US20180127564A1 - Filled polymer-based compositions with low viscosity, good mechanical properties and adhesion - Google Patents
Filled polymer-based compositions with low viscosity, good mechanical properties and adhesion Download PDFInfo
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- US20180127564A1 US20180127564A1 US15/574,272 US201615574272A US2018127564A1 US 20180127564 A1 US20180127564 A1 US 20180127564A1 US 201615574272 A US201615574272 A US 201615574272A US 2018127564 A1 US2018127564 A1 US 2018127564A1
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
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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
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
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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
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/17—Viscosity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/18—Bulk density
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- high flow ethylene-based polymers can be highly filled with fillers such as talc, CaCO3, or coal fly ash to improve mechanical properties and increased abrasion and scratch resistance.
- fillers such as talc, CaCO3, or coal fly ash
- high filler loadings typically increase the viscosity of the final composition, and thus reduced flow properties.
- plasticizers such as oils, can reduce the compositions viscosity and improve the flow characteristics, but, such additions typically result in poor mechanical properties and poor adhesion properties.
- the invention provides a composition comprising the following:
- A) a first polymer composition comprising an anhydride functionalized ethylene-based polymer, and optionally, an ethylene-based polymer;
- anhydride functionalized ethylene-based polymer has a density from 0.855 g/cc to 0.900 g/cc and a melt viscosity, at 177° C., from 1000 to 50,000 cP.
- inventive compositions described herein provide improved mechanical properties, which can be achieved using a highly filled composition with good high flow characteristics. It has been discovered that such compositions containing an anhydride functionalized ethylene-based polymer and high amounts of filler have an improved balance of mechanical and flow properties. Also, surprisingly, it has been discovered that the inventive compositions shown improved adhesion to paint, making such compositions well suited as substrates for painted and printed articles.
- composition comprising the following:
- A) a first polymer composition comprising an anhydride functionalized ethylene-based polymer, and optionally, an ethylene-based polymer;
- anhydride functionalized ethylene-based polymer has a density from 0.855 g/cc to 0.900 g/cc, and a melt viscosity, at 177° C., from 1000 to 50,000 cP.
- An inventive composition may comprise a combination of two or more embodiments as described herein.
- the anhydride functionalized ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
- the filler may comprise a combination of two or more embodiments as described herein.
- the composition comprises greater than, or equal to, 1.0 wt %, or greater than, or equal to, 1.2 wt %, or greater than, or equal to, 1.4 wt %, or greater than, or equal to, 1.6 wt %, or greater than, or equal to, 1.8 wt %, of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises greater than, or equal to, 2.0 wt %, or greater than, or equal to, 2.2 wt %, or greater than, or equal to, 2.4 wt %, or greater than, or equal to, 2.6 wt %, or greater than, or equal to, 2.8 wt %, of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises less than, or equal to, 75.0 wt %, or less than, or equal to, 70.0 wt %, or less than, or equal to, 65.0 wt %, less than, or equal to, 60.0 wt %, of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises less than, or equal to, 50.0 wt %, or less than, or equal to, 45.0 wt %, or less than, or equal to, 40.0 wt %, of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises ⁇ 1.0 wt %, or ⁇ 1.5 wt %, or ⁇ 2.0 wt %, or ⁇ 3.0 wt % of the anhydride functionalized ethylene-based polymer, based on the weight of the composition. In one embodiment, the composition comprises ⁇ 75 wt %, or ⁇ 60 wt %, or ⁇ 50 wt %, or ⁇ 40 wt % of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises from 1.0 wt % to 75.0 wt %, or from 1.5 wt % to 70.0 wt %, or from 2.0 wt % to 65.0 wt % of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the composition comprises from 1.0 wt % to 50.0 wt %, or from 1.5 wt % to 40.0 wt %, or from 2.0 wt % to 30.0 wt % of the anhydride functionalized ethylene-based polymer, based on the weight of the composition.
- the anhydride functional ethylene-based polymer comprises from 0.5 wt % to 3.0 wt %, or from 0.5 to 2.5 wt %, or from 0.5 to 2.0 wt % anhydride, based on the weight of the functional polymer.
- the weight ratio of the first polymer composition to the filler is from 1.0/1.0 to 1.0/5.0, or from 0.5/1.0 to 1.0/5.0, or from 0.6/1.0 to 1.0/5.0.
- the anhydride functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene-based polymer, and further a maleic anhydride grafted ethylene-based polymer.
- the anhydride functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene/alpha-olefin interpolymer, and further a maleic anhydride grafted ethylene/alpha-olefin interpolymer.
- Preferred ⁇ -olefins include, but are not limited to, C3-C20 ⁇ -olefins, and preferably C3-C10 ⁇ -olefins. More preferred ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include propylene, 1-butene, 1-hexene and 1-octene.
- the anhydride functionalized ethylene-based polymer is a maleic anhydride functionalized ethylene/alpha-olefin copolymer, and further a maleic anhydride grafted ethylene/alpha-olefin copolymer.
- Preferred ⁇ -olefins include, but are not limited to, C3-C20 ⁇ -olefins, and preferably C3-C10 ⁇ -olefins. More preferred ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include propylene, 1-butene, 1-hexene and 1-octene.
- the composition further comprises a tackifier, and further from 2.0 to 25.0 wt %, or from 5.0 to 20.0 wt %, or from 10.0 to 16.0 wt % tackifier, based on the weight of the composition.
- the composition comprises a tackifier, and the weight ratio of the tackifier to the filler is from 0.2:1 to 1:1, or from 0.28:1 to 0.7:1, or from 0.2:1 to 0.35:1.
- Tackifiers are typically chemical compounds, used in adhesive formulation or other formulations, to increase the tack (stickiness) of the formulation.
- example tackifiers include rosins and their derivates; terpenes and modified terpenes; aliphatic, cycloaliphatic and aromatic resins (for example, C5 aliphatic resins, C9 aromatic resins, and C5/C9 aliphatic/aromatic resins); hydrogenated hydrocarbon resins; mixtures of hydrogenated hydrocarbon resins; and terpene-phenol resins.
- the tackifier is selected from hydrogenated hydrocarbon resins and mixtures of hydrogenated hydrocarbon resins.
- the first composition comprises the ethylene-based polymer.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer.
- the weight ratio of the ethylene-based polymer to the anhydride functionalized ethylene-based polymer is from 1/1 to 6/1, or from 1/1 to 5/1.
- the ratio of “the density of the anhydride functionalized ethylene-based polymer” to “the density of the ethylene-based polymer” is from 0.7 to 1.3, or from 0.8 to 1.2, further from 0.9 to 1.1.
- the ratio of “the melt viscosity, at 177° C., of the anhydride functionalized ethylene-based polymer” to “the melt viscosity, at 177° C., of the ethylene-based polymer” is from 1.0 to 2.0, further from 1.2 to 1.8, further from 1.5 to 1.7.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/alpha-olefin interpolymer, and further an anhydride functionalized ethylene/alpha-olefin copolymer.
- the anhydride functionalized ethylene/alpha-olefin interpolymer, and further copolymer has a density from 0.855 to 0.890 g/cc, or from 0.855 to 0.885 g/cc, or from 0.860 to 0.885 g/cc, or from 0.860 to 0.880 g/cc.
- the anhydride functionalized ethylene/alpha-olefin interpolymer, and further copolymer has a molecular weight distribution (MWD) from 1.5 to 5.0, or from 1.5 to 4.0, or from 1.5 to 3.0, or from 1.5 to 2.5.
- MWD molecular weight distribution
- the first composition is present in an amount from 10 to 80 weight percent, or from 14 to 70 weight percent, or from 20 to 65 weight percent, based on the weight of the composition.
- the composition comprises greater than, or equal to, 70 wt %, or greater than, or equal to, 72 wt %, or greater than, or equal to, 75 wt %, or greater than, or equal to, 80 wt %, or greater than, or equal to, 85 wt %, of the sum weight of component A and component B, based on the weight of the composition.
- the composition has viscosity (V0.1 at 0.1 rad/s and 100° C.) from 1,000 to 10,000 Pa ⁇ s, or from 1,000 to 8,000 Pa ⁇ s, or from 1,000 to 6,000 Pa ⁇ s.
- the composition has viscosity (V0.1 at 0.1 rad/s and 100° C.) from 1,000 to 5,000 Pa ⁇ s, or from 1,000 to 4,000 Pa ⁇ s, or from 1,000 to 3,000 Pa ⁇ s. In one embodiment, the composition has a rheology ratio (V0.1/V100, at 100° C.) from 5.5 to 10.5, or from 6.0 to 10.0, or from 6.5 to 9.5.
- the composition has tan delta (DMS, 23° C.) from 0.10 to 0.18, or from 0.11 to 0.18, or from 0.12 to 0.18.
- the composition has a Shore A Hardness from 20 to 80, or from 30 to 75, or from 40 to 70.
- the composition has a melting temperature, Tm, from 30° C. to 70° C., or from 40° C. to 70° C., or from 50° C. to 70° C., or from 52° C. to 68° C.
- the composition has a melting temperature, Tc, from 25° C. to 55° C., or from 30° C. to 52° C., or from 35° C. to 50° C.
- the composition has a 10% Modulus ⁇ 90 psi, or ⁇ 100 psi, or ⁇ 110 psi, or ⁇ 120 psi, or ⁇ 130 psi, or ⁇ 140 psi, or ⁇ 150 psi, or ⁇ 200 psi, or ⁇ 250 psi, or ⁇ 300 psi, or ⁇ 350 psi.
- the composition has a 10% Modulus ⁇ 1000 psi, or ⁇ 950 psi, or ⁇ 900 psi, or ⁇ 800 psi, or ⁇ 750 psi, or ⁇ 700 psi.
- the composition has a 10% Modulus from 90 to 800 psi, or from 100 to 750 psi, or from 110 to 700 psi.
- the composition has a Tear Strength from 30 to 200 lbf/in, or from 40 to 180 lbf/in, or from 50 to 150 lbf/in.
- the weight ratio of the first composition to tackifier is from 1:1 to 6:1, or from 2:1 to 6:1, or from 3:1 to 5.5:1, or from 4:1 to 5.25:1, or from 4.5:1 to 5.25:1.
- the composition comprises the following: a) from 2.0 to 90.0 wt %, or from 2.0 to 70.0 wt %, or from 2.0 to 50.0 wt %, or from 2.0 to 40.0 wt %, or from of the anhydride functionalized ethylene-based polymer; b) from 0 to 90.0 wt %, or from 5.0 to 80.0 wt %, or from 10.0 to 75.0 wt %, or from 20 to 70.0 wt %, of the ethylene-based polymer, c) from 25.0 to 80.0 wt %, or from 30.0 to 75.0 wt %, or from 40.0 to 70.0 wt %, or from 50.0 to 70.0 wt %, of the filler (e.g., talc, coal fly ash, CaCO 3 ); and d) from 0 to 15 wt %, or from 2.0 to 25.0 wt %, or from 5.0 to 20.0 wt %, or from
- the composition comprises less than 1000 ppm, further less than 500 ppm of an alkylacrylate copolymer, based on the weight of the composition.
- the composition does not comprise an alkylacrylate copolymer.
- the composition comprises less than 1000 ppm, further less than 500 ppm of a propylene-based polymer, based on the weight of the composition.
- the composition does not comprise a propylene-based polymer.
- the filler is selected from the following: talc, calcium carbonate, carbon black, coal fly ash, glass fibers, polymeric fibers (including nylon, rayon, cotton, polyester, and polyaramide), metal fibers, flakes or particles, clays, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon whiskers, carbon fibers, wollastonite, graphite, zeolites, silicon carbide, silicon nitride, titanates (e.g., titanium dioxide), or combinations thereof.
- the filler is selected from the following: talc, calcium carbonate, coal fly ash, or combinations thereof.
- the composition comprises ⁇ 15.0 wt %, or ⁇ 20.0 wt %, or ⁇ 25.0 wt %, or ⁇ 30.0 wt %, or ⁇ 35.0 wt %, or ⁇ 40.0 wt %, or ⁇ 45.0 wt %, or ⁇ 50.0 wt %, of the filler (e.g., talc, coal fly ash, CaCO 3 ).
- the filler e.g., talc, coal fly ash, CaCO 3
- the composition comprises ⁇ 85.0 wt %, or ⁇ 80.0 wt %, or ⁇ 75.0 wt %, or ⁇ 70.0 wt %, or ⁇ 65.0 wt % of the filler (e.g., talc, coal fly ash, CaCO 3 ).
- the filler e.g., talc, coal fly ash, CaCO 3
- the inventive composition may comprise a combination of two or more embodiments as described herein.
- the invention also provides an article comprising at least one component formed from an inventive composition of any one or more embodiments described herein.
- the article further comprises a substrate.
- An inventive article may comprise a combination of two or more embodiments as described herein.
- the anhydride functionalized ethylene-based polymer of component A has a density greater than, or equal to, 0.857 g/cc, further greater than, or equal to, 0.860 g/cc, add further greater than, or equal to, 0.865 g/cc.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- Preferred ⁇ -olefins include, but are not limited to, C3-C20 ⁇ -olefins, and preferably C3-C10 ⁇ -olefins. More preferred ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include propylene, 1-butene, 1-hexene and 1-octene.
- the anhydride functionalized ethylene-based polymer of component A has a density less than, or equal to, 0.892 g/cc, further less than, or equal to, 0.890 g/cc, and further less than, or equal to, 0.885 g/cc.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a density from 0.857 g/cc to 0.892 g/cc, further from 0.860 g/cc to 0.890 g/cc, and further from 0.865 g/cc to 0.885 g/cc.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of Component A comprises from 0.5 to 3.0 weight percent, further from 0.5 to 2.5 weight percent, further from 0.5 to 2.0 weight percent of the anhydride functionality, based on the weight of the polymer.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of Component A has a melt viscosity less than, or equal to, 40,000 cP, further less than, or equal to, 30,000 cP, further less than, or equal to, 20,000 cP, and further less than, or equal to, 15,000 cP, at 350° F. (177° C.).
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- anhydride functionalized ethylene-based polymer of Component A has a melt viscosity greater than, or equal to, 2,000 cP, further greater than, or equal to, 3,000 cP, further greater than, or equal to, 4,000 cP, and further greater than, or equal to, 5,000 cP, at 350° F. (177° C.).
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of component A has a melt viscosity from 2,000 cP to 50,000 cP, further from 3,000 cP to 40,000 cP, further from 4,000 cP to 30,000 cP, at 350° F. (177° C.), and further from 5,000 cP to 20,000 cP, at 350° F. (177° C.).
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a molecular weight distribution (Mw/Mn) less than, or equal to, 5.0, further less than, or equal to, 4.0, further less than, or equal to, 3.0.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a molecular weight distribution (Mw/Mn) greater than, or equal to, 1.5, further greater than, or equal to, 2.0, and further greater than, or equal to, 2.5.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of component A has a weight average molecular weight (Mw) less than, or equal to, 50,000 g/mole, further less than, or equal to, 40,000 g/mole, further less than, or equal to, 30,000 g/mole.
- Mw weight average molecular weight
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of component A has a weight average molecular weight (Mw) greater than, or equal to, 3000 g/mole, further greater than, or equal to, 5000 g/mole, further greater than, or equal to, 10000 g/mole, further greater than, or equal to, 15000 g/mole.
- Mw weight average molecular weight
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- the anhydride functionalized ethylene-based polymer of component A has a melt index (I2), or calculated melt index (I2), greater than, or equal to, 300 g/10 min, further greater than, or equal to, 400 g/10 min, and more further greater than, or equal to, 500 g/10 min.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a melt index (I2), or calculated melt index (I2), less than, or equal to, 1500 g/10 min, further less than, or equal to, 1200 g/10 min, and more further less than, or equal to, 1000 g/10 min.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a percent crystallinity of less than, or equal to, 40 percent, further less than, or equal to, 35 percent, further less than, or equal to, 30 percent, further less than, or equal to, 25 percent, and further less than, or equal to, 20 percent, as determined by DSC.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer. Some preferred ⁇ -olefins are discussed above.
- the anhydride functionalized ethylene-based polymer of component A has a percent crystallinity of greater than, or equal to, 2 percent, further greater than, or equal to, 5 percent, and further greater than, or equal to, 10 percent, as determined by DSC.
- the anhydride functionalized ethylene-based polymer is an anhydride functionalized ethylene/ ⁇ -olefin interpolymer, and further an anhydride functionalized ethylene/ ⁇ -olefin copolymer.
- Suitable functionalized copolymers include MAH-grafted copolymers (for example, AFFINITY GA 1000R Polyolefin Plastomers, available from The Dow Chemical Company).
- An anhydride functionalized ethylene-based polymer may comprise a combination of two or more embodiments as described herein.
- the anhydride functionalized ethylene/alpha-olefin interpolymer of component A may comprise a combination of two or more embodiments as described herein.
- the anhydride functionalized ethylene/alpha-olefin copolymer of component A may comprise a combination of two or more embodiments as described herein.
- component A) comprises the ethylene-based polymer, and further an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer.
- Preferred ⁇ -olefins include, but are not limited to, C3-C20 ⁇ -olefins, and preferably C3-C10 ⁇ -olefins. More preferred ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably include propylene, 1-butene, 1-hexene and 1-octene.
- the ethylene-based polymer of component A has a melt viscosity less than, or equal to, 40,000 cP, further less than, or equal to, 30,000 cP, further less than, or equal to, 20,000 cP, and further less than, or equal to, 10,000 cP, at 350° F. (177° C.).
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- ethylene-based polymer of component A has a melt viscosity greater than, or equal to, 2,000 cP, further greater than, or equal to, 3,000 cP, further greater than, or equal to, 4,000 cP, and further greater than, or equal to, 5,000 cP, at 350° F. (177° C.).
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a melt viscosity from 2,000 cP to 40,000 cP, further from 3,000 cP to 30,000 cP, further from 4,000 cP to 20,000 cP, at 350° F. (177° C.), and further from 5,000 cP to 10,000 cP, at 350° F. (177° C.).
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a molecular weight distribution (Mw/Mn) less than, or equal to, 3.5, further less than, or equal to, 3.0, further less than, or equal to, 2.5, and further less than, or equal to, 2.3.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a molecular weight distribution (Mw/Mn) greater than, or equal to, 1.1, further greater than, or equal to, 1.3, further greater than, or equal to, 1.5, and further greater than, or equal to, 1.7.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer, and further ethylene/alpha-olefin interpolymer, and further copolymer of component A has a weight average molecular weight distribution (Mw) less than, or equal to, 50,000 g/mole, further less than, or equal to, 40,000 g/mole, further less than, or equal to, 30,000 g/mole.
- Mw weight average molecular weight distribution
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a weight average molecular weight (Mw) greater than, or equal to, 5000 g/mole, further greater than, or equal to, 10000 g/mole, further greater than, or equal to, 12000 g/mole, further greater than, or equal to, 15000 g/mole.
- Mw weight average molecular weight
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a melt index (12 or MI), or calculated melt index (12 or MI), greater than, or equal to, 200 g/10 min, further greater than, or equal to, 500 g/10 min, and more further greater than, or equal to, 800 g/10 min.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a melt index (12 or MI), or calculated melt index (12 or MI), less than, or equal to, 2000 g/10 min, further less than, or equal to, 1500 g/10 min, and further less than, or equal to, 1200 g/10 min.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a percent crystallinity of less than, or equal to, 50 percent, further less than, or equal to, 40 percent, and further less than, or equal to, 30 percent, further less than, or equal to, 20 percent as determined by DSC.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a percent crystallinity of greater than, or equal to, 2 percent, further greater than, or equal to, 5 percent, and further greater than, or equal to, 10 percent, as determined by DSC.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a density greater than, or equal to, 0.855 g/cc, further greater than, or equal to, 0.860 g/cc, further greater than, or equal to, 0.865 g/cc.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a density less than, or equal to, 0.900 g/cc, further less than, or equal to, 0.895 g/cc, further less than, or equal to, 0.890 g/cc, and further less than, or equal to, 0.885 g/cc.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer of component A has a density from 0.855 g/cm 3 to 0.900 g/cm 3 , further from 0.860 g/cm 3 to 0.895 g/cm 3 , and further from 0.865 g/cm 3 to 0.890 g/cm 3 .
- Preferred alpha-olefins are discussed above.
- the ethylene-based polymer is an ethylene/alpha-olefin interpolymer, and further an ethylene/alpha-olefin copolymer. Preferred alpha-olefins are discussed above.
- the ethylene-based polymer, and further ethylene/ ⁇ -olefin interpolymer, of component A is a homogeneously branched linear interpolymer, and further a copolymer, or a homogeneous branched substantially linear interpolymer, and further a copolymer.
- Preferred alpha-olefins are discussed above.
- the ethylene-based polymer, and further ethylene/ ⁇ -olefin interpolymer, of component A is a homogeneously branched linear interpolymer, and further a copolymer.
- the ethylene-based polymer, and further ethylene/ ⁇ -olefin interpolymer, of component A is a homogeneous branched substantially linear interpolymer, and further a copolymer.
- ethylene/ ⁇ -olefin copolymers include AFFINITY GA Polyolefin Plastomers, available from The Dow Chemical Company, and LICOCENE Performance Polymers from Clariant.
- ethylene/ ⁇ -olefin interpolymers suitable for the invention, include the ultra low molecular weight ethylene polymers described in U.S. Pat. Nos. 6,335,410, 6,054,544 and 6,723,810, each fully incorporated herein by reference.
- the ethylene-based polymer of component A may comprise a combination of two or more embodiments as described herein.
- the ethylene/alpha-olefin interpolymer of component A may comprise a combination of two or more embodiments as described herein.
- the ethylene/alpha-olefin copolymer of component A may comprise a combination of two or more embodiments as described herein.
- An inventive composition may comprise one or more additives.
- polymers used in the invention are treated with one or more stabilizers, for example, antioxidants, such as, for example, IRGANOX 1010, IRGANOX 1076, and IRGAFOS 168, now supplied by BASF.
- stabilizers for example, antioxidants, such as, for example, IRGANOX 1010, IRGANOX 1076, and IRGAFOS 168, now supplied by BASF.
- Polymers are typically treated with one or more stabilizers before an extrusion or other melt processes.
- Other polymeric additives include, but are not limited to, ultraviolet light absorbers, antistatic agents, pigments and dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, waxes, and anti-blocking agents.
- the inventive compositions may also contain one or more thermoplastic polymers.
- the inventive compositions may be prepared by standard melt blending procedures.
- the maleic anhydride-grafted polymer or blend, tackifier(s) and other components may be melt blended, until a homogeneous mix is obtained.
- Any mixing method producing a homogeneous blend, without degrading the adhesive components, is satisfactory, such as a vessel equipped with a stirrer, and an optional heating mechanism.
- the adhesives can be provided in forms, such as pellets, pillows, chiclets, drags, or any other desired configurations.
- inventive compositions may also be used in a variety of application.
- the invention provides for an article comprising at least one component formed from an inventive composition.
- Articles include, but not limited to, painted substrates, packages, automotive components, graphic arts, nonwovens, tapes, hot melt adhesives, coatings, inks, personal care and cosmetic products, sealants, color and additive concentrates, carpet components, and furniture.
- composition includes a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
- polymer refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
- the generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term interpolymer as defined hereinafter. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer.
- interpolymer refers to polymers prepared by the polymerization of at least two different types of monomers.
- the generic term interpolymer thus includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
- olefin-based polymer refers to a polymer that comprises, in polymerized form, a majority amount of olefin monomer, for example ethylene or propylene (based on the weight of the polymer), and optionally may comprise one or more comonomers.
- ethylene-based polymer refers to a polymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers.
- ethylene/ ⁇ -olefin interpolymer refers to an interpolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the interpolymer), and at least one ⁇ -olefin.
- ethylene/ ⁇ -olefin copolymer refers to a copolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer), and an ⁇ -olefin, as the only two monomer types.
- propylene-based polymer refers to a polymer that comprises, in polymerized form, a majority amount of propylene monomer (based on the weight of the polymer), and optionally may comprise one or more comonomers.
- anhydride functionalized ethylene-based polymer refers to an ethylene-based polymer comprising bonded anhydride groups (for example, bonded MAH (bonded maleic anhydride), and further grafted MAH (grafted maleic anhydride)). It is understood that a minor portion of the bonded anhydride may hydrolyzed into acid groups.
- the term “fully hydrogenated,” as used herein, refers to a hydrogenation level greater than 90%.
- non-hydrogenated refers to a hydrogenation level less than 50%.
- the hydrogenation level can be determined by those skilled in the art, for example, by proton (1H) NMR.
- compositions claimed through use of the term “comprising” may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary.
- the term, “consisting essentially of” excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability.
- the term “consisting of” excludes any component, step or procedure not specifically delineated or listed.
- Melt viscosity is measured in accordance with ASTM D 3236 (350° F.), using a Brookfield Digital Viscometer (Model DV-III, version 3), and disposable aluminum sample chambers.
- the spindle used in general, is a SC-31 hot-melt spindle, suitable for measuring viscosities in the range from 10 to 100,000 centipoise.
- the sample (polymer or adhesive composition) is poured into the chamber, which is, in turn, inserted into a Brookfield Thermosel, and locked into place.
- the sample chamber has a notch on the bottom that fits the bottom of the Brookfield Thermosel, to ensure that the chamber is not allowed to turn when the spindle is inserted and spinning.
- the sample (approximately 8-10 grams of resin) is heated to the required temperature, until the melted sample is about one inch below the top of the sample chamber.
- the viscometer apparatus is lowered, and the spindle submerged into the sample chamber. Lowering is continued, until the brackets on the viscometer align on the Thermosel.
- the viscometer is turned on, and set to operate at a shear rate, which leads to a torque reading in the range of 40 to 60 percent of the total torque capacity, based on the rpm output of the viscometer. Readings are taken every minute for about 15 minutes, or until the values stabilize, at which point, a final reading is recorded.
- melt index (I2, or MI) of an ethylene-based polymer is measured in accordance with ASTM D-1238, condition 190° C./2.16 kg.
- melt index is preferably calculated from Brookfield viscosity as described in U.S. Pat. Nos. 6,335,410; 6,054,544; 6,723,810.
- the average molecular weights and molecular weight distributions for ethylene-based polymers are determined with a chromatographic system, consisting of either a Polymer Laboratories Model PL-210 or a Polymer Laboratories Model PL-220.
- the column and carousel compartments are operated at 140° C. for ethylene-based polymers.
- the columns are three Polymer Laboratories 10-micron, Mixed-B columns.
- the solvent is 1,2,4-trichloro-benzene.
- the samples are prepared at a concentration of “0.1 gram of polymer’ in “50 milliliters” of solvent.
- the solvent used to prepare the samples contains 200 ppm of butylated hydroxytoluene (BHT).
- Samples are prepared by agitating lightly, for two hours, at 160° C.
- the injection volume is “100 microliters,” and the flow rate is 1.0 milliliters/minute.
- Calibration of the GPC column set is performed with narrow molecular weight distribution polystyrene standards, purchased from Polymer Laboratories (UK).
- the polystyrene standard peak molecular weights are converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
- M polyethylene A ⁇ ( M polystyrene ) B ,
- M is the molecular weight
- A has a value of 0.4315 and B is equal to 1.0.
- Polyethylene equivalent molecular weight calculations were performed using VISCOTEK TriSEC software, Version 3.0.
- the column and carousel compartments are operated at 160° C.
- DSC Differential Scanning calorimetry
- PE ethylene
- PP propylene
- melting point(s) (T m ) and glass transition temperature (Tg) of each polymer is determined from the second heat curve obtained from DSC, as described above.
- the crystallization temperature (T a ) is measured from the first cooling curve.
- Density is measured in accordance with ASTM D-792. The density measured is a “quick density,” meaning that the density is determined after one hour from the time of molding. Test samples are compression molded at a temperature of 20° C. higher than the melting point of polymer, and at a pressure of 10 MPa for five minutes (dimensions of molded sample: 50 cm 2 ⁇ 1-2 mm).
- FTIR Fourier Transform Infrared Spectroscopy
- the concentration of maleic anhydride is determined by the ratio of peak heights of the maleic anhydride at wave number 1791 cm ⁇ 1 to the polymer reference peak, which, in case of polyethylene, is at wave number 2019 cm ⁇ 1 .
- Maleic anhydride content is calculated by multiplying this ratio with the appropriate calibration constant.
- the equation used for maleic grafted polyolefins (with reference peak for polyethylene) has the following form, as shown in Equation 1.
- MAH (wt %) A * ⁇ [FTIR PeakArea@1791 cm ⁇ 1]/[FTIR PeakArea 2019 cm ⁇ 1]+ B *[FTIR PeakArea@1712 cm ⁇ 1]/[FTIR_PeakArea@2019 cm ⁇ 1] ⁇ (Eqn. 1)
- the calibration constant A can be determined using C13 NMR standards.
- the actual calibration constant may differ slightly, depending on the instrument and polymer.
- the second component, at wave number 1712 cm ⁇ 1 accounts for the presence of maleic acid, which is negligible for freshly grafted material. Over time however, maleic anhydride is readily converted to maleic acid in the presence of moisture. Depending on surface area, significant hydrolysis can occur in just a few days under ambient conditions. The acid has a distinct peak at wave number 1712 cm ⁇ 1 .
- the constant B in Equation 1 is a correction for the difference in extinction coefficients between the anhydride and acid groups.
- the sample preparation procedure begins by making a pressing, typically 0.05 to 0.15 millimeters in thickness, in a heated press, between two protective films, at 150-180° C. for one hour.
- MYLAR and TEFLON are suitable protective films to protect the sample from the platens.
- Aluminum foil must never be used (maleic anhydride reacts with aluminum). Platens should be under pressure ( ⁇ 10 ton) for about five minutes.
- the sample is allowed to cool to room temperature, placed in an appropriate sample holder, and then scanned in the FTIR. A background scan should be run before each sample scan, or as needed. The precision of the test is good, with an inherent variability of less than ⁇ 5%. Samples should be stored with desiccant to prevent excessive hydrolysis.
- Moisture content in the product has been measured as high as 0.1 weight percent.
- the conversion of anhydride to acid however is reversible with temperature, but may take up to one week for complete conversion.
- the reversion is best performed in a vacuum oven at 150° C.; a good vacuum (near 30 inches Hg) is required. If the vacuum is less than adequate, the sample tends to oxidize, resulting in an infrared peak at approximately 1740 cm ⁇ 1 , which will cause the values for the graft level to be too low.
- Maleic anhydride and acid are represented by peaks at about 1791 and 1712 cm ⁇ 1 , respectively.
- the dynamic mechanical measurements (loss and storage modulus vs. temperature) are measured on TA instruments ARES.
- the dynamic modulus measurements were performed in torsion on a solid bar of about 2 mm thickness, 5 mm wide and about 10 mm in length, cut from a compression molded plaque (see experimental section). The data was recorded at a constant frequency of 10 rad/s, and at a heating/cooling rate of 5° C./min. The temperature sweeps were performed from ⁇ 50 to 190° C. at 5° C./min.
- Reported values include the G′ and the tan delta (ratio of G′′ and G′ response) at 23° C.
- V0.1/V100 also referred to as “RR”
- Tear Strength (lbf/in) was determined using ASTM D624; Thermoplastic Type C, with five samples to obtain the average tear value.
- ASTM D 624 can be used to measure the resistance to the formation of a tear (tear initiation) and the resistance to the expansion of a tear (tear propagation). The sample is held between two holders and a uniform pulling force applied until the aforementioned deformation occurs. Tear resistance is then calculated by dividing the force applied by the thickness of the material. Each test sample was cut from a compression molded plaque (see experimental section).
- Tensile properties were measured using specimens which were die cut, using a small “dog bone” shaped micro tensile die, having the dimensions described in ASTM D-1708. The die cut specimens were cut from the compression molded plaques—see experimental section below. Tensile properties (tensile strength and elongation) were measured at room temperature, using an INSTRON MODEL 1122, made by INSTRU-MET. The “stress versus strain” measurement provides the values for the 10% Modulus (psi)—modulus measured at 10% strain, strain at break (%), and stress at break (psi). An average of five test samples was reported.
- Sample specimens (3 cm by 3 cm) were cut from compression molded plaques, which were prepared as described in the experimental section below.
- Shore A hardness was measured per ASTM D2240, on a Shore A Durometer Model 2000, made by INSTRON, with a Durometer Stand Model 902. This method permits hardness measurements, based on either initial indentation, or indentation after a specific period of time, or both. As used herein, the indentation was measured at a specified time of ten seconds.
- composition properties are shown in Tables 2 and 3.
- Table 1 shows the comparative and inventive compositions.
- the components were melt compounded, under a nitrogen purge, in a Laboratory HAAKE mixer (45 gram, small bowl) at a temperature of 150° C. Each composition was then compression molded for further testing.
- compositions were compression molded at 150 C.
- the pressure was set at 3000 lbs for 6 minutes, and then increased to 15 tons for 20-25 minutes. The pressure was maintained, while cooling to 30 C at a rate of 15° C./min.
- Each composition was molded into a “7 inch ⁇ 7 inch ⁇ 0.075 inch” plaque. Microtensile and C-tear specimens were cut from the plaques using a punch press. Tables 2 and 3 summarize the mechanical, Shore A, DSC, and DMS solid state, and DMS melt state properties of the compositions.
- inventive compositions showed improved solid phase elasticity, as indicated by the lower tan delta values from 0.13 to 0.18, as compared to values from 0.19 to 0.25 for the comparative compositions (DMS solid test method). It was also discovered that the inventive compositions had increased melt phase interaction, as indicated by a higher viscosity (V0.1 at 0.1 rad/s, 100° C.) for the inventive compositions (DMS melt test method). Also, the DMS (solid test method) tan delta, at 23° C., of the inventive compositions decreased, when compared to the respective comparative compositions. The observed improvement in these rheological properties suggests increased interaction and compatibility between the filler and the MAH-P of the inventive compositions.
- the DMS melt test method
- V0.1N100 ratio also significantly increased, indicating that viscosity of the inventive compositions, at high shear, decreases, which, in turn, indicates the inventive compositions should flow well at high shear rate.
- the inventive compositions have the benefits of higher melt strength and good flow at high shear rates, which are desirable processing features.
- Each plaque was spray painted with a “SEM SURECOAT” waterborne paint, to form a painted plaque with a paint layer of around 1 mil in thickness. The painted surface and allowed to dry for 24 hours prior to testing. No other surface modification or cleaning was performed prior to the application of the paint.
- Crosshatch adhesion is a common industrial method for evaluating adhesion strength of a coating to a substrate.
- a crosshatch scribe is used to make parallel linear cuts through the surface coating.
- a similar set of linear cuts is made perpendicular to the original cuts, in order to obtain a checker board pattern.
- the total number of individual, scribed squares is 100.
- the surface area of the scribed surface was about “1 inch ⁇ 1 inch.”
- a tape (Scotch Tape 3M #810) was applied to the scribed surface, and the tape-covered area was rubbed with fingers, in order to apply adequate pressure, ensuring intimate contact with the surface (approximate 50 g force).
- the painted plaque was allowed to sit for 10-30 seconds, and then the loose end of the tape was hand pulled, smoothly at an angle of about 135 degrees, to remove the tape from the surface.
- the coated surface was then visually evaluated for adhesion (ASTM D3359), and ranked using a numerical scaling, to provide an indication of the adhesion strength (or the adhesion between the paint and the substrate).
- 5B 100% area covered (with paint)/no adhesion failure; 4B: >95% to ⁇ 100% area covered; 3B: >85% to 95% area covered; 2B: >65% to 85% area covered; 1B: >35% to 65% area covered 0B: ⁇ 35% area covered (or ⁇ 65% of painted surface peeled off with the tape).
- composition properties are shown in Table 6.
- the components were melt compounded, under a nitrogen purge, in a Laboratory HAAKE mixer (45 gram, small bowl) at a temperature of 150° C. Each composition was then compression molded, as discussed above, for further testing.
- compositions were tested up to approx. 71 wt % calcium carbonate and 15 wt % hydrocarbon tackifier.
- inventive composition showed excellent mechanical properties: tear strength+30%, 10% modulus+100%, tensile strain @ break+100%.
- Shore A of the inventive composition increased, when compared to the respective comparative composition. The observed improvement in properties suggests increased interaction and compatibility between the filler and the MAH-P of the inventive compositions.
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US12031020B2 (en) | 2018-07-03 | 2024-07-09 | Dow Global Technologies Llc | Olefin-based polymer compositions for flooring applications |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080306217A1 (en) * | 2005-12-29 | 2008-12-11 | Karjala Teresa P | Low Molecular Weight Ethylene Interpolymers, Methods of Making, and Uses Thereof |
US20100160497A1 (en) * | 2006-06-15 | 2010-06-24 | Teresa P Karjala | Functionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the same |
US20160304650A1 (en) * | 2013-12-30 | 2016-10-20 | Dow Global Tecnologies LLC | Method to produce functionalized, low viscosity ethylene-based polymers |
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US3963850A (en) | 1970-09-29 | 1976-06-15 | Phillips Petroleum Company | Adhesive formulation improved with solid fillers |
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JPH0578589A (ja) | 1991-09-19 | 1993-03-30 | Mitsubishi Petrochem Co Ltd | 樹脂組成物 |
JPH09286878A (ja) | 1996-04-23 | 1997-11-04 | Ube Ind Ltd | ポリオレフィン組成物およびそのシート |
KR20000075675A (ko) * | 1997-02-28 | 2000-12-26 | 그래햄 이. 테일러 | 충전된 폴리에틸렌 조성물 |
TR200001723T2 (tr) * | 1997-10-21 | 2000-10-23 | The Dow Chemical Company | Termoplastik işaretleme karışımları |
JP2001302991A (ja) * | 2000-04-20 | 2001-10-31 | Lintec Corp | 塗装用粘着テープ |
US7550528B2 (en) | 2002-10-15 | 2009-06-23 | Exxonmobil Chemical Patents Inc. | Functionalized olefin polymers |
EP1964884A1 (en) | 2002-10-17 | 2008-09-03 | Dow Global Technologies Inc. | Highly filled polymer compositions |
KR101399699B1 (ko) * | 2005-03-17 | 2014-05-27 | 다우 글로벌 테크놀로지스 엘엘씨 | 관능화된 에틸렌/α-올레핀 혼성중합체 조성물 |
DE102006039833A1 (de) | 2006-08-25 | 2008-03-20 | Henkel Kgaa | Schmelzklebstoff mit verbesserter Haftung |
WO2013185340A1 (en) * | 2012-06-15 | 2013-12-19 | Dow Global Technologies Llc | Adhesive compositions containing modified ethylene-based polymers |
CN103389791B (zh) | 2013-06-25 | 2016-10-05 | 华为技术有限公司 | 数据系统的功率控制方法及装置 |
AU2014293082B2 (en) | 2013-07-24 | 2018-05-10 | Dow Global Technologies Llc | Adhesive compositions containing functionalized ethylene/alpha-olefin interpolymers and rosin-based tackifiers |
JP2015063588A (ja) * | 2013-09-24 | 2015-04-09 | ヘンケルジャパン株式会社 | ホットメルト接着剤 |
EP3087152A1 (en) | 2013-12-26 | 2016-11-02 | Dow Global Technologies LLC | Adhesive compositions containing modified ethylene-based polymers and compatible tackifiers |
WO2016026121A1 (en) | 2014-08-21 | 2016-02-25 | Dow Global Technologies Llc | Adhesive compositions comprising low molecular weight functionalized olefin-based polymers |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080306217A1 (en) * | 2005-12-29 | 2008-12-11 | Karjala Teresa P | Low Molecular Weight Ethylene Interpolymers, Methods of Making, and Uses Thereof |
US20100160497A1 (en) * | 2006-06-15 | 2010-06-24 | Teresa P Karjala | Functionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the same |
US20150361315A1 (en) * | 2006-06-15 | 2015-12-17 | Dow Global Technologies Llc | Functionalized olefin interpolymers, compositions and articles prepared therefrom, and methods for making the same |
US20160304650A1 (en) * | 2013-12-30 | 2016-10-20 | Dow Global Tecnologies LLC | Method to produce functionalized, low viscosity ethylene-based polymers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11098144B2 (en) | 2016-06-30 | 2021-08-24 | Dow Global Technologies Llc | Ethylene/alpha-olefin/polyene interpolymers and compositions containing the same |
US12031020B2 (en) | 2018-07-03 | 2024-07-09 | Dow Global Technologies Llc | Olefin-based polymer compositions for flooring applications |
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US11542383B2 (en) | 2023-01-03 |
ES2940657T3 (es) | 2023-05-10 |
KR20180021792A (ko) | 2018-03-05 |
AU2016284025B2 (en) | 2020-04-23 |
KR102566182B1 (ko) | 2023-08-14 |
US20200172700A1 (en) | 2020-06-04 |
JP2018518570A (ja) | 2018-07-12 |
CN107709448B (zh) | 2021-05-04 |
BR112017025503A2 (pt) | 2018-08-07 |
CN107709448A (zh) | 2018-02-16 |
JP6946198B2 (ja) | 2021-10-06 |
EP3313936A1 (en) | 2018-05-02 |
EP3313936B1 (en) | 2023-02-15 |
BR112017025503B1 (pt) | 2022-01-04 |
AU2016284025A1 (en) | 2018-02-01 |
WO2016209754A1 (en) | 2016-12-29 |
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