CN104736575A - Metal polymeryls and the polymer solubilized surfaces derived therefrom - Google Patents
Metal polymeryls and the polymer solubilized surfaces derived therefrom Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
Abstract
Disclosed herein are certain propylene-based metal polymerals and their use in modifying surfaces, and, in general, metal polymerals used in modifying surfaces. In one aspect is a metal polymeryl comprising compounds having the general formula: MR3-nR'n; wherein each R group is a hydrogen or C1 to C10 or C20 alkyl, and each R' group is selected from propylene-based polymers having an Mn of at least 300 g/mol; n is 1, 2, or 3; and M is a Group 12 or 13 metal, preferably aluminum or zinc; wherein the first portion of the R' group bound to the metal M is a- CH2CH2- group, and the terminal portion of the R group is isobutyl. Surfaces that are modified or "solubilized" include particles of silica or alumina, glass, metal, clay and other hydroxyl-containing materials of all sizes.
Description
Contriver: Matthew W.Holtcamp, Patrick Brant, Donna J.Crowther, John R.Hagadorn, and Gregory S.Day
The cross reference of related application
This application claims the provisional application No.61/740 submitted on December 20th, 2012, the rights and interests of the EP 13162542.8 that on April 5th, 169 and 2013 submits to.
Invention field
The present invention relates in general to the reaction between the solid of hydroxyl and polymer-based metal, more particularly relates to and forms polymer-based metal by the polypropylene of ethenyl blocking and form the solid surface comprising hydroxyl of polymer-based carbon modification.
Background of invention
Seek a kind of simple, cheap coupling approach, thus form the nano composite material of easy good distribution and pigment and other solid reagent to improve polyolefin properties or to bring key property.Especially, expect solid material such as silicon-dioxide or aluminum oxide are combined with polymkeric substance such as polyolefine and form good mixing or " solubilsed " system, be similar to what is called " polymer brush ", " the Polymer Brushes " of S.T.Milner, 251Science 905-914 (1991).This contriver finds, by forming polymer-based metal and define such system, this polymer-based metal can react with the solid of hydroxyl (or surface) with modification or the such surface of solubilising.Expect that method that is such and that be correlated with can provide the competitive of silane coupling chemistry to substitute.
Related art comprises U.S. Patent Application Publication No.2011/0028654; The people such as I.Tritto. " Evidence of Zirconium-Polymeryl Ion pairsfrom
13c NMR in situ
13c
2h
4polymerization withCp
2zr (
13cH
3)
2-Based Catalysts ", 32Macromolecules 264-269 (1999); " the Polymeryl Exchange betweenansa-Zirconocene Catalysts for Norbornene-EtheneCopolymerization and Aluminum or Zinc Alkyls " of the people such as N.Bhriain, 38Macromolecules 2056-2063 (2005); " the Chaintransfer to Aluminum in MAO-activated Metallocene-catalyzedPolymerization Reactions " of the people such as E.Quintanilla, Chem.Commun.4309-4311 (2006); " the Modeling of α-olefin Copolymerization withChain-Shuttling Chemistry Using Dual Catalysts inStirred-Tank Reactors:Molecular Weight Distributions andCopolymer Compositions " of the people such as M.Zhang, 49Ind.Eng.Chem.Res.8135-8146 (2010); " the In Situ Catalytic Encapsulation ofCore-Shell Nanoparticles Having Variable Shell Thickness:Dielectric and Energy Storage Propert ies ofHigh-Permittivity Metal Oxide Nanocomposites " of the people such as Z.Li, 22Chem.Mater.5154-5164 (2010); And " the Zirconium-Catalyzed Carboalumination of α-olefins andChain Growth of Aluminum Alkyls:Kinetics and Mechanism " of the people such as J.M.Camara, 133J.Am.Chem.Soc.5263-5273 (2011).
Summary of the invention
The invention disclosed herein comprises some specifically based on the metal-containing polymer material (polymeral) of propylene and their purposes in modified surface, and in general, for the metal-containing polymer material on modification or " solubilising " surface.Therefore, inventors have discovered that a kind of polymer-based metal, it comprises the compound with following general formula: MR
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is selected from Mn is at least 300 grams/polymkeric substance based on propylene that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc; Wherein be connected to the first part of the R ' group of described metal M for-CH
2cH
2-group, and the end bit position of R ' group is isobutyl-.
Further disclose the surface " S " of solubilize polymers, it comprises multiple hydroxyl (" S-OH "), and wherein at least one hydroxyl is the S-O-MR according to following formula modification
2-nr'
n, wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1 or 2; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.
And disclosing the surface of solubilize polymers, it comprises following reaction product: the surface and the polymer-based metal MR that comprise hydroxylic moiety
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.
And disclose the method preparing polymer-based metal, comprising: be at least 300 grams by the Mn of ethenyl blocking/polymkeric substance based on propylene that rubs and MR
3merge; Wherein each R group is independently selected from hydrogen or C
1-C
10alkyl, M is the 12nd or 13 race's metals, preferred aluminium or zinc; And be separated the polymer-based metal with following structure: MR
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is the described polymkeric substance based on propylene; N is 1,2 or 3; Wherein be connected to the first part of the R ' group of described metal M for-CH
2cH
2-group, and the end bit position of R ' group is isobutyl-.
Further, finally, disclose the method on the surface of preparing polymkeric substance solubilising, comprising the Mn of ethenyl blocking is polyolefine and the MR of at least 300g/mol
3merge; Wherein each R group is independently selected from hydrogen or C
1-C
10alkyl, M is the 12nd or 13 race's metals, preferred aluminium or zinc; Be separated the polymer-based metal with following structure: MR
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is described polyolefine; N is 1,2 or 3; Described polymer-based metal and the surface comprising hydroxylic moiety are merged the surface to form polymkeric substance solubilising.
Accompanying drawing explanation
Fig. 1 is the scheme on the surface forming solubilize polymers of the present invention, and wherein said surface is the particle containing oxyhydroxide.
Fig. 2 is suspended in the Cabosil in the polymer melt in comparative example 1 for (1)
tMthe previous shot of silicon-dioxide, with (2) to utilize the photo after the solubilsed identical Cabosil of embodiment 1 polymer-based metal.
Describe in detail
Contriver finds that a kind of will be that solid or insoluble material and polymeric matrix merge with the close blend forming insoluble material and polymkeric substance or " solution " as described herein originally.In the material that solubilising is such, the region being at least exposed to solvent of this material is by the reaction modifying with polymer-based metal.Therefore, this document describes the method on the surface that the solid of solubilize polymers or surface " S " and solubilising are such, this solubilsed surface comprises multiple hydroxyl (" S-OH "), wherein at least one hydroxyl by least one number-average molecular weight (Mn) be at least 300 grams/rub oligopolymer or polymkeric substance (" polymkeric substance ") radicals R ' modification.Rephrase the statement, contriver finds that the surface of polymkeric substance solubilising comprises following reaction product: the surface and the polymer-based metal MR that comprise hydroxylic moiety
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, each R ' group is described polymkeric substance; And M is the 4th, 12 or 13 race's metals, preferred aluminium or zinc, and n is 1,2 or 3.
The polymkeric substance solubilising of this surface or reaction product can with preparation after the polyolefine of former state have in a reactor of in-situ blending ability or two reactors and carry out, or can implement continuously, such as, make inorganic materials carry out chemistry with the polymkeric substance comprising polyolefine in an extruder to fetter.In all cases, the practical benefits of method of the present invention can comprise: the rigidity improving per unit volume filler best, the rigidity-toughness of improvement, the barrier of improvement, resistance to cracking and fracture-resistant, and uniform color divergence.Further, expect that these novel composition can be designed to be dissolved in the viscosity characteristics of also their uniquenesses of susceptible of proof in hydrocarbon liquid.These can be designed to and be used as the new coating under suitable controlled condition, and provide the New Policy to reducing burn into bonding etc.Segmented copolymer should also can based on such method.Expect that the present invention and relevant method provide to substitute the competitive of silane coupling chemistry.
The present invention has many application, although be called on " surface of solubilize polymers ", in fact, polymer-based metal as herein described can be used for applying or otherwise modification still keeps their main body solid form and do not have the surface of " solubilising ".The actual example becoming solubilsed surface in fig. 2, wherein Cabosil
tMsilicon-dioxide is dispersed in the polypropylene of the ethenyl blocking as described in comparative example 1.Fig. 2 (1) visually shows the result of this mixture.In embodiment 1, molten polymer base is added into the suspension of Cabosil, and this suspension immerses molten polymer and bleach along with the silicon-dioxide dispersion suspended, and this is vision display in Fig. 2 (2).The present invention for therefore can be used for following application, such as, forms polymkeric substance/filler nanometer matrix material, and the coating on solid (metal, polymkeric substance, glass etc.) surface is to improve their character, and other application.
As described herein, " solid " or " surface " is such material, it is insoluble to organic thinner, such as hexane, toluene or fused polyolefin, and comprises at least one oh group that can be used for carrying out with polymer-based metal as described herein condensation or substitution reaction.The example on surface comprises (having any size) silicon-dioxide, silica-alumina, aluminum oxide (and spray-dried forms), glass, clay and ceramic particle; Glass fibre or particle; Glass surface; Graphene oxide, carbon black; Calcium carbonate; The polyolefin film of oxidation; Transition metal nanoparticles and metal oxide nanoparticles; And metallic surface.Particularly preferred surface comprises the particle of silicon-dioxide, silica-alumina, aluminum oxide or their mixture, and the median size of described particle is the scope of 1 or 4 or 10 μm to 20 or 50 or 100 μm.In certain embodiments, described surface also can be described as comprising the particle comprising surface hydroxyl part or one or more macro surface that are insoluble to solvent.
As described herein, " polymer-based carbon material " or " polymer-based metal " they are a kind of compounds, it comprises metal and number-average molecular weight is at least 300 grams/and the polymeric groups that rubs.Described metal can be in most of the cases any metal, but preferred the 4th, 12 or 13 race's metal, most preferably aluminium or zinc.Polymer moieties derives from the polymkeric substance of any expectation, this polymkeric substance have on the polymer one or more position, preferably on only have a position to have can to form vinyl or the other parts of chemical bond with metal.The particularly preferred polymkeric substance obtaining polymer-based carbon is the polymkeric substance of ethenyl blocking, and the polymkeric substance based on propylene of ethenyl blocking is most preferred.The polymer-based carbon aluminium deriving from the polymkeric substance based on propylene of ethenyl blocking of the present invention as herein described has Al-CH
2cH
2the feature of (polymkeric substance)
1h NMR signal, and under condition described in an embodiment 0.25 or 0.30 or 0.32 to 0.40 or 0.42 or 0.45ppm (wide region) δ scope in.Once this polymer-based carbon aluminium and oxidant reaction, this Al-OCH
2cH
2the feature of (polymkeric substance)
1under the condition that H NMR signal is described in an embodiment reference deuterate benzene or toluene 3.2 or 3.5 or 3.8 to 4.2 or 4.5 or 4.8ppm (wide region) δ scope in.
As described herein, " polymkeric substance based on propylene " is such polymkeric substance, it comprises and is greater than the unit that 50wt% or 60wt% or 70wt% or 80wt% derives from propylene, preferably comprise the unit that 50wt% or 60wt% or 80wt% to 95wt% or 99wt% or 100wt% derives from propylene, all the other are for deriving from ethene or C
4-C
10the unit of alpha-olefin.The polymkeric substance based on propylene expected comprises homopolymer, multipolymer, elastomerics, impact copolymer, segmented copolymer, isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, and their mixture.These can be ethenyl blocking arbitrarily, as described below, and/or can containing the multiple vinyl groups from polymer chain pendency.
Finally, as described herein, " polyolefine of ethenyl blocking ", " polymkeric substance based on propylene of ethenyl blocking " and other " ethenyl blocking " polymkeric substance are the polymkeric substance as described in U.S. Patent Application Publication No.2009/0318644, and it has the end group (CH that at least one formula (I) represents
2cH-CH
2-oligopolymer or polymkeric substance):
Allyl group formula vinyl ends (I)
Wherein "
" represent described oligopolymer or polymer chain.In a preferred embodiment, allyl chain ends is represented by formula (II):
The amount of allyl chain ends uses
1h NMR uses deuterate tetrachloroethane to determine on 500MHz equipment as solvent at 120 DEG C, and is passing through in some cases
13c NMR confirms.These (I) and (II) group and above-mentioned metal reaction form chemical bond, thus form M-CH
2cH
2-polymkeric substance.In all cases, Resconi distributes to the proton of the propene polymer of ethenyl blocking and carbon that (pure deuterate tetrachloroethane of crossing is used for proton spectra, and common tetrachloroethane and the 50:50 mixture crossing deuterate tetrachloroethane are used for carbon spectrum; All spectrograms record proton when operating under 300MHz on Bruker AM 300 spectrograph for 100 DEG C and record carbon when 75.43MHz operates) be reported in the people such as Resconi, in 114J.Am.Chem.Soc.1025-1032 (1992), this can be used in the present invention.
The polymkeric substance based on propylene of ethenyl blocking also can contain the isobutyl-end of the chain." the isobutyl-end of the chain " is defined as the oligopolymer with the end group that at least one formula (III) represents:
In a preferred embodiment, the isobutyl-end of the chain is represented by one of following formula:
The per-cent of isobutyl cardinal extremity end group uses
13c NMR (as described in embodiment part) determines, and chemical shift distribute as in Resconi to 100% propylene oligomer.Preferably, the polymkeric substance of ethenyl blocking described herein has allyl group formula end group, and has isobutyl-end group in the opposite end of this polymkeric substance.
Therefore, polymer-based carbon material (polymeryl) as herein described can have structure M-CH
2cH
2-polymkeric substance, most preferably M-CH
2cH
2-polymkeric substance isobutyl-, based on the polymkeric substance based on propylene of the polymer-based carbon material of propylene based on ethenyl blocking preferably.When the polymer modification based on propylene with ethenyl blocking, solubilsed surface as herein described will have structure S-CH
2cH
2-polymkeric substance isobutyl-or S-OCH
2cH
2-polymkeric substance isobutyl-, wherein " S " is the surface of hydroxyl.The polymkeric substance based on propylene of ethenyl blocking only can have an end position vinyl groups, but can have multiple vinyl groups in whole polymer chain in some embodiments.
Polymer-based carbon material is not limited to the polymer-based carbon material based on propylene.The solubilsed surface of solvent described herein can be formed by the polymer-based carbon material made with the polymkeric substance of any expectation, the polymkeric substance particularly polyolefine of described expectation, such as polyethylene, branched polyethylene, high density polyethylene(HDPE), straight-chain low density polyethylene, polystyrene, polybutene, ethylene-propylene copolymer, ene-propylene-butene ter-polymers, EPDM ter-polymers, and other alpha-olefin or styrenic homopolymer and multipolymer.When comprising " the polymer-based carbon material " of " polymkeric substance " when mentioning, should understand this polymkeric substance is polymer chain, it has at least one reactive group such as vinyl groups, this group metal reaction is also attached to metal thus, therefore, strictly speaking, described polymer-based carbon material comprises metal and polymeric groups.
Therefore, especially contriver finds that the specific polymkeric substance based on propylene is new.This polymer-based metal comprises the compound with following general formula: MR
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is selected from Mn is at least 300 grams/polymkeric substance based on propylene that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.These first parts based on the R ' group being connected to described metal M in the polymer-based metal material of propylene are-CH
2cH
2-group, and the end bit position of R ' group is isobutyl-.The polymer-based carbon aluminium deriving from the polymkeric substance based on propylene of ethenyl blocking as herein described has Al-C
h 2cH
2the feature of (polymkeric substance)
1h NMR signal, and have under condition described in an embodiment 0.25 or 0.30 or 0.32 to 0.40 or 0.42 or 0.45ppm (wide region) δ scope in.This polymer-based carbon aluminium and oxidant reaction, feature
1h NMR signal Al-OC
h 2cH
2(polymkeric substance) and 3.2 or 3.5 or 3.8 to 4.2 or 4.5 or 4.8ppm (wide region) δ scope in.
Described polymer-based metal, aluminium or other, there is many purposes.Polymer-based carbon material can be formed as metal alkylide or metal alkoxide bunch.In addition, polymer-based carbon material can with comprise the surface bonding of hydroxylic moiety to form modification or solubilsed surface.Characteristic and the situation on surface are not important, can occur to make the reaction between this surface and polymer-based carbon as long as it comprises hydroxyl.Described surface comprises the particle of silicon-dioxide, silica-alumina, aluminum oxide (and spray-dried forms), glass, clay, pottery; Glass fibre; Glass surface; Graphene oxide, carbon black; Calcium carbonate; The polyolefin film of oxidation; And metallic surface, and other is surperficial as described herein.
M-OCH
2cH
2(polymkeric substance) derives from and makes polymer-based metal and oxidant reaction, makes the oxygen in key insert metal center.What oxygenant can be known in the art is suitable for this type of any reagent reacted, and comprises oxygen or amine-N-oxide compound.
The polymkeric substance based on propylene of ethenyl blocking is the homopolymer of propylene, or propylene and ethene or C
4-C
10the multipolymer of alpha-olefin, and be selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, and propylene-ethylene copolymers (random, elastomeric and/or block).Preferably, the Mn value scope of the polymkeric substance based on propylene of ethenyl blocking 300 or 400 or 500 grams/rub to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 gram/rub.
Modification or " solubilsed " surface can be described to the surface " S " comprising multiple hydroxyl (" S-OH ") of polymkeric substance solubilising, wherein at least one hydroxyl is according to following formula modification: S-O-MR
2-nr'
n, wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1 or 2; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.Change a kind of saying, the surface of polymkeric substance solubilising is following reaction product, at least comprises surface and the polymer-based metal MR of hydroxylic moiety
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, preferred R is selected from C
3-C
6alkyl; And each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.This polymkeric substance can be as above based on the polymkeric substance of propylene, or can be in most of the cases the polymkeric substance of other type any.Preferably, R' is selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, polyethylene, ethylene-propylene copolymer, with their combination, they have separately at least 300 grams/Mn that rubs or value scope 300 or 400 or 500 grams/rub to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 gram/Mn that rubs.In some embodiments, the Mn of polymeric groups R' can be low to moderate 100 or 200 grams/rub.
The present inventor has also found the method preparing polymer-based metal, comprises (or being substantially made up of following steps): the polymkeric substance based on propylene of ethenyl blocking and MR
3; Wherein each R group is independently selected from hydrogen or C
1-C
10alkyl, M is the 12nd or 13 race's metals, preferred aluminium or zinc; And be separated the polymer-based metal MR with following structure
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and the Mn based on propylene that each R ' group is ethenyl blocking be at least 300 grams/polymkeric substance that rubs; N is 1,2 or 3; Wherein be connected to the first part of the R ' group of described metal M for-CH
2cH
2-group, and the end bit position of R ' group is isobutyl-.The present inventor also finds, this polymer-based metal can by the reaction with oxygenant such as oxygen or amine-N-oxide compound stabilization.
Once formed, based on propylene polymer-based carbon material can with formation metal alkylide or metal alkoxide bunch other identical or different polymer-based carbon material be combined.In alternate ways, these polymer-based carbon materials based on propylene can with comprise the surface bonding of hydroxylic moiety to form the surface of polymkeric substance solubilising.As mentioned above, R ' group or the polymkeric substance based on propylene are the homopolymer of propylene or propylene and ethene or C
4-C
10the multipolymer of alpha-olefin, and be preferably selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, and propylene-ethylene copolymers (random, elastomeric, anti-impact, and/or block).
The surface of polymkeric substance solubilising is prepared by the following method, comprising: by the polyolefine of ethenyl blocking and MR
3merge; Wherein each R group is independently selected from hydrogen or C
1-C
10alkyl, M is the 12nd or 13 race's metals, preferred aluminium or zinc; Be separated the polymer-based metal MR with following structure
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1,2 or 3; This polymer-based metal and the surface comprising hydroxylic moiety are merged the surface to form polymkeric substance solubilising.Here, polymkeric substance can be any polymkeric substance, as mentioned above, such as any based on propylene, based on ethene and/or the polymkeric substance of styrene-based.R ' group can be identical or different, and can comprise the mixture of any these type polymers as herein described.The present inventor also finds, combine polymer-based metal surface can by the reaction with oxygenant such as oxygen or amine-N-oxide compound stabilization.
The polyolefine of ethenyl blocking can be any polyolefine with vinyl terminal position as above group, for the polypropylene of ethenyl blocking, be preferably selected from the isotactic polyprophlene of ethenyl blocking, atactic polypropylene(APP), syndiotactic polypropylene, propylene-ethylene copolymers is (random, elastomeric, anti-impact, and/or block), with their combination, they have at least 300 grams/Mn that rubs separately.Preferably, the polyolefine being greater than the ethenyl blocking of 90% or 94% or 96% comprises end position vinyl groups, or in the scope of 10% or 20% or 30% to 50% or 60% or 80% or 90% or 95% or 98% or 100%.As mentioned above, the polyolefinic Mn value scope of ethenyl blocking 300 or 400 or 500 grams/rub to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 gram/rub.
The surface of polymkeric substance solubilising can be prepared with intermittent mode in the reactor, or continuous production, such as, form the pellet of the final polymer product wherein with solubilsed silicon-dioxide, aluminum oxide, clay or other particle in an extruder simultaneously.The polyolefine of ethenyl blocking and metal alkylide preferably merge as melt; And preferably merge in the temperature being greater than 110 DEG C or 120 DEG C or 140 DEG C or 160 DEG C.Merging can carried out in identical or lower temperature in a solvent.One of combining step or both carry out in an extruder, define that to be selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene and propylene-ethylene copolymers (random, elastomeric, anti-impact, and/or block) pellet.Final product can be the material of the surface modification of any expectation, such as nano composite material, and it comprises the surface of polymkeric substance solubilising and Mn is at least 10,000 gram/polyolefine that rubs or elastomerics, or comprises the surface of coating of this polymer-based carbon material.
As mentioned above, based on propylene, or based on the polymer-based carbon material of polymkeric substance, there is many application on the whole, comprise the nano composite material being formed and improve, electrical condenser, the film surface of modification, the metallic surface of modification to improve erosion resistance, or reduces the coating of other character expected rubbing or improve surface generally.
Herein to the surface of polymer materials and modification, or disclose the various descriptive element disclosed by method on surface of preparation this polymkeric substance als and modification and numerical range can be combined to describe the present invention with other descriptive element and numerical range; Furthermore, for given key element, any numerical upper limits described herein can be combined with any numerical lower limits described herein.Embodiment provided herein is that representativeness of the present invention described here describes, and is not intended to limit the present invention.
Embodiment
summation
Triisobutyl aluminium (TIBAL) purchased from Akzo Nobel and former state use.The atactic polypropylene(APP) of ethenyl blocking synthesizes by such described in the U.S. Patent Application Publication No.2009/0318644A1 submitted on June 20th, 2008.Cab-o-sil
tM(" Cabosil ") EH-5 silicon-dioxide is purchased from Cabot Corp.And before use at 200 DEG C of calcining overnight.All
1h NMR spectrum at room temperature takes from Bruker 400MHz spectrograph, or at the temperature of the rising of each reaction, take from Bruker 500MHz.All deuterated solvents are purchased from Cambridge Isotope Laboratories, Inc. and by 3 dust molecular sieve dryings.Spectral reference residual solvent protons.
embodiment 1 (3:1aPP:TIBAL → Cabosil → CO
2
)
In 10ml bottle, be that atactic polypropylene(APP) and the triisobutyl aluminium (0.1584g, 0.7987mmol) of about 1800g/mol and 95% ethenyl blocking merges by the Mn of the amounts of 4.35 grams (about 2.32mmol).This little bottle cap lid is also under agitation heated to 140 DEG C, produces the melt of polymkeric substance and aluminum alkyls.After 30 minutes, bottle is opened wide and stirs and spend the night.Cabosil (0.3346g) is added bottle and temperature is risen to 170 DEG C.Bottle is stirred 8 hours, produce smooth, uniform colloid, as (note, the white solid in bottom the middle bottle of Fig. 2 (2) is magnetic stirring bar) in Fig. 2 (2).Then bottle is loaded CO
2for being heated to 210 DEG C and spending the night in the Parr bottle of 200psi.Resulting materials is clear, viscous oil.Have collected 3.7600g.
comparative example 1
In 10ml bottle, the Mn of 4.37g amount (about 2.32mmol) is about 1800g/mol and the Cabosil of the amount of the atactic polypropylene(APP) of 95% ethenyl blocking and 0.314 gram merges, and 140 DEG C are heated under trial is stirred, produce the melt of polymkeric substance and aluminum alkyls.Obtain opaque gelatinous mixture, as shown in Fig. 2 (1).
embodiment 2 (1:1aPP:TIBAL → Cabosil)
In 10ml bottle, the Mn of the amounts of 1.81 grams (about 0.953mmol) is about 1800g/mol and the atactic polypropylene(APP) of 95% ethenyl blocking and triisobutyl aluminium (0.126g, 0.0984mmol) merge.This little bottle cap lid is also under agitation heated to 150 DEG C, produces the melt of polymkeric substance and aluminum alkyls.After about 2 hours, reaction is opened wide, and reheats 20 minutes.Reaction 170 DEG C is heated 30min further, then adds Cabosil (0.1256g), and at 170 DEG C of heating 2hr.Have collected 1.6388g viscous oil.
embodiment 3 (3:1iPP:TIBAL → Cabosil)
In 10ml bottle, by Mn about 5000 and iPP (the 3.0349g of about 92% ethenyl blocking, 0.5324mmol) be merged together with triisobutyl aluminium (36.8mg, 0.186mmol) and be heated to 180 DEG C, producing the melt of polymkeric substance and aluminum alkyls.After about 1 hour, reaction is opened wide, then stir and spend the night.Add Cabosil (0.2299g), and bottle is heated to 210 DEG C.By reaction stirring 6 hours, afterwards bottle be placed in Parr bottle and use 200psiCO
2pressurization.Parr bottle is put into the oil bath 2 hours of 230 DEG C.Have collected the slightly opaque material of 2.8302g.
NMR
embodiment 4 (isobutyl-)
3-n
al-(aPP)
n
5.41 grams of aPP (Mn=1894,99.9% vinyl) are placed in 20ml bottle.The triisobutyl aluminium of the amount of 0.195 gram and this polymkeric substance are merged, and reaction is under agitation heated under nitrogen atmosphere 170 DEG C two hours.Collect 5.15 grams of clear gels.
1H NMR400MHz(C6D6)：δ0.28(d，0.83H)，0.44(br s，2.00H)，0.9-1.8(mn，278H)，4.56-5.92(mn，1.27H)。
embodiment 5 (isobutyl-)
3-n
al-(iPP)
n
0.6611 gram of iPP (Mn=6511,94% ethenyl blocking) is placed in 20ml bottle.The triisobutyl aluminium of the amount of 0.0457 gram and this polymkeric substance are merged, and reaction is under agitation heated under nitrogen atmosphere 190 DEG C two hours.Collect 0.5511 gram of white solid.
1h NMR 500MHz 360K (toluene-d8): δ 0.4 (br, 2.00H), 0.97 (br, d, 614H), 1.38 (quintet, 161H), 1.71 (septet, 151H).
embodiment 6 (isobutyl-)
3-n
al-(PE)
n
1.6366 grams of PE (Mn=863,82.5% vinyl) are placed in 15ml bottle.The triisobutyl aluminium of the amount of 0.1317 gram and this polymkeric substance are merged, and reaction is under agitation heated under nitrogen atmosphere to 190 DEG C two hours.Collect 1.58 grams of white solids.
1hNMR 500Hz 355K (toluene-d8): δ 0.322 (br, 2H), 0.89-1.6 (mn, 131.56H), 5.4 (br, s, 0.10H).
embodiment 7 (isobutyl-)
3-n
al-(EP)
n
5.1 grams of EP (Mn=1750, Mw=3061,83%wt ethene, 92% vinyl) are placed in 15ml bottle.The triisobutyl aluminium of the amount of 0.19 gram and this polymkeric substance are merged, and reaction is under agitation heated under nitrogen atmosphere 190 DEG C 3 hours 40 minutes.Collect 4.93 grams of white solids.
1h NMR 500MHz 350K (toluene-d8): δ 0.30 (br, 2H), 0.89-1.58 (m, 361.3H), 5.41 (s, 0.65H).
embodiment 8 [(isobutyl-O)
3-n
al-O (aPP)
n
]
x
In 20mL bottle, aPP (5.4153g, 2.860mmol) and TIBAL (0.195g, 0.985mmol) is merged 2 hours at 170 DEG C.By Me
3nO (0.199g, 2.65mmol) adds reaction.Reaction is stirred at 230 DEG C under lid lid and spends the night.Observe and smolder.Product jaundice is spent the night.Collect 4.69g yellow gel.
1H NMR 400MHz(C6D6)：δ0.8-1.7(mn，240H)，3.8-4.3(br，mn，2.00H)，4.7-5.8(mn，1.26H)。
embodiment 9 [(isobutyl-O)
2-n
al-O (aPP)
n
]
x
-Cabosil
In 20mL bottle, aPP (3.2208g, 1.701mmol) and TIBAL (0.1280g, 0.6454mmol) are stirred 2 hours 40 minutes at 180 DEG C together.Cabosil (0.2143g) is added gel and stirs 1 hour at 190 DEG C.Then by Me
3nO (0.1058g, 1.409mmol) adds gel, spends the night 230 DEG C of stirrings.NMR measurement is carried out to clear gel/liquid, obtains signal, but do not know this signal whether from Cabosil or some their combinations of residual polymer base aluminium, modification:
1h NMR400MHz (C
6d
6): δ 0.9-1.7 (mn, 1676.07H), 4.8-5.1 (br, mn, 1.31H), 5.1-5.4 (br, mn, 2.00H), 5.75 (br, 0.174H).
Other embodiment
embodiment 10EP-OAl (OCH
2
cHMe
2
)
2
(NMe
3
)
EP macromole (48g, Mn=6635g/mol, the 80% vinyl end of the chain) is dissolved in 200ml toluene.Add DIBAl AlH (CH
2cHMe
2)
2(1.03g, 99%Aldrich), and reaction is heated to 100 DEG C.The aliquots containig of 2 hours shows, all vinyl end of the chains are consumed.
1H NMR(500MHz，C
2D
2Cl
4)δppm；5.1(.1H)，4.9-4.7(.2H)，2.2-0.5(1080H)，0.45-0.10(6H)。
Reaction is stirred 2 hours again, and by Me
3nO (1.8g) adds reaction mixture.Reaction is cooled and stirs a weekend (about 48 hours).Aliquots containig shows, there occurs considerably less reaction.
1H NMR(500MHz，C
2D
2Cl
4)δppm；2.2-0.5(1112H)，0.45-0.1(6H)。Reaction mixture is heated to 100 DEG C.The aliquots containig of 15 hours shows, drops to 0.1ppm according to resonance from 0.45, and reaction completes 83%.The aliquots containig of 48 hours shows, reaction completes 99%.
1H NMR(500MHz，C
2D
2Cl
4)δppm；3.48-3.44(m，3.4H)，3.44-3.40(m，2.0H)，3.22(s，9.0)，2.2-0.5(m，631H)。
embodiment 11 EP-I
EP macromole (20g, Mn=6635g/mol, the 80% vinyl end of the chain) is dissolved in 200ml heptane.Add DIBAl AlH (CH
2cHMe
2)
2(0.45g, 99%Aldrich), and reaction is heated to 90 DEG C 15 hours.Aliquots containig shows, all vinyl end of the chains are consumed.Reaction mixture is cooled to room temperature, adds solid I
2(2.7g).Show the analysis of aliquots containig after 1 hour, the resonance of all 0.45-0.1ppm disappears.
1H NMR(500MHz，C
2D
2Cl
4)δppm；3.2(m，1H)，2.0-0.5(752H)。Reduce volatile matter in a vacuum to produce sticky oil product.
To the law area under one's jurisdiction that all " including in by reference " principles are suitable for, all testing method, patent disclosure, patent and articles of reference are all included in herein with their entirety or the relevant portion of quoting them by reference at this.
Claims (20)
1. a polymer-based metal, it comprises the compound with following general formula:
MR
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is selected from Mn is at least 300 grams/polymkeric substance based on propylene that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc;
Wherein be connected to the first part of the R ' group of described metal M for-CH
2cH
2-group, and the end bit position of R ' group is isobutyl-.
2. polymer-based metal according to claim 1, wherein said polymer-based carbon is formed as metal alkylide or metal alkoxide bunch.
3. the polymer-based metal described in claim 1 and 2, wherein said polymer-based carbon and the surface bonding comprising hydroxylic moiety.
4. polymer-based metal according to claim 3, wherein said surface comprises: the particle of silicon-dioxide, silica-alumina, aluminum oxide (and spray-dried forms), glass, clay; Glass fibre; Glass surface; Graphene oxide, carbon black; Calcium carbonate; The polyolefin film of oxidation; And metallic surface.
5. the polymer-based metal described in aforementioned any one of claim, the wherein said polymkeric substance based on propylene is the homopolymer of propylene or propylene and ethene or C
4-C
10the multipolymer of alpha-olefin.
6. polymer-based metal according to claim 5, the wherein said polymkeric substance based on propylene is selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, and propylene-ethylene copolymers (random, elastomeric and/or block).
7. the polymer-based metal described in aforementioned any one of claim, comprises further and being combined with described polymer-based metal by oxygenant; Wherein said oxygenant is oxygen or amine-N-oxide compound.
8. the polymer-based metal described in aforementioned any one of claim, the Mn value scope of the wherein said polymkeric substance based on propylene 300 or 400 or 500 grams/rub to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 gram/rub.
9. high-k material, it comprises the polymer-based metal described in aforementioned any one of claim.
10. the surface " S " of polymkeric substance solubilising, it comprises multiple hydroxyl (" S-OH "), and wherein at least one hydroxyl is according to following formula modification:
S-O-MR
2-nR'
n,
Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1 or 2; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.
The surface of 11. polymkeric substance solubilisings, it comprises following reaction product:
Comprise surface and the polymer-based metal MR of hydroxylic moiety
3-nr'
n; Wherein each R group is hydrogen or C
1-C
10or C
20alkyl, and each R ' group is Mn is at least 300 grams/polymkeric substance that rubs; N is 1,2 or 3; And M is the 12nd or 13 race's metals, preferred aluminium or zinc.
The surface of the polymkeric substance solubilising described in 12. claims 10 and 11, wherein R' is selected from isotactic polyprophlene, atactic polypropylene(APP), syndiotactic polypropylene, polyethylene, ethylene-propylene copolymer and their combination, and they have at least 300 grams/Mn that rubs separately.
The surface of the polymkeric substance solubilising described in 13. claim 10-12, wherein R is selected from C
3-C
6alkyl.
The surface of the polymkeric substance solubilising described in 14. any one of claim 10-13, the Mn value scope of wherein said polymkeric substance 300 or 400 or 500 grams/rub to 20,000 or 30,000 or 40,000 or 50,000 or 100,000 or 200,000 or 300,000 gram/rub.
15. the surface of the polymkeric substance solubilising described in any one of claim 10-14, wherein said polymkeric substance is the homopolymer of propylene or propylene and ethene or C
4-C
10the multipolymer of alpha-olefin.
The surface of the polymkeric substance solubilising described in 16. claim 10-15, comprises further and being combined with described polymer-based metal by oxygenant; Wherein said oxygenant is oxygen or amine-N-oxide compound.
17. 1 kinds of nano composite materials, it comprises the surface of the polymkeric substance solubilising described in any one of claim 10-16 and Mn is at least 10,000 gram/polyolefine that rubs or elastomerics.
18. 1 kinds of coatings, it comprises the surface of the polymkeric substance solubilising described in claim 10-17.
19. 1 kinds of polymer-based carbon aluminium, it derives from the polymkeric substance based on propylene of the ethenyl blocking any one of aforementioned claim, has Al-C
h 2cH
2the feature of (polymkeric substance)
1h NMR signal and under condition described in an embodiment δ scope 0.25 or 0.30 or 0.32 to 0.40 or 0.42 or 0.45ppm (wide region); Once this polymer-based carbon aluminium and oxidant reaction, Al-OC
h 2cH
2the feature of (polymkeric substance)
1h NMR signal 3.2 or 3.5 or 3.8 to 4.2 or 4.5 or 4.8ppm δ within the scope of (wide region).
20. the polymer-based carbon any one of aforementioned claim or the surface of solubilize polymers are as the purposes of the filler in nano composite material or the coating on solid surface.
Applications Claiming Priority (5)
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| US201261740169P | 2012-12-20 | 2012-12-20 | |
| US61/740,169 | 2012-12-20 | ||
| EP13162542 | 2013-04-05 | ||
| EP13162542.8 | 2013-04-05 | ||
| PCT/US2013/073832 WO2014099440A1 (en) | 2012-12-20 | 2013-12-09 | Metal polymeryls and the polymer solubilized surfaces derived therefrom |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923918A (en) * | 1987-06-10 | 1990-05-08 | Chisso Corporation | Process for producing modified propylene polymer composition |
| CN1093382A (en) * | 1993-02-10 | 1994-10-12 | 哈克罗斯颜料有限公司 | The particle of surface modification and manufacture method thereof |
| CN102066440A (en) * | 2008-06-20 | 2011-05-18 | 埃克森美孚化学专利公司 | Functionalized high vinyl terminated propylene based oligomers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3914342A (en) * | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
| US8399725B2 (en) * | 2008-06-20 | 2013-03-19 | Exxonmobil Chemical Patents Inc. | Functionalized high vinyl terminated propylene based oligomers |
| WO2011016992A2 (en) * | 2009-07-29 | 2011-02-10 | Dow Global Technologies Inc. | Polymeric chain transfer/shuttling agents |
| WO2012061706A1 (en) * | 2010-11-04 | 2012-05-10 | Dow Global Technologies Llc | Double shuttling of polyolefin polymeryl chains |
-
2013
- 2013-12-09 EP EP13863793.9A patent/EP2935360A4/en not_active Withdrawn
- 2013-12-09 CN CN201380055373.2A patent/CN104736575A/en active Pending
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4923918A (en) * | 1987-06-10 | 1990-05-08 | Chisso Corporation | Process for producing modified propylene polymer composition |
| CN1093382A (en) * | 1993-02-10 | 1994-10-12 | 哈克罗斯颜料有限公司 | The particle of surface modification and manufacture method thereof |
| CN102066440A (en) * | 2008-06-20 | 2011-05-18 | 埃克森美孚化学专利公司 | Functionalized high vinyl terminated propylene based oligomers |
Non-Patent Citations (1)
| Title |
|---|
| M.J. YANJARAPPA等: "Recent developments in the synthesis of functional poly(olefin)s", 《PROGESS IN POLYMER SCIENCE》, vol. 27, 31 December 2002 (2002-12-31), pages 1347 - 1398, XP 002510488, DOI: doi:10.1016/S0079-6700(02)00011-4 * |
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| EP2935360A1 (en) | 2015-10-28 |
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