WO2018057078A1 - Compositions de copolymères séquencés d'oléfine et d'élastomères à base de propylène - Google Patents

Compositions de copolymères séquencés d'oléfine et d'élastomères à base de propylène Download PDF

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WO2018057078A1
WO2018057078A1 PCT/US2017/038122 US2017038122W WO2018057078A1 WO 2018057078 A1 WO2018057078 A1 WO 2018057078A1 US 2017038122 W US2017038122 W US 2017038122W WO 2018057078 A1 WO2018057078 A1 WO 2018057078A1
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ethylene
propylene
composition
range
previous
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PCT/US2017/038122
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English (en)
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Jingwen Zhang
Carlos R. LOPEZ-BARRON
Jan Kalfus
Abdul M. JANGDA
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Exxonmobil Chemical Patents Inc.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/005—Modified block copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the present invention relates to olefin block copolymer blends with an elastomer, and more particularly to blends of olefin block copolymers with propylene-based elastomers suitable for elastic hygiene articles.
  • the elastic hygiene market is a large and fast growing market.
  • Elastic polymers that are able to keep their shape upon deformation are highly desirable in elastic hygiene articles such as diapers.
  • Styrenic block copolymers SBC's
  • SBC's Styrenic block copolymers
  • OBC's block copolymers
  • PBEs VistamaxxTM propylene-based elastomers
  • a polymer blend comprising (or consisting essentially of, or consisting of) at least one olefin block copolymer ("OBC”), preferably poly(ethylene-b- ethylene/propylene-b-ethylene); and at least one propylene -based elastomer.
  • OBC olefin block copolymer
  • a polymer blend comprising within a range from 5, or 10, or 15 wt% to 30, or 40, or 50, or 60 wt% of the OBC, and within a range from 40, or 50, or 60, or 70 wt% to 85, or 90, or 95 wt% of the propylene-based elastomer.
  • an OBC comprising an ethylene/propylene block having a propylene content within a range from 50 wt% to 70 wt% by weight of the ethylene/propylene block.
  • an OBC comprising an ethylene block having a C3 to C8 content within a range from 2 wt% to 6, or 8, or 10, or 15 wt% by weight within each ethylene block.
  • FIG. 1 is a gel permeation chromatographic (GPC) trace of the neat EEP r E of the examples.
  • FIG. 2 is an NMR spectrum of the neat EEP r E of the examples.
  • FIG. 3 is an AFM image (Phase 1) of the neat EEP r E of the examples at 2.5 ⁇ , darker regions are softer.
  • FIG. 4 is a SAXS/MAXS/WAXS spectra at 25 °C of the neat EEP r E of the examples.
  • FIG. 5 are WAXS traces at 25 °C after 2 days of aging of the neat EEP r E of the examples and other benchmark polymers as labeled.
  • FIG. 6 are WAXS traces at 37°C after 2 days of aging of the neat EEP r E of the examples and other benchmark polymers as labeled.
  • composition comprising (or consisting essentially of, or consisting of) at least one OBC; and at least one propylene-based elastomer.
  • the OBC is poly(ethylene-b- ethylene/propylene-b-ethylene).
  • the poly(ethylene-b-ethylene/propylene- b-ethylene) is derived from hydrogenated poly(l,4-butadiene-b-isoprene-b-l,4-butadiene) preferably made in a living anionic polymerization process.
  • the composition comprises within a range from 5, or 10, or 15 wt% to 30, or 40, or 50, or 60 wt% of the OBC, and within a range from 40, or 50, or 60, or 70 wt% to 85, or 90, or 95 wt% of the propylene -based elastomer.
  • the compositions disclosed herein are useful in elastic hygienic articles such as infant and adult diapers, disposable cloths, surgical wear, other hygiene wear and undergarments, and other absorbent wear.
  • the OBCs of the present invention(s) preferably comprise alternating blocks of a crystalline poly olefin "A" and an amorphous poly olefin "B.”
  • the OBCs are formed by first synthesizing a pre -polymer, typically by living anionic polymerization, followed by hydrogenation of the product.
  • the OBCs comprise one or more crystalline- amorphous units, wherein each crystalline-amorphous unit is composed of a single crystalline "A" block and a single amorphous "B" block.
  • Such a structure can be represented by the following formula:
  • n is an integer of at least 1, preferably greater than 0.5, or 1, or 2, or 4, or 10, or 20; or within a range from 1, or 2, or 4, to 10, or 20.
  • n is within a range from 0.5 to 3 or 4.
  • n is 1 for triblock or 0.5 for diblock.
  • anionic polymerization of multi-olefin monomers such as isoprene and butadiene is well known in the art.
  • the anionic polymerization is lithium-ion initiated.
  • Suitable lithium-ion initiators include, but are not limited to, organolithium compounds, more preferably a compound formed from diisopropenylbenzene and a tertiary alkyl lithium compound, for example, m-di- (1 -methyl- 3,3- dimethylbutyllithio)benzene.
  • the anionic polymerization process can be run at temperatures varying from 0°C to 200 °C as limited by thermal stability of the monomer, the lithium initiator, and the poly olefin "A" and/or "B" pre-polymer products. Temperatures between 0°C and 150°C are preferred, more preferably from 30°C to 100°C, most preferably from 40°C to 60°C. Polymerization times may range between several seconds and a few days, more preferably ranging from one to ten hours.
  • solvents and/or solvent blends may be used as the medium in which the anionic polymerization is run.
  • Solvents that are particularly suited for solvating the lithium initiator include, but are not limited to cyclohexane, tetrahydrofuran (THF) and diethyl ether.
  • a high polarity solvent is preferred for synthesizing polybutadiene with a vinyl content, that is, 1,2-addition content, of preferably greater than 25 mol%, and most preferably greater than 35 mol%.
  • the OBC comprising the polyolefin "A” and polyolefin “B” pre-polymer could by synthesized via hydrogenating from blocks of "A” and “B” that contains double bonds. Such hydrogenation may be carried out by any conventional methods known in the art.
  • substantially saturated as it refers to the OBC means that the copolymer includes on average fewer than 5 double bonds, or fewer than 3 double bonds, or fewer than 1 double bond, or fewer than 0.5 double bond per one hundred carbon in the copolymer chain.
  • Hydrogenation can be carried out in the process of the present disclosure by any known catalysis system, including heterogeneous systems and soluble systems.
  • a transition metal based catalyst more preferably a ruthenium or rhodium based catalyst, most preferably Wilkinson's catalyst (chlorotris(triphenylphosphine) rhodium(I)), is used to catalyze the hydrogenation.
  • the hydrogenation may be performed in the absence of a catalyst.
  • Non-catalyzed hydrogenation is preferably performed using an inorganic reducing agent, preferably a diimide.
  • the diimide is generated through thermal treatment of an arenesulfonylhydrazide, most preferably p-toluenesulfonulhydrazide.
  • the hydrogenation reaction herein can be accomplished at a temperature high enough to prevent hydrogenated polyolefins from crystallizing in solution, preferably at a temperature ranging from 40°C to 160°C and most preferably from 60°C to 150°C. Different substrates being hydrogenated will require different optimum temperatures, which can be determined by experimentation.
  • the initial hydrogenation pressures may range up to 3,000 psi partial pressure, at least part of which is present due to the hydrogen. Pressures from 1 to 7500 psig are suitable. Preferred pressures are up to 2000 psig, and most preferred pressures are from 100 to 1000 psig are employed.
  • the reactive conditions are determined by the particular choices of reactants and catalysts.
  • the process may be either batch or continuous. In a batch process, reaction times may vary widely, such as between 0.01 seconds to 10 hours. In a continuous process, reaction times may vary from 0.1 seconds to 120 minutes and preferably from 0.1 seconds to 10 minutes.
  • the polyolefin "A" of the OBC pre-polymer is synthesized via the anionic polymerization of butadiene.
  • the "A” block is a crystalline block comprising ethylene and less than 5, or 4, or 3, or 2, or 1 wt% C3 to C8 a-olefin derived units by weight of the "A" block.
  • the "A" blocks comprise greater than 85 or 95 wt% ethylene and are thus called “ethylene blocks," wherein each ethylene block of the A-B-A OBC, poly(ethylene-b-ethylene/propylene-b-ethylene), has a C3 to C8 content within a range from 1, or 2, or 3 wt% to 5, or 6, or 8, or 10, or 15 wt% by weight within each ethylene block. More preferably, in any embodiment the ethylene blocks consist of ethylene-derived units and C3 to C8-derived units, most preferably ethylene- and 1-butene-derived units.
  • the crystalline polyolefin "A" block(s) of the OBC comprise ethylene derived monomer units.
  • each polyolefin "A” block has an ethylene content of greater than 90 mol% based on the total moles of the monomers of polyolefin “A.” More preferably, each polyolefin "A” block has an ethylene content of greater than 95, or 98, or 99 mol%. Most preferably, each polyolefin "A” block has an ethylene content of greater than 99.9 mol%.
  • each polyolefin "A” block has a degree of crystallinity greater than 50%, more preferably greater than 60%, and most preferably greater than 70%.
  • the polyolefin "B" component of the pre -polymer is synthesized via the anionic polymerization of isoprene monomer. Once hydrogenated, the "B" block is a non-crystalline or elastomeric a-olefin copolymer comprising alternating ethylene- and propylene-derived units with 50 mol% propylene-derived units.
  • the "B" block is an ethylene/propylene block of the poly(ethylene-b-ethylene/propylene-b- ethylene) has a propylene content within a range from 50 wt% to 70 wt% by weight of the ethylene/propylene block; wherein the ethylene/propylene block consists of ethylene-derived units and propylene-derived units.
  • the A-B-A OBC described herein is preferably a poly(ethylene-b- ethylene/propylene-b-ethylene) block copolymer ("EEP r E") and has many desirable properties.
  • OBC has a melting point temperature T m within a range from 60, or 70, or 80 to 110, or 120°C.
  • the OBC has a crystallization temperature Tc within a range from 50, or 60 to 70, or 80°C.
  • the OBC has a number average molecular weight (Mn) within a range from 50, or 100 kg/mole to 200, or 300 kg/mole.
  • the OBC has a weight average molecular weight (Mw) within a range from 50, or 100 kg/mole to 200, or 300 kg/mole. In any embodiment, the OBC has a Mw/Mn value within a range from 0.9, or 1, or 1.1 to 1.2, or 1.3, or 1.4, or 1.5, or 1.8, or 2. In any embodiment, the OBC comprises lamella having a spacing within a range from 10, or 12 nm to 20, or 24, or 26, or 30 nm (SAXS/MAXS/WAXS at 20°C).
  • the propylene-based elastomer is a random copolymer having crystalline regions interrupted by non-crystalline regions and within the range from 5 to 25 wt%, by weight of the propylene-based elastomer, of ethylene or C4 to CIO alpha-olefin derived units, and optionally diene-derived units, the remainder of the polymer being propylene-derived units.
  • the noncrystalline regions may result from regions of non-crystallizable polypropylene segments and/or the inclusion of comonomer units.
  • the crystallinity and the melting point of the propylene-based elastomer are reduced compared to highly isotactic polypropylene by the introduction of errors (stereo and region defects) in the insertion of propylene and/or by the presence of comonomer.
  • the copolymer contains at least 60 wt% propylene-derived units by weight of the propylene-based elastomer.
  • the propylene-based elastomer is a propylene-based elastomer having limited crystallinity due to adjacent isotactic propylene units and a melting point as described herein.
  • the propylene-based elastomer is generally devoid of any substantial intermolecular heterogeneity in tacticity and comonomer composition, and also generally devoid of any substantial heterogeneity in intramolecular composition distribution.
  • the propylene-based elastomer contains greater than 50 wt%, preferably greater than 60 wt%, more preferably greater than 65 wt%, even more preferably greater than 75 wt% and up to 99 wt% propylene-derived units, based on the total weight of the propylene-based elastomer.
  • the propylene-based elastomer includes propylene-derived units in an amount based on the weight of propylene-based elastomer of from 75 wt% to 95 wt%, more preferably 75 wt% to 92.5 wt%, and even more preferably 82.5 wt% to 92.5 wt%, and most preferably 82.5 wt% to 90 wt%.
  • the units, or comonomers, derived from at least one of ethylene or a C4 to CIO alpha-olefin may be present in an amount of 5, or 10, or 14 wt% to 22, or 25 wt% by weight of the elastomer.
  • the comonomer content may be adjusted so that the propylene-based elastomer having a heat of fusion of 100 J/g or less, or 75 J/g or less, a melting point (T m ) of 100°C or 90°C or less, and crystallinity of 2% to 65% of isotactic polypropylene, and preferably a melt flow rate ("MFR"), as measured at 230°C and 2.16 kg weight, of less than 800 g/10 min.
  • MFR melt flow rate
  • the propylene-based elastomer may comprise more than one comonomer.
  • Preferred embodiments of a propylene-based elastomer have more than one comonomer including propylene-ethylene-octene, propylene-ethylene-hexene, and propylene-ethylene- butene copolymers.
  • the amount of each comonomer may be less than 5 wt% of the propylene-based elastomer, but the combined amount of comonomers by weight of the propylene-based elastomer is 5 wt% or greater.
  • the comonomer is ethylene, 1-hexene, or 1-octene, and preferably in an amount of 5, or 10, or 14 wt% to 22, or 25 wt% based on the weight of the propylene-based elastomer.
  • the propylene-based elastomer comprises ethylene-derived units.
  • the propylene-based elastomer may comprise 5, or 10, or 14 wt% to 22, or 25 wt% of ethylene-derived units by weight of the propylene-based elastomer.
  • the propylene-based elastomer consists essentially of units derived from propylene and ethylene, i.e., the propylene-based elastomer does not contain any other comonomer in an amount typically present as impurities in the ethylene and/or propylene feedstreams used during polymerization or an amount that would materially affect the heat of fusion, melting point, crystallinity, or melt flow rate of the propylene-based elastomer, or any other comonomer intentionally added to the polymerization process.
  • diene comonomer units are included in the propylene-based elastomer.
  • diene include, but not limited to, 5-ethylidene-2-norbornene, 5- vinyl-2-norbornene, divinylbenzene, 1,4-hexadiene, 5-methylene-2-norbornene, 1,6- octadiene, 5-methyl-l, 4-hexadiene, 3,7-dimethyl-l,6-octadiene, 1,3-cyclopentadiene, 1,4- cyclohexadiene, dicyclopentadiene, or a combination thereof.
  • the amount of diene comonomer is equal to or more than 0 wt%, or 0.5 wt%, or 1 wt%, or 1.5 wt% and lower than, or equal to, 5 wt%, or 4 wt%, or 3 wt% or 2 wt% based on the weight of propylene-based elastomer.
  • the propylene-based elastomer has a heat of fusion ("Hf"), as determined by the Differential Scanning Calorimetry ("DSC”), of 100 J/g or less, or 75 J/g or less, 70 J/g or less, 50 J/g or less, or 35 J/g or less.
  • the propylene-based elastomer may have a lower limit Hf of 0.5 J/g, 1 J/g, or 5 J/g.
  • the Hf value may be anywhere from 1.0, 1.5, 3.0, 4.0, 6.0, or 7.0 J/g, to 30, 35, 40, 50, 60, 70, or 75 J/g.
  • the propylene-based elastomer may have a percent crystallinity, as determined according to the DSC procedure described herein, of 2% to 65%, preferably 0.5% to 40%, preferably 1% to 30%, and more preferably 5% to 35%, of isotactic polypropylene.
  • the thermal energy for the highest order of propylene i.e., 100% crystallinity
  • the copolymer has a crystallinity in the range of 0.25% to 25%, or 0.5% to 22% of isotactic polypropylene.
  • the propylene-derived units of the propylene-based elastomer have an isotactic triad fraction of 50% to 99%, more preferably 65% to 97% and more preferably 75% to 97%.
  • the first polymer has a triad tacticity as measured by 13 C NMR, of 75% or greater, 80% or greater, 82% or greater, 85% or greater, or 90% or greater.
  • the triad tacticity of a polymer is the relative tacticity of a sequence of three adjacent propylene units, a chain consisting of head to tail bonds, expressed as a binary combination of m and r sequences.
  • the triad tacticity (mm fraction) of a propylene copolymer can be determined from a 13 C NMR spectrum of the propylene copolymer. The calculation of the triad tacticity is described in the US 5,504,172, the entire contents of which are incorporated herein by reference.
  • the propylene-based elastomer may have a single peak melting transition as determined by DSC.
  • the copolymer has a primary peak transition of 90°C or less, with a broad end-of-melt transition of 110°C or greater.
  • the peak "melting point" (“Tm”) is defined as the temperature of the greatest heat absorption within the range of melting of the sample.
  • the copolymer may show secondary melting peaks adjacent to the principal peak, and/or at the end-of-melt transition. For the purposes of this disclosure, such secondary melting peaks are considered together as a single melting point, with the highest of these peaks being considered the T m of the propylene-based elastomer.
  • the propylene-based elastomer may have a T m of 100°C or less, 90°C or less, 80°C or less, or 70°C or less.
  • the propylene-based elastomer has a T m of 25°C to 100°C, 25°C to 85°C, 25°C to 75 °C, or 25 °C to 65 °C.
  • the propylene-based elastomer has a T m of 30°C to 80°C, preferably 30°C to 70°C.
  • DSC Differential Scanning Calorimetry
  • the propylene-based elastomer may have a Mooney viscosity [ML (1+4) @ 125°C], as determined according to ASTM D-1646, of less than 100, in other embodiments less than 75, in other embodiments less than 60, and in other embodiments less than 30.
  • the propylene-based elastomer may have a density of 0.850 g/cm 3 to 0.920 g/cm 3 , 0.860 g/cm 3 to 0.900 g/cm 3 , preferably 0.860 g/cm 3 to 0.890 g/cm 3 , at room temperature as measured per ASTM D-1505.
  • the first polymer preferably has a melt flow rate ("MFR") greater than 0.5 g/10 min, and less than or equal to 1,000 g/10 min, or less than or equal to 800 g/10 min, more preferably less than or equal to 500 g/10 min, more preferably less than or equal to 200 g/10 min, more preferably less than or equal to 100 g/10 min, more preferably less than or equal to 50 g/10 min.
  • MFR melt flow rate
  • Particularly preferred embodiments include a propylene-based elastomer with an MFR of less than or equal to 25 g/10 min, such as from 1 to 25 g/10 min, more preferably 1 to 20 g/10 min.
  • the MFR is determined according to ASTM D-1238, condition L (2.16 kg, 230°C).
  • the propylene-based elastomer may have a weight average molecular weight ("Mw”) of 5,000 to 5,000,000 g/mole, preferably 10,000 to 1,000,000 g/mole, and more preferably 50,000 to 400,000 g/mole; a number average molecular weight ("Mn") of 2,500 to 2,500,00 g/mole, preferably 10,000 to 250,000 g/mole, and more preferably 25,000 to 200,000 g/mole; and/or a z-average molecular weight (“Mz”) of 10,000 to 7,000,000 g/mole, preferably 80,000 to 700,000 g/mole, and more preferably 100,000 to 500,000 g/mole.
  • the propylene- based elastomer may have a molecular weight distribution (Mw/Mn, or "MWD”) of 1.5 to 20, or 1.5 to 15, preferably 1.5 to 5, and more preferably 1.8 to 5, and most preferably 1.8 to 4.
  • the propylene-based elastomer may have an Elongation at Break of less than 2000%, less than 1000%, or less than 800%, as measured per ASTM D412.
  • a polymer composition comprising (or consisting essentially of, or consisting of) at least OBC; and at least one propylene-based elastomer, but most preferably only one propylene-based elastomer.
  • the composition comprises within a range from 5, or 10, or 15 wt% to 30, or 40, or 50, or 60 wt% of the OBC, and within a range from 40, or 50, or 60, or 70 wt% to 85, or 90, or 95 wt% of the propylene-based elastomer.
  • the at least one OBC is poly(ethylene-b-ethylene/propylene-b-ethylene) comprising blocks comprising "ethylene” and blocks of "ethylene/propylene", which represents ethylene-propylene copolymer.
  • the ethylene/propylene block of the poly(ethylene-b- ethylene/propylene-b-ethylene) has a propylene content within a range from 50, or 55, or 60 wt% to 65, or 70 wt% by weight of the ethylene/propylene block.
  • the ethylene/propylene block consists of ethylene-derived units and propylene-derived units.
  • each ethylene block of the poly(ethylene-b- ethylene/propylene-b-ethylene) has a C3 to C8 content within a range from 2 wt% to 6, or 8, or 10, or 15 wt% by weight within each ethylene block; wherein the ethylene blocks consist of ethylene-derived units and C3 to C8-derived units, most preferably 1-butene-derived units.
  • the OBC preferably comprises two "ethylene" blocks for every one ethylene/propylene block.
  • Most preferably the at least one OBC is the poly(ethylene-b- ethylene/propylene-b-ethylene) is derived from hydrogenated poly(l,4-butadiene-b-isoprene- b-l,4-butadiene).
  • compositions described herein are solution blends of the at least one OBC and the at least one propylene-based elastomer. This can be accomplished by combining the ingredients together in a solvent such as toluene or xylene at an elevated temperature until dissolved, then isolating the composition by evaporating the solvent.
  • the compositions can also be formed by extrusion blending, or reactor blending wherein the ingredients in their respective solvents of polymerization are combined in series or parallel, followed by removal of the solvents.
  • the OBC's described herein have a permanent set (7 day aging, 0 sec hold, 200% strain) within a range from 30, or 35, or 40 to 50, or 55% at 37°C, and within a range from 15, or 10 to 20, or 25% at 20°C.
  • styrenic block copolymers are absent from the composition.
  • styrenic block copolymers what is meant are copolymer comprising at least one polymeric block having at least one styrene-derived unit.
  • the styrenic block copolymers referred to can be of the "A-B” type, "B-A-B” type, or "A-B- A” type.
  • the compositions described herein styrenic polymers are absent from the composition, where "styrenic polymers” are any polymers containing at least 1, or 2, or 5 wt% styrene-derived units.
  • absent what is meant is that none of the named materially is purposefully added to the composition at any stage of forming the composition, and if present, is below the limit of commercially occurring impurities in the components of the composition.
  • compositions described herein have a number of uses.
  • the invention described herein includes fibers and fabrics comprising the composition.
  • the composition is formed into, or made part of an elastic article.
  • Some examples of elastic articles include diapers, surgical wear, hygiene wear, undergarments, and absorbent wear.
  • DSC Measurements Differential Scanning Calorimetry (DSC) was carried out on the OBC and blends using a TA Instrument Model Q-200. DSC measures the amount of energy absorbed or released by a sample when it is heated or cooled, providing quantitative and qualitative data on endothermic (heat absorption) and exothermic (heat evolution) processes.
  • the sample was placed in a Zero Hermetic Pan and encapsulated with lid using a pan press. It sits upon a disc on a platform in the DSC cell. An empty reference pan sits on a symmetric platform in the DSC cell. Heat flow was measured by comparing the difference in temperature across the sample and the reference.
  • Sample sizes are from 3.5 mg to 5 mg and were heated at rate of 10°C/min from -90°C to 220°C in nitrogen gas flowing at a rate of 50 ml/min.
  • the samples were first heated from room temperature to 220°C to remove any thermal history. Then they are cooled from 220°C to -90°C, i.e. first cooling and heating back up from -90°C to 220°C, i.e. second heating processes. All the DSC plots on first cooling and second heating were recorded.
  • the melting point temperature, Tm was recorded during the second heating and the crystallization temperature, Tc, was recorded during the first cooling.
  • GPC Measurements The column is calibrated with polystyrene and the mass is calibrated with NBS1475.
  • the molecular weight modeling is analyzed as a random EP copolymer with 35 wt% of ethylene from GPC- 3D and GPC-4D, using a polystyrene standard; type of detectors: DRI (if 3D); Infrared (if 4D) (the trace shown in FIG.
  • NMR Measurements 500 MHz NMR instrument in TCE-d2 solvent at 75 °C and 4096 scans. NMR data of the EEPrE with and without dibutylhydroxytoluene (BHT) were collected after compression molding on the 2-day and 7-day aged samples. The samples are dissolved in TCE-d2 in 5 mm NMR tube at 135°C until the sample is dissolved. There is no standard used. The TCE-d2 shows a peak at 5.98 ppm and used as the reference peak for our samples.
  • BHT dibutylhydroxytoluene
  • SAXS/MAXS/WAXS Measurements All small- and wide-angle X-ray scattering (SAXS/WAXS) were performed using an in-house SAXSLAB Ganesha 300XL+. The same sample preparation methods were used for X-ray measurements as for the elastic testing described below. Each sample was placed in a Linkam TST350 portable tensile stage, which was aligned to the X-ray beam. These samples provided good thermal contact and were controlled at 25°C + 0.1°C, and then at 37°C + 0.1°C. The incident wavelength was 0.154 nm from a CuK microfocus sealed tube source (Xenocs).
  • Peak load load at first cycle strain
  • Hysteresis area inside total first cycle curve
  • Neat Olefin Block Copolymer The model olefin block copolymer (OBC) system was synthesized via living anionic polymerization of poly(l,4-butadiene-£>-isoprene-£>-l,4- butadiene) triblock copolymers followed by hydrogenation, resulting in a tri-block copolymer of poly(ethylene/butene-b-ethylene/propylene-b-ethylene/butene) (EEP r E).
  • the GPC data of the unhydrogenated first block, diblock and triblock are listed in Table 1.
  • the M n values of each PE, EP r (random EP copolymer) and PE blocks are 23k- 129k- 18k, respectively.
  • the PE blocks contain 6-8 wt% butene. Due to the nature of living anionic polymerization, there is always a certain amount of 1,2-butadiene insertion instead of 1 ,4-butadiene insertion, thus some butene-units remain after hydrogenation. If it were 100% 1 ,4-butadiene, then there would be 100% polyethylene blocks without any butene. In any case, the resultant unhydrogenated triblock molecular weight distribution is very narrow with an Mw/Mn of 1.03.
  • FIG. 1 shows an AFM image (Phase 1) of EEP r E at 2.5 ⁇ . Some hexagonal spheres were noted, but not rods. Some parts appear to be bi-continuous structures. The AFM did not resolve the lamellae within the hard (PE) domains as the contrast between the soft (PEP) domains and the overall PE domains is much higher than between amorphous and lamellar within the PE domains.
  • FIG. 4 shows the SAXS/MAXS/WAXS data obtained for the exemplary inventive EEP r E.
  • the peak corresponding to the block segregation (d of 43 nm) is faint because the long distance peak (d of 16 nm) is also present.
  • the BCP peak is consistent with the distance observed in AFM.
  • Table 2 shows the hysteresis plots and the numerical hysteresis values at 200% strain on EEP r E, KratonTM ("KG”) 1567, and VistamaxxTM propylene -based elastomers ("VM”) at body and room temperatures (37°C and 25°C, respectively).
  • the EEP r E approximates Kraton polymers in terms of the peak load and the permanent set, but does have larger mechanical hysteresis.
  • Vistamaxx propylene-based elastomer has softer stretch and larger permanent set and hysteresis.
  • Table 3 lists the NMR, density, MI, GPC and DSC results on the EEP r E, commercial Kraton, poly(styrene-b-ethylene/butene-b-styrene) (“SEBS”) purchased from Sigma-Aldrich, Vistamaxx 6102, and Vistamaxx 7010, propylene-based elastomers, and commercial Dow InfuseTM ethylene-octene block copolymers (OBC-1 and OBC-2, corresponding to D9107 and D9507, respectively).
  • Tables 4A and 4B show the first permanent set of the model system and some benchmark materials at room and body temperatures (25 °C and 37°C, respectively) after 200% strain at 0, 30 seconds and 180 seconds holding.
  • the elastic performance depends on the holding time and the temperature. In general, the permanent set values increases with temperature and prolonged holding.
  • the model OBC system EEP r E approximates Kraton polymer at 25°C and 37°C and it maintains a permanent set at 37°C. In addition, EEP r E has the smallest change in permanent set values from 25 °C to 37 °C.
  • FIG. 5 and FIG. 6 show the WAXS data of EEP r E, Kraton, Vistamaxx propylene- based elastomer and commercial OBC polymers after 2-days of aging at 20°C and 37°C respectively. Similar crystallinity behavior is observed for each category of the materials. Kraton polymers do not have crystalline peaks due to the lack of crystalline blocks. The crystallinity percentage decreases dramatically with temperature for olefinic polymers. At 20°C, there are orthorhombic peaks for PE in EEP r E and overall crystallinity is 5.6%.
  • Alpha crystals of PP are present for Vistamaxx propylene-based elastomer yet due to the breadth of these peaks, we can say that these crystals are very small and possess many defects. Due to no SAXS signal, it appears that the Vistamaxx crystals do not stack into a regular ordered array.
  • Commercial OBC polymers display ethylene crystallinity at levels of 6-7%. In addition these polymers also exhibit a monoclinic crystalline phase, typically observed for crystals with a high defect density. At 37°C, little crystallinity ( ⁇ 1%) was left for EEP r E and commercial OBC polymers. For Vistamaxx propylene-based elastomer materials, the crystallinity appears to completely go away based on the data. The crystallinity percentage relates to the elastomeric properties for olefinic polymers.
  • Blends of Olefin Block Copolymer and propylene-based elastomer had targeted concentrations of 10, 25 and 50 wt% of EEP r E in VM 6102.
  • inventive compositions had targeted concentrations of 10, 25 and 50 wt% of EEP r E in VM 6102.
  • VM 6102 concentration of 10 wt% of EEP r E in VM 6102.
  • All solid ingredients were added to a round bottom flask with a magnetic stir bar, including about 0.2 to 1 grams of EEP r E, then xylenes (80-100 mL) were added to the solids, followed by heated stirring, setting the temperature of the heating block at 110°C. The mixture was then stirred at 110°C for 3 hr to form a homogeneous solution.
  • Table 5 lists the composition of three solution blends of EEP r E model OBC and Vistamaxx 6102 propylene-based elastomer in xylene.
  • the target OBC wt% is 10, 25 and 50 wt%, respectively. Each contains 0.2 wt% of IrganoxTM 1010.
  • Table 5 Composition of solution blends of EEP r E and VistamaxxTM 6102 polymers
  • Tables 6A and 6B show the first permanent set values of the neat materials and, the three solution blends and two commercial OBCs after 7-day aging at 20°C.
  • the tensile testing was conducted at 20°C and 37°C with 0, 30 and 180 seconds holding.
  • the blend with 10 wt% of OBC does not perform as well as the neat Vistamaxx 6102 propylene-based elastomer.
  • With higher OBC content of 25 wt% and 50 wt% the blends show smaller permanent set values than the neat Vistamaxx 6102 propylene-based elastomer in general.
  • the blends approximates the 37°C performance of EEPrE.
  • composition includes only the named components and no additional components that will alter its measured properties by any more than 20%, and most preferably means that additional components are present to a level of less than 5, or 4, or 3, or 2 wt% by weight of the composition.
  • additional components can include, for example, fillers, colorants, antioxidants, anti-UV additives, curatives and cross-linking agents, aliphatic and/or cyclic containing oligomers or polymers, often referred to as hydrocarbon resins, and other additives well known in the art.

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Abstract

L'invention concerne des mélanges de polymères comprenant au moins un copolymère séquencé d'oléfine tel que le poly(éthylène-b-éthylène/propylène-b-éthylène), et au moins un élastomère à base de propylène tel qu'un copolymère aléatoire de propylène-éthylène, de tels mélanges utiles dans des articles d'hygiène élastiques. Les mélanges ont une déformation permanente améliorée par rapport à l'élastomère à base de propylène seul.
PCT/US2017/038122 2016-09-21 2017-06-19 Compositions de copolymères séquencés d'oléfine et d'élastomères à base de propylène WO2018057078A1 (fr)

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WO2002066540A2 (fr) 2001-01-10 2002-08-29 Basell Poliolefine Italia S.P.A. Copolymeres blocs et leur procede de preparation
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
EP1623822A1 (fr) 2003-05-15 2006-02-08 Asahi Kasei Chemicals Corporation Lamine contenant des copolymeres hydrogenes
EP1858942A2 (fr) 2005-03-17 2007-11-28 Dow Gloval Technologies Inc. Melanges de polymeres a base d'un interpolymere d'ethylene/alphaolefine, a compatibilite amelioree
EP1871816A2 (fr) 2005-03-17 2008-01-02 Dow Global Technologies Inc. Melanges polymeres a base d'interpolymeres d'ethylene/alpha-olefines et articles moules souples ainsi obtenus
EP1882715A1 (fr) 2005-05-18 2008-01-30 Toray Industries, Inc. Mousse de resine de polyolefine reticulee
US7858706B2 (en) 2004-03-17 2010-12-28 Dow Global Technologies Inc. Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
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US5504172A (en) 1993-06-07 1996-04-02 Mitsui Petrochemical Industries, Ltd. Propylene polymer, propylene copolymer, and propylene elastomer prepared using novel bridged indenyl containing metallocenes
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
WO2002066540A2 (fr) 2001-01-10 2002-08-29 Basell Poliolefine Italia S.P.A. Copolymeres blocs et leur procede de preparation
EP1623822A1 (fr) 2003-05-15 2006-02-08 Asahi Kasei Chemicals Corporation Lamine contenant des copolymeres hydrogenes
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EP1858942A2 (fr) 2005-03-17 2007-11-28 Dow Gloval Technologies Inc. Melanges de polymeres a base d'un interpolymere d'ethylene/alphaolefine, a compatibilite amelioree
EP1871816A2 (fr) 2005-03-17 2008-01-02 Dow Global Technologies Inc. Melanges polymeres a base d'interpolymeres d'ethylene/alpha-olefines et articles moules souples ainsi obtenus
EP1882715A1 (fr) 2005-05-18 2008-01-30 Toray Industries, Inc. Mousse de resine de polyolefine reticulee
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EP2832171A1 (fr) 2012-03-29 2015-02-04 Intel Corporation Système de communication sans fil à deux modes
EP2831171A1 (fr) * 2012-03-30 2015-02-04 Dow Global Technologies LLC Formulations d'élastomères polyoléfiniques

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