (en) 1999-12-10 2003-02-04 Dow Global Technologies Inc. Substituted group 4 metal complexes, catalysts and olefin polymerization process
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
WO2003040195A1 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Catalyseurs sur support utilises pour produire des polymeres
WO2003078483A1 (fr) 2002-03-14 2003-09-25 Dow Global Technologies Inc. Complexes metalliques a substitution indenyle et procede de polymerisation
WO2003078480A2 (fr) 2002-03-14 2003-09-25 Dow Global Technologies Inc. Composes polycycliques a heterocycles fusionnes, complexes metalliques et procede de polymerisation
US6696379B1 (en) 1997-09-19 2004-02-24 The Dow Chemical Company Supported modified alumoxane catalyst activator
US20040220050A1 (en) 2003-05-02 2004-11-04 Frazier Kevin A. High activity olefin polymerization catalyst and process
WO2005073283A1 (fr) 2004-01-22 2005-08-11 Dow Global Technologies Inc. Compositions elastomeres fonctionnalisees
WO2005090425A1 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Compositions catalytiques de formation de copolymeres d'ethlyene contenant un agent navette
WO2005090426A1 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Composition catalytique contenant un agent navette permettant une formation superieure de copolymeres multiblocs d'olefines
WO2005090427A2 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Composition de catalyseur comportant un agent de transfert pour la formation de copolymere d'ethylene multibloc
US20060199930A1 (en) 2004-03-17 2006-09-07 Dow Global Technologies Inc. Ethylene/alpha-olefins block interpolymers
WO2006101595A1 (fr) 2005-03-17 2006-09-28 Dow Global Technologies Inc. Composition catalytique comprenant un agent navette pour la formation d'un copolymere multiblocs a regions irregulieres
US7163907B1 (en) 1987-01-30 2007-01-16 Exxonmobil Chemical Patents Inc. Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization
WO2007035492A1 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Copolymeres blocs olefiniques catalytiques obtenus par l'intermediaire d'un agent navette polymerisable
WO2007035485A1 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Copolymeres sequences d'olefines catalytiques a distribution de sequences par blocs commandee
WO2007035493A2 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Regulation de l'architecture et de la distribution du poids moleculaire des polymeres par le biais d'un agent navette multicentre
WO2008027283A2 (fr) 2006-08-25 2008-03-06 Dow Global Technologies Inc. Production de copolymères métabloc par échange de segments polymères
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
WO2009012215A1 (fr) 2007-07-13 2009-01-22 Dow Global Technologies Inc. INTERPOLYMÈRES ÉTHYLÈNE/α-OLÉFINE CONTENANT DES BLOCS DURS DE FAIBLE CRISTALLINITÉ
WO2009097565A1 (fr) 2008-01-30 2009-08-06 Dow Global Technologies Inc. INTERPOLYMÈRES BLOCS D'ÉTHYLÈNE/α-OLÉFINE
US20100298515A1 (en) 2008-01-30 2010-11-25 Dow Global Technologies Inc. Ethylene/alpha-olefin block copolymers

Patent Citations (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2580852A (en) 1946-01-11 1952-01-01 Shaw Clifford Preparation of siloxanes by reacting dialkyldichlorosilanes with cupric oxide
US2571884A (en) 1950-07-19 1951-10-16 Dow Corning Method of preparing chlorosiloxanes
US2629726A (en) 1950-07-19 1953-02-24 Dow Corning Method of preparing halosiloxanes
US2853504A (en) 1955-05-05 1958-09-23 Kali Chemie Ag Alkylation of organopolysiloxanes using a hydrocarbon aluminum compound
US3110720A (en) 1960-11-01 1963-11-12 Union Carbide Corp Process for producing cyclic diorganosiloxanes from diorganodihalosilanes and alkaliand alkali earth metal oxides and carbonates
DD152136A1 (de) * 1980-07-14 1981-11-18 Klaus Prof Dr Rer Na Ruehlmann Verfahren zur stabilisierung von polymeren durch zumischen von polymeren antioxydanzien
US4578494A (en) 1985-06-14 1986-03-25 Dow Corning Corporation Preparation of polysiloxanes from halosilanes
US7163907B1 (en) 1987-01-30 2007-01-16 Exxonmobil Chemical Patents Inc. Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization
US5153157A (en) 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US4990555A (en) 1987-10-24 1991-02-05 Dow Corning S.A. Preparation of hydroxy terminated polysiloxanes
US5169900A (en) 1988-08-05 1992-12-08 Du Pont Canada Inc. Polyolefin coatings and films having release characteristics
US5229179A (en) 1989-08-14 1993-07-20 Minnesota Mining And Manufacturing Company General purpose siloxane release coatings
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5321106A (en) 1990-07-03 1994-06-14 The Dow Chemical Company Addition polymerization catalyst with oxidative activation
US5721185A (en) 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
US5296433A (en) 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
US5350723A (en) 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
WO1994000500A1 (fr) 1992-06-26 1994-01-06 Exxon Chemical Patents Inc. Procede de polymerisation en solution utilisant un catalyseur metallocene pour la production de polymeres olefiniques
US5425872A (en) 1993-06-24 1995-06-20 The Dow Chemical Company Electrochemical preparation of addition polymerization catalysts
US5470993A (en) 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
US5625087A (en) 1994-09-12 1997-04-29 The Dow Chemical Company Silylium cationic polymerization activators for metallocene complexes
US5728469A (en) 1995-06-06 1998-03-17 Avery Dennison Corporation Block copolymer release surface for pressure sensitive adhesives
US5883204A (en) 1996-03-27 1999-03-16 The Dow Chemical Company Solution polymerization process with dispersed catalyst activator
US5919983A (en) 1996-03-27 1999-07-06 The Dow Chemical Company Highly soluble olefin polymerization catalyst activator
US6268444B1 (en) 1996-08-08 2001-07-31 Dow Chemical Company 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
US6015868A (en) 1996-10-03 2000-01-18 The Dow Chemical Company Substituted indenyl containing metal complexes and olefin polymerization process
US5783512A (en) 1996-12-18 1998-07-21 The Dow Chemical Company Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same
US6034022A (en) 1996-12-19 2000-03-07 The Dow Chemical Company Fused ring substituted indenyl metal complexes and polymerization
US5866704A (en) 1996-12-19 1999-02-02 The Dow Chemical Company 3-aryl substituted indenyl containing metal complexes and polymerization process
US6103657A (en) 1997-07-02 2000-08-15 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6320005B1 (en) 1997-07-02 2001-11-20 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers
US6150297A (en) 1997-09-15 2000-11-21 The Dow Chemical Company Cyclopentaphenanthrenyl metal complexes and polymerization process
US6696379B1 (en) 1997-09-19 2004-02-24 The Dow Chemical Company Supported modified alumoxane catalyst activator
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
US20030004286A1 (en) 1999-12-10 2003-01-02 Jerzy Klosin Alkaryl-substituted Group 4 metal complexes, catalysts and olefin polymerization process
US6515155B1 (en) 1999-12-10 2003-02-04 Dow Global Technologies Inc. Substituted group 4 metal complexes, catalysts and olefin polymerization process
WO2002002577A1 (fr) 2000-06-30 2002-01-10 Dow Global Technology Inc. Composes polycycliques a cycles accoles, complexes metalliques et procede de polymerisation
WO2002038628A2 (fr) 2000-11-07 2002-05-16 Symyx Technologies, Inc. Ligands de pyridylamine substitues, complexes, catalyseurs et procedes pour la polymerisation, et polymeres
WO2002092610A1 (fr) 2001-05-14 2002-11-21 Dow Global Technologies Inc. Complexes metalliques a substitution aryle en 3, et processus de polymerisation
WO2003040195A1 (fr) 2001-11-06 2003-05-15 Dow Global Technologies Inc. Catalyseurs sur support utilises pour produire des polymeres
WO2003078480A2 (fr) 2002-03-14 2003-09-25 Dow Global Technologies Inc. Composes polycycliques a heterocycles fusionnes, complexes metalliques et procede de polymerisation
WO2003078483A1 (fr) 2002-03-14 2003-09-25 Dow Global Technologies Inc. Complexes metalliques a substitution indenyle et procede de polymerisation
US20040220050A1 (en) 2003-05-02 2004-11-04 Frazier Kevin A. High activity olefin polymerization catalyst and process
WO2005073283A1 (fr) 2004-01-22 2005-08-11 Dow Global Technologies Inc. Compositions elastomeres fonctionnalisees
US20090186985A1 (en) 2004-01-22 2009-07-23 Kuhlman Roger L Functionalized elastomer compositions
US20070167315A1 (en) 2004-03-17 2007-07-19 Arriola Daniel J Catalyst composition comprising shuttling agent for ethylene copolymer formation
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7858706B2 (en) * 2004-03-17 2010-12-28 Dow Global Technologies Inc. Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
WO2005090427A2 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Composition de catalyseur comportant un agent de transfert pour la formation de copolymere d'ethylene multibloc
WO2005090425A1 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Compositions catalytiques de formation de copolymeres d'ethlyene contenant un agent navette
US20080311812A1 (en) 2004-03-17 2008-12-18 Arriola Daniel J Catalyst Composition Comprising Shuttling Agent for Higher Olefin Multi-Block Copolymer Formation
US20060199930A1 (en) 2004-03-17 2006-09-07 Dow Global Technologies Inc. Ethylene/alpha-olefins block interpolymers
WO2005090426A1 (fr) 2004-03-17 2005-09-29 Dow Global Technologies Inc. Composition catalytique contenant un agent navette permettant une formation superieure de copolymeres multiblocs d'olefines
US20070167578A1 (en) 2004-03-17 2007-07-19 Arriola Daniel J Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
US20080262175A1 (en) 2005-03-17 2008-10-23 Arriola Daniel J Catalyst Composition Comprising Shuttling Agent for Regio-Irregular Multi-Block Copolymer Formation
WO2006101595A1 (fr) 2005-03-17 2006-09-28 Dow Global Technologies Inc. Composition catalytique comprenant un agent navette pour la formation d'un copolymere multiblocs a regions irregulieres
WO2007035493A2 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Regulation de l'architecture et de la distribution du poids moleculaire des polymeres par le biais d'un agent navette multicentre
US20080269412A1 (en) 2005-09-15 2008-10-30 Dow Global Technologies Inc. Catalytic Olefin Block Copolymers with Controlled Block Sequence Distribution
US20080275189A1 (en) 2005-09-15 2008-11-06 Dow Global Technologies Inc. Control of Polymer Architecture and Molecular Weight Distribution Via Multi-Centered Shuttling Agent
WO2007035485A1 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Copolymeres sequences d'olefines catalytiques a distribution de sequences par blocs commandee
WO2007035492A1 (fr) 2005-09-15 2007-03-29 Dow Global Technologies Inc. Copolymeres blocs olefiniques catalytiques obtenus par l'intermediaire d'un agent navette polymerisable
US7858707B2 (en) 2005-09-15 2010-12-28 Dow Global Technologies Inc. Catalytic olefin block copolymers via polymerizable shuttling agent
WO2008027283A2 (fr) 2006-08-25 2008-03-06 Dow Global Technologies Inc. Production de copolymères métabloc par échange de segments polymères
US20100069573A1 (en) 2006-08-25 2010-03-18 Dow Global Technologies Inc. Production of meta-block copolymers by polymer segment interchange
WO2009012215A1 (fr) 2007-07-13 2009-01-22 Dow Global Technologies Inc. INTERPOLYMÈRES ÉTHYLÈNE/α-OLÉFINE CONTENANT DES BLOCS DURS DE FAIBLE CRISTALLINITÉ
WO2009097565A1 (fr) 2008-01-30 2009-08-06 Dow Global Technologies Inc. INTERPOLYMÈRES BLOCS D'ÉTHYLÈNE/α-OLÉFINE
US20100298515A1 (en) 2008-01-30 2010-11-25 Dow Global Technologies Inc. Ethylene/alpha-olefin block copolymers

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NOSHAY; MCGRATH: "Block Copolymers", 1977, ACADEMIC PRESS, pages: 156 - 162
RANDALL, J.C., JMS-REV. MACROMOL. CHEM. PHYS., vol. C29, 1989, pages 201 - 317

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