WO2007027862A2 - Soft polymer compositions having improved high temperature properties - Google Patents
Soft polymer compositions having improved high temperature properties Download PDFInfo
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- WO2007027862A2 WO2007027862A2 PCT/US2006/033985 US2006033985W WO2007027862A2 WO 2007027862 A2 WO2007027862 A2 WO 2007027862A2 US 2006033985 W US2006033985 W US 2006033985W WO 2007027862 A2 WO2007027862 A2 WO 2007027862A2
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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
- C08L23/02—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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
- C08L23/0876—Salts thereof, i.e. ionomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- C08L23/02—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
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
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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
- C08L23/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/71—Resistive to light or to UV
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2509/00—Household appliances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/08—Cars
Definitions
- This invention relates to a soft polymer composition
- a soft polymer composition comprising an ethylene/alkyl (meth)acrylate copolymer and a crystalline polyolefin, such as polypropylene homopolymer or polypropylene copolymer and to the preparation and use of the composition.
- Blends of an ethylene/alkyl acrylate copolymer with an ethylene/propylene copolymer having a melting point greater than 100 0 C, or polypropylene with an ethylene/ethyl acrylate copolymer in the presence of a peroxide have been disclosed. See, e.g., Japanese Patent Application JP6329744A and US Patent 4,234,656.
- Thermoplastic elastomer compositions made by dynamic crosslinking have also been disclosed. See, e.g., US Patent 4,710,544 and EP0964890 B1.
- This invention provides a composition
- a composition comprising (a) a blend of from about 20 to about 50 weight % of at least one crystalline polyolefin and from about 50 to about 80 weight % of at least one ethylene/alkyl (meth)acrylate copolymer with a higher melt viscosity than the polyolefin (at an apparent shear rate of about 1 ,000 sec "1 ).
- the composition optionally has a Shore D hardness of less than 50 comprising a blend of from 25 to 45 weight % of at least one polypropylene homopolymer or polypropylene copolymer; and from 55 to 75 weight % of at least one ethylene/alkyl acrylate copolymer with a higher melt viscosity (at an apparent shear rate of about 1,000 sec "1 ) than the polyolefin, preferably ethylene/alkyl acrylate copolymer to the melt viscosity of the propylene is greater than 1.25, more preferably greater than 1.5.
- composition 5 described above further comprises (b) from about 1 to about 10 weight % of one or more components that can improve the scratch-and-mar properties of the composition.
- composition described above further comprises (c) from 0.01 to 20 weight % of at least
- plasticizers one additional component selected from the group consisting of plasticizers, stabilizers, antioxidants, UV absorbers, antistatic agents, dyes, pigments or other coloring agents, fluorescent whitening agents, inorganic fillers, delustrants, terminating agents, fire-retardants, lubricants, reinforcing agents, foaming or blowing agents, processing aids, slip
- plasticizers stabilizers, antioxidants, UV absorbers, antistatic agents, dyes, pigments or other coloring agents, fluorescent whitening agents, inorganic fillers, delustrants, terminating agents, fire-retardants, lubricants, reinforcing agents, foaming or blowing agents, processing aids, slip
- This invention also provides articles prepared from the compositions described above; including articles such as films, multilayer laminates, extruded sheets, coated fabrics, and articles that can be 20 shaped by injection molding, extrusion molding, profile-extrusion or thermoforming.
- Copolymer means polymers containing two or more different monomers.
- Thermoplastic compositions are polymeric materials that can flow when heated under pressure.
- Melt index (Ml) is the mass rate of flow of a polymer through a specified capillary under controlled conditions of temperature and pressure. Melt indices reported herein are determined according to ASTM 1238 at 19O 0 C using a 2160 g weight, with values of
- the limit of high temperature properties of a material can be measured in different ways, such as by the deflection of a beam under a given load, or by the indentation of a "foot” into a block of material under a load.
- the heat deflection temperature (HDT) according to ASTM D648,
- the Vicat temperature determines the temperature at which a standard indenter penetrates one mm below the surface of a test
- compositions as described herein wherein the composition has a Vicat temperature of at least 60 0 C, preferably greater 20 than 65 0 C.
- heat deflection temperatures are compared by testing a sample with a span of 50 mm, and a height of 6.35 mm, with a 16.5 psi (0.116 MPa) load at a heating rate of 2°C/min to a deflection of 500 ⁇ .
- compositions as described herein wherein a molded sample of the composition with a height of 6.35 mm, with a 16.5 psi (0.116 MPa) load at the mid-point of a 50-mm span in a 3-point bending of 2°C/min, deflects to 500 ⁇ at temperatures greater than 60, or greater than 70 0 C.
- UST upper service temperature
- TMA thermomechanical analyzer
- TA Instruments Inc A force of one Newton is applied to the probe as it rests on the surface of the specimen, in a chamber where the temperature 10 is ramped at a rate of 5°C/min.
- the UST documents the point where the material has lost most of its resistance to deformation, with an upper limit that approaches the melting point of the material.
- compositions as described herein wherein a molded sample of the composition having a thickness of about 3 mm, heated in a 15 chamber at a rate of 5°C/min, is penetrated by a probe of 0.89 mm contact diameter with an applied force of one Newton to a depth of 900 micrometers at temperatures greater than 105, greater than 120, or greater than 14O 0 C.
- a composition comprises a blend of at least one crystalline 20 polyolefin, such as polypropylene, and at least one ethylene/alkyl
- the polyolefin such as polypropylene homopolymer or polypropylene copolymer
- the 25 composition approaches a structure in which the two polymers are co- continuous. This is evidenced by transmission electron micrographs where the polypropylene phase is seen to have a very large aspect ratio, or even where it is impossible to decide if the polypropylene is in fact continuous or not. In this way the structure contributes significantly to the 30 properties of the blend, especially at high temperatures.
- Polypropylene (PP) polymers can include homopolymers, random copolymers, block copolymers and terpolymers of propylene.
- Copolymers include copolymers of propylene with other olefins such as ethylene, ⁇ / ikf i n' v nd he various pentene isomers, etc. and notably copolymers of propylene with ethylene.
- Terpolymers of propylene include copolymers of propylene with ethylene and one other olefin.
- Random copolymers also known as statistical copolymers, are polymers in which 5 the propylene and the comonomer(s) are randomly distributed throughout the polymeric chain in ratios corresponding to the feed ratio of the propylene to the comonomer(s).
- Block copolymers are made up of chain segments consisting of propylene homopolymer and of chain segments consisting of, for example, random copolymers of propylene and ethylene. 10
- polypropylene when used herein is used generically to refer to any or all of the polymers comprising propylene described above.
- the polypropylenes used herein have a melting point above 100 0 C, more preferably above 130 0 C.
- Polypropylenes disclosed can be manufactured by any known 15 process.
- polypropylene polymers can be prepared in the presence of Ziegler-Natta catalyst systems, based on organometallic compounds and on solids containing titanium trichloride.
- Block copolymers can be manufactured similarly, except that propylene is generally first polymerized by itself in a first stage and
- propylene and additional comonomers such as ethylene are then polymerized, in a second stage, in the presence of the polymer obtained during the first.
- Each of these stages can be carried out, for example, in suspension in a hydrocarbon diluent, in suspension in liquid propylene, or else in gaseous phase, continuously or noncontinuously, in the same
- (Meth)acrylate and “alkyl (meth)acrylate” mean ester(s) of methacrylic acid and/or acrylic acid.
- "Ethylene/alkyl acrylate copolymer” includes copolymer of ethylene and at least one alkyl acrylate, preferably wherein the alkyl moiety contains from 1 to 12 carbon atoms. Examples of IR !C me thyl acrylate, ethyl acrylate and butyl acrylate.
- Ethylene/methyl acrylate means a copolymer of ethylene and methyl acrylate (EMA), "ethylene/ethyl acrylate” means a copolymer of ethylene and ethyl acrylate (EEA) and "ethylene/butyl acrylate” means a copolymer 5 of ethylene and butyl acrylate (EBA).
- the relative amount of the alkyl acrylate comonomer incorporated into ethylene/alkyl acrylate copolymers can vary broadly from a few weight percent (e.g., 2 or 5) up to as high as 40 weight percent of the total copolymer or even higher.
- the alkyl group varies from a simple methyl
- the relative amount and choice of the alkyl group present in the alkyl acrylate ester comonomer can establish how and to what degree the resulting ethylene copolymer is to be viewed as a polar polymeric constituent in the thermoplastic composition.
- the alkyl group in the alkyl (meth)acryiate comonomer preferably has from 1 to 4 carbon atoms and the alkyl (meth)acrylate comonomer can have a concentration range of (meth)acrylate monomer from 5 to 40, or from 10 to 35, weight percent in the ethylene/alkyl (meth)acrylate copolymer.
- alkyl (meth)acrylate can be methyl acrylate
- Ethylene/alkyl (meth)acrylate copolymers can be prepared by processes well known in the polymer art using either autoclave or tubular reactors. The copolymerization can be run as a continuous process in an autoclave: ethylene, the alkyl (meth)acrylate, and optionally a solvent
- reaction mixture such as methanol (see US Patent Number 5,028,674) are fed continuously into a stirred autoclave such as the type disclosed in US Patent 2,897,183, together with an initiator, the description of which is omitted herein for the interest of brevity.
- a telogen such as propane
- the copolymer is separated from the unreacted monomers and solvent (if solvent was used) by means such as vaporizing materials and solvent under reduced pressure and at an elevated temperature.
- Tubular reactor produced ethylene/alkyl (meth)acrylate copolymer can be distinguished from the autoclave produced ethylene/alkyl 5 (meth)acrylate as known in the art.
- the term or phrase "tubular reactor produced" ethylene/alkyl (meth)acrylate copolymer denotes an ethylene copolymer produced at high pressure and elevated temperature in a tubular reactor or the like, wherein the inherent consequences of dissimilar reaction kinetics for the respective ethylene and alkyl (meth)acrylate
- Tubular reactor produced ethylene/alkyl acrylate copolymers are commercially available from E. I. du Pont de Nemours and Company, Wilmington, Delaware (DuPont).
- the ethylene/alkyl acrylate copolymers can vary in melt index numerically in terms of a fraction (e.g., 0.1 , 0.2, or 0.4) up to about 10.
- the specific selection of the grade of ethylene/alkyl acrylate copolymer pGh ⁇ M ⁇ S) ⁇ i® « m used will be influenced by balancing factors such as viscosities, melt indices or melt flow rates, and melting points of the copolymer and the polypropylene.
- composition may optionally further comprise additive(s) (e.g., 1 to 10 wt %) that improve the scratch-and-mar performance of the compositions.
- additive(s) e.g., 1 to 10 wt % that improve the scratch-and-mar performance of the compositions.
- compositions can also comprise additives including plasticizers, stabilizers including viscosity stabilizers, thermal stabilizers, ultraviolet (UV) stabilizers and hydrolytic stabilizers, primary and secondary antioxidants, UV absorbers, anti-static agents, dyes, pigments or other coloring agents, fluorescent whitening agents, inorganic fillers such as CaCO 3 , delustrants such as TiO 2 , terminating agents, fire- retardants, lubricants, reinforcing agents such as glass fiber and flakes, foaming or blowing agents, processing aids, slip additives, antiblock agents such as silica or talc, release agents, tackifying resins and/or mixtures thereof. See, e.g., Kirk Othmer Encyclopedia of Chemical Technology.
- additives may be present in the compositions of this invention in quantities from 0.01 to 20 weight % or 0.01 to 15 weight %, or 0.01 to 10 weight %. Many such additives may be present in from 0.01 to 5 weight %.
- additive(s) into the compositions can be carried out by any known process. This incorporation can be carried out, for example, by dry blending, by extruding a mixture of the various constituents, or the like.
- compositions of this invention are suitable for replacement for flexible polyvinyl chloride (f-PVC).
- Flexible PVC contains a plasticizer, typically a phthalate plasticizer, to enhance flexibility and softness.
- the plasticizer can migrate out of the PVC composition over time, decreasing flexibility and softness and potentially contaminating materials in contact with the composition.
- Shore D hardness range of 35 to 45 that can perform over a range of temperatures similar to f-PVC.
- Flexible PVC often has a Vicat temperature in the range of 60 to 70 0 C, but also is known to maintain some strength up to much higher temperatures.
- 5 compositions of this invention having Shore D hardness of from 35 to 45, optionally having vicat temperature of from 60 to 70 0 C.
- Thermoplastic polyolefins including reactively modified polyolefin blends have been used in place of f-PVC in some applications, and the compositions of the present invention could be an alternative to them.
- the 10 compositions of the present invention also have advantages compared to polyolefin-based blends in that the polarity of the acrylate copolymer may give superior properties in such areas as adhesion, paintability, and resistance to hydrocarbon solvents.
- the composition may be formed into articles of manufacture such 15 as parts, sheets, or other forms using any of a number of conventional procedures for processing polymeric materials.
- the compositions can also be formed into films, multilayer laminates or extruded sheets, injection molded into shaped articles such as knobs or handles for appliances or consumer goods, used for profile-extruded 20 articles such as tubing, or for coated fabrics or other film and sheet applications.
- the composition may also be used in thermoforming, such as those compositions with high melt strength.
- the compositions may be useful in the manufacture of automobile interior parts, automobile exterior parts, consumer goods with soft-touch grips, and consumer appliances 25 with soft-touch surfaces. Other applications may be possible and are within the knowledge of those skilled in the art.
- compositions described herein were prepared by mixing the components on a 30mm W&P twin-screw extruder. The product was strand cut and dried, and injection molded to give 3 inch by 3 inch by cm by 32 mm) plaques and 1/8-inch (3.2 mm) microtensile bars. Hardness (Shore D) was measured according to ASTM D-2240, and tensile properties, such as tensile strength and extension, according to ASTM D-412.
- EMA-1 Ethylene/alkyl acrylate copolymer (tubular) with 25 weight % methyl acrylate, a melting point of 88°C, a Ml of 0.4 g/10min and a viscosity of 262 Pa-s.
- EMA-2 Ethylene/alkyl acrylate copolymer (tubular) with 10 24 weight % methyl acrylate, a melting point of 92°C, a Ml of 2.0 g/10min and a viscosity of 153 Pa-s.
- EMA-3 Ethylene/alkyl acrylate copolymer (autoclave) with 23.5 weight % methyl acrylate, a melting point of 76°C, a Ml of 1.0 g/10min and a viscosity of 206 Pa-s.
- EBA-1 Ethylene/alkyl acrylate copolymer with 35 weight % butyl acrylate, a melting point of 78°C, a Ml of 1.0 g/10min and a viscosity of 181 Pa-s.
- PP-1 Polypropylene homopolymer with MFR of 3.0 g/1 Omin, a flexural modulus of 260,000 psi, a HDT at 0.455 MPa of 104 0 C, and a 20 viscosity of 150 Pa-s; sold as Marlex HGH030, by Chevron Phillips Chemical Co.
- PP-2 Polypropylene homopolymer with MFR of 0.65 g/1 Omin, a flexural modulus of 190,000 psi, a HDT at 0.455 MPa of 86 0 C, and a viscosity of 242 Pa-s; sold as Marlex HHX007, by Chevron Phillips 25 Chemical Co.
- PP-3 Polypropylene homopolymer with MFR of 12 g/1 Omin, a flexural modulus of 200,000 psi, a HDT at 0.455 MPa of 82.2°C, and a viscosity of 106 Pa-s; sold as Profax 1274 by Montell Co. (now Basell).
- Polypropylene homopolymers had melting points of about 165°C.
- 30 PP-4 Polypropylene copolymer with MFR of 8.0 g/1 Omin, a melting point of 142°C, a flexural modulus of 110,000 psi, and a viscosity of 120 Pa-s; sold as DS6D21 by Dow Chemical Co.
- the viscosity ratio was the viscosity of the 5 ethylene/alkyl acrylate copolymer divided by the viscosity of the PP polymer.
- Example 1 has a higher viscosity than EMA-2, providing a higher viscosity ratio.
- Example 1 had somewhat better high temperature properties and improved tensile properties compared to Example 2.
- Example 3 showed an autoclave EMA with a viscosity ratio 15 between the EMA-1 and EMA-2 used in Examples 1 and 2. The high temperature properties were lower than those of both Examples 1 and 2. This demonstrates that using a tubular reactor produced ethylene acrylate copolymer gave better results.
- the polypropylene homopolymer PP-2, used in Examples 5 and 6, 20 has a higher viscosity than PP-1 (used in Examples 1 and 4), resulting in a lower viscosity ratio.
- the tensile properties of Examples 5 and 6 are lower than the corresponding Examples 1 and 4.
- Example 1 and Example 5 have similar modified HDT and vicat temperatures, but Example 1 has a higher UST, providing a better range of service temperatures.
- the viscosity of PP-1 is low enough to cause better enhancement in properties in a 40/60 mix than in a 30/70 mix, compared to PP-2.
- Comparative Examples C9 and C10 were compositions in which the ethylene/alkyl acrylate had a lower viscosity than the polypropylene (see viscosity ratio). Comparison of Examples 7 and 8 with Examples C9 and C10 shows that improved high temperature properties were achieved using a higher viscosity ratio. Examples 7 and 8 also had good tensile properties.
- Examples 11 to 14 show that using a polypropylene (PP-3) with a lower viscosity than PP-1 (also having a higher MFR) enhanced HDT due to higher viscosity ratios. See, e.g., Examples 11 , 12 and 14 (comparable py y, respectively) show 8 to 15 0 C improvement in the modified HDT.
- the UST's were not as good, probably because the higher MFR material lost strength at a lower temperature (note that pure PP-3 had a lower heat deflection temperature than PP-1). These blends were characterized by maintaining good strength at lower temperatures and then having little physical integrity at temperatures approaching the upper service temperature due to the low strength of the PP-3.
- Examples 15 to 19 show the results using polypropylene copolymers, which were softer than the homopolymers, contributing to lower Shore D hardness, but had lower melting points, which reduced high temperature properties of the resulting blends.
- Example 15 and 16 compared to Example 1.
- Example 15, with a higher viscosity ratio than Example 1 showed a lower Shore D and a higher HDT than Example 1.
- Example 16 with a viscosity ratio lower than that of Example 15, was softer but also had a lower HDT than Example 1.
- Example 17 compared with Example 4. It was softer but also had a much lower HDT, vicat temperature and UST.
- Examples 18 and 19 compared with Example 8 and both are much softer.
- Example 18 had reduced HDT, while Example 19 had significantly lower HDT than Example 8. The UST's of all of these blends were not as good as the blends containing homopolymers probably due to approaching the lower melting points of the copolymers used.
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Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006800320319A CN101253239B (zh) | 2005-09-01 | 2006-08-31 | 具有改善的高温性能的软聚合物组合物 |
| EP06813995A EP1928950A2 (en) | 2005-09-01 | 2006-08-31 | Soft polymer compositions having improved high temperature properties |
| JP2008529265A JP2009507107A (ja) | 2005-09-01 | 2006-08-31 | 改善された高温特性を有する軟質ポリマー組成物 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71343805P | 2005-09-01 | 2005-09-01 | |
| US60/713,438 | 2005-09-01 |
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| WO2007027862A2 true WO2007027862A2 (en) | 2007-03-08 |
| WO2007027862A3 WO2007027862A3 (en) | 2007-04-26 |
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| PCT/US2006/033985 Ceased WO2007027862A2 (en) | 2005-09-01 | 2006-08-31 | Soft polymer compositions having improved high temperature properties |
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| Country | Link |
|---|---|
| US (1) | US7655731B2 (https=) |
| EP (1) | EP1928950A2 (https=) |
| JP (1) | JP2009507107A (https=) |
| CN (1) | CN101253239B (https=) |
| WO (1) | WO2007027862A2 (https=) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570617B (zh) * | 2008-04-30 | 2012-11-07 | 日立电线株式会社 | 无卤阻燃树脂组合物及使用该树脂组合物的电线·电缆 |
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| US8949266B2 (en) * | 2007-03-07 | 2015-02-03 | Vlingo Corporation | Multiple web-based content category searching in mobile search application |
| US20080221884A1 (en) * | 2007-03-07 | 2008-09-11 | Cerra Joseph P | Mobile environment speech processing facility |
| US20110054900A1 (en) * | 2007-03-07 | 2011-03-03 | Phillips Michael S | Hybrid command and control between resident and remote speech recognition facilities in a mobile voice-to-speech application |
| US20090030685A1 (en) * | 2007-03-07 | 2009-01-29 | Cerra Joseph P | Using speech recognition results based on an unstructured language model with a navigation system |
| US20110060587A1 (en) * | 2007-03-07 | 2011-03-10 | Phillips Michael S | Command and control utilizing ancillary information in a mobile voice-to-speech application |
| US8949130B2 (en) * | 2007-03-07 | 2015-02-03 | Vlingo Corporation | Internal and external speech recognition use with a mobile communication facility |
| US20090030691A1 (en) * | 2007-03-07 | 2009-01-29 | Cerra Joseph P | Using an unstructured language model associated with an application of a mobile communication facility |
| US8886545B2 (en) * | 2007-03-07 | 2014-11-11 | Vlingo Corporation | Dealing with switch latency in speech recognition |
| US20110054898A1 (en) * | 2007-03-07 | 2011-03-03 | Phillips Michael S | Multiple web-based content search user interface in mobile search application |
| US8635243B2 (en) | 2007-03-07 | 2014-01-21 | Research In Motion Limited | Sending a communications header with voice recording to send metadata for use in speech recognition, formatting, and search mobile search application |
| US8886540B2 (en) * | 2007-03-07 | 2014-11-11 | Vlingo Corporation | Using speech recognition results based on an unstructured language model in a mobile communication facility application |
| US20090030687A1 (en) * | 2007-03-07 | 2009-01-29 | Cerra Joseph P | Adapting an unstructured language model speech recognition system based on usage |
| US20080312934A1 (en) * | 2007-03-07 | 2008-12-18 | Cerra Joseph P | Using results of unstructured language model based speech recognition to perform an action on a mobile communications facility |
| US20080221900A1 (en) * | 2007-03-07 | 2008-09-11 | Cerra Joseph P | Mobile local search environment speech processing facility |
| US20110054895A1 (en) * | 2007-03-07 | 2011-03-03 | Phillips Michael S | Utilizing user transmitted text to improve language model in mobile dictation application |
| US20110054899A1 (en) * | 2007-03-07 | 2011-03-03 | Phillips Michael S | Command and control utilizing content information in a mobile voice-to-speech application |
| US8838457B2 (en) | 2007-03-07 | 2014-09-16 | Vlingo Corporation | Using results of unstructured language model based speech recognition to control a system-level function of a mobile communications facility |
| US20110054896A1 (en) * | 2007-03-07 | 2011-03-03 | Phillips Michael S | Sending a communications header with voice recording to send metadata for use in speech recognition and formatting in mobile dictation application |
| US10056077B2 (en) * | 2007-03-07 | 2018-08-21 | Nuance Communications, Inc. | Using speech recognition results based on an unstructured language model with a music system |
| US20090030688A1 (en) * | 2007-03-07 | 2009-01-29 | Cerra Joseph P | Tagging speech recognition results based on an unstructured language model for use in a mobile communication facility application |
| CN102947384B (zh) | 2010-03-17 | 2016-08-10 | 北欧化工股份公司 | 具有优异电特性的适于电线电缆应用的聚和物组合物 |
| CA2792989C (en) | 2010-03-17 | 2018-08-14 | Borealis Ag | Polymer composition for w&c application with advantageous electrical properties |
| EP2571934A1 (en) | 2010-05-21 | 2013-03-27 | Borealis AG | Composition |
| WO2011144703A1 (en) | 2010-05-21 | 2011-11-24 | Borealis Ag | Composition |
| JP5551656B2 (ja) | 2010-07-20 | 2014-07-16 | ローム アンド ハース カンパニー | オレフィン/アクリルポリマーブレンド |
| BR112015004926B1 (pt) | 2012-09-25 | 2021-03-02 | Dow Global Technologies Llc | composição polimérica e composição |
| CN104558810A (zh) * | 2014-12-30 | 2015-04-29 | 南京金杉汽车工程塑料有限责任公司 | 一种低光泽度聚丙烯复合材料及其制备方法 |
| CN106046555A (zh) * | 2016-07-28 | 2016-10-26 | 宁夏易兴实业有限公司 | 一种聚丙烯功能涂覆料及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234656A (en) * | 1978-12-20 | 1980-11-18 | Union Carbide Corporation | Reprocessable thermoplastic graft copolymer of propylene polymer and ethylene copolymer |
| US4500681A (en) * | 1982-12-27 | 1985-02-19 | Exxon Research & Engineering Co. | Thermoplastic blend of polyolefin, isobutylene-backbone elastomer and ethylene copolymer |
| US4710544A (en) * | 1985-11-07 | 1987-12-01 | E. I. Du Pont De Nemours And Company | Thermoplastic composition of polyolefin and high ethylene content ethylene/alkyl acrylate elastomer |
| JPH0788446B2 (ja) * | 1986-08-07 | 1995-09-27 | 旭化成工業株式会社 | フイルム成形用樹脂組成物 |
| US4957974A (en) * | 1988-03-29 | 1990-09-18 | Rohm And Haas Company | Graft copolymers and blends thereof with polyolefins |
| US5571878A (en) * | 1991-09-24 | 1996-11-05 | Chevron Chemical Company | Ethylene-alkyl acrylate copolymers and derivatives having improved melt-point temperatures and adhesive strength and processes for preparing same |
| JP2700290B2 (ja) | 1993-05-17 | 1998-01-19 | 三洋化成工業株式会社 | 塗料組成物 |
| JP3545808B2 (ja) * | 1994-08-05 | 2004-07-21 | アキレス株式会社 | カレンダー成形用ポリオレフィン組成物 |
| CN1249771A (zh) | 1997-03-07 | 2000-04-05 | 杜邦唐弹性体公司 | 具有改进的耐磨性、摩擦系数和热生胶强度的弹性体组合物 |
| US6397709B1 (en) | 1999-08-13 | 2002-06-04 | Dean Wall | Handtool with rotatable arms |
| FR2828493B1 (fr) * | 2001-08-07 | 2005-06-03 | Atofina | Composition a base de polypropylene et d'un copolymere ethylene/acrylate d'alkyle |
| JP2004238559A (ja) * | 2003-02-07 | 2004-08-26 | Fujikura Ltd | 難燃性樹脂組成物 |
| DE602005014443D1 (de) * | 2004-01-08 | 2009-06-25 | Du Pont | Ethylencopolymere und polyolefin enthaltende zusammensetzung |
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2006
- 2006-08-18 US US11/506,553 patent/US7655731B2/en not_active Expired - Fee Related
- 2006-08-31 EP EP06813995A patent/EP1928950A2/en not_active Withdrawn
- 2006-08-31 JP JP2008529265A patent/JP2009507107A/ja active Pending
- 2006-08-31 CN CN2006800320319A patent/CN101253239B/zh not_active Expired - Fee Related
- 2006-08-31 WO PCT/US2006/033985 patent/WO2007027862A2/en not_active Ceased
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570617B (zh) * | 2008-04-30 | 2012-11-07 | 日立电线株式会社 | 无卤阻燃树脂组合物及使用该树脂组合物的电线·电缆 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009507107A (ja) | 2009-02-19 |
| US7655731B2 (en) | 2010-02-02 |
| CN101253239B (zh) | 2011-04-13 |
| EP1928950A2 (en) | 2008-06-11 |
| WO2007027862A3 (en) | 2007-04-26 |
| CN101253239A (zh) | 2008-08-27 |
| US20070049682A1 (en) | 2007-03-01 |
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