WO2006026058A1 - Thermoformable propylene polymer compositions - Google Patents
Thermoformable propylene polymer compositions Download PDFInfo
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- WO2006026058A1 WO2006026058A1 PCT/US2005/027760 US2005027760W WO2006026058A1 WO 2006026058 A1 WO2006026058 A1 WO 2006026058A1 US 2005027760 W US2005027760 W US 2005027760W WO 2006026058 A1 WO2006026058 A1 WO 2006026058A1
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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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
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- 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
- C08L23/06—Polyethene
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/04—Combined thermoforming and prestretching, e.g. biaxial stretching
- B29C51/06—Combined thermoforming and prestretching, e.g. biaxial stretching using pressure difference for prestretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/08—Deep drawing or matched-mould forming, i.e. using mechanical means only
- B29C51/082—Deep drawing or matched-mould forming, i.e. using mechanical means only by shaping between complementary mould parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/08—Copolymers of ethylene
- B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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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
- C08L2023/40—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 by reaction with compounds changing molecular weight
- C08L2023/44—Coupling; Molecular weight increase
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/07—Long chain branching
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- 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
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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
- C08L23/0807—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- This invention relates to thermoformable propylene polymer compositions and fabricated articles thereof.
- Polypropylene has been used in many applications in the form of injection molded and extruded articles, film, sheet, etc., because it is excellent in molding processability, toughness, moisture resistance, gasoline resistance, chemical resistance, has a low specific gravity, and is inexpensive. Advances in impact modification have further expanded the versatility and uses of propylene polymers. The use of propylene polymers is expanding at an increasing rate in the fields of exterior and interior automotive trims, in electrical and electrical equipment device housings and covers as well as other household and personal articles.
- Automotive articles are ordinarily processed by injection molding. However, there are many components of automobiles wherein such parts are hollow and to manufacture these by injection molding is very difficult and expensive. Many such parts, particularly large parts, can conceivably be made by thermoforming provided the polymer has adequate processing properties such as high melt strength and end product properties such as toughness, especially low temperature toughness. It is known that commercially available propylene polymers for injection molding and extrusion have excellent properties, but lack a combination of good melt strength and toughness. Higher toughness and good melt strength are attributes of grades of propylene polymers with higher molecular weights, however, melt processing machine outputs tend to be inversely related to polymer molecular weights.
- the propylene polymer is an impact propylene copolymer.
- the coupling agent is a bis(sulfonyl azide).
- the coupled propylene polymer composition optionally comprises one or more of a polyolefin elastomer, a thermoplastic polymer or a filler. The invention further involves a process to thermoform articles from a coupled propylene polymer composition.
- the automotive article is a seat back, a head rest, a knee bolster, glove box door, an instrument panel, a bumper facia, a bumper beam, a center console, an intake manifold, a spoiler, a side molding, a pillar, a door trim, an airbag cover, a HVAC duct, a spare tire cover, a fluid reservoir, a rear window shelf, a resonator, a trunk board or an arm rest.
- recreational vehicle articles include all terrain vehicle (ATV) body panels, golf cart body panels, snow mobile cowling and body panels, personal water craft cowling and body panels, and the like.
- ATV all terrain vehicle
- the appliance covers include covers (sometimes referred to as side panels, enclosures, housings, and the like) for applications such as a washing machine, a dryer, a refrigerator, a freezer, an oven, a microwave, a dish washer, a furnace, an air conditioner, a television set, or a vacuum cleaner.
- covers sometimes referred to as side panels, enclosures, housings, and the like
- applications such as a washing machine, a dryer, a refrigerator, a freezer, an oven, a microwave, a dish washer, a furnace, an air conditioner, a television set, or a vacuum cleaner.
- Other applications include small appliance and power tool housings, furniture and shelves, electronic device housings, and lawn and garden tractor articles.
- the thermoformed articles of the present invention are produced from a coupled propylene polymer composition.
- the coupled propylene polymer composition involves coupling of a propylene polymer using a coupling agent.
- the propylene polymer is a propylene homopolymer, preferably a propylene copolymer or most preferably an impact propylene copolymer.
- the propylene polymer suitable for use in this invention is well known in the literature and can be prepared by various processes, for example, in a single stage or multiple stages, by such polymerization method as slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization or a combination thereof using a metallocene catalyst or a so-called Ziegler- Natta catalyst, which usually is one comprising a solid transition metal component comprising titanium.
- a catalyst consisting of, as a transition metal/solid component, a solid composition of titanium trichoride which contains as essential components titanium, magnesium and a halogen; as an organometalic component an organoaluminum compound; and if desired an electron donor.
- Preferred electron donors are organic compounds containing a nitrogen atom, a phosphorous atom, a sulfur atom, a silicon atom or a boron atom, and preferred are silicon compounds, ester compounds or ether compounds containing these atoms.
- Propylene polymers are commonly made by catalytically reacting propylene in a polymerization reactor with appropriate molecular weight control agents. Nucleating agent may be added after the reaction is completed in order to promote crystal formation.
- the polymerization catalyst should have high activity and be capable of generating highly tactic polymer.
- the reactor system must be capable of removing the heat of polymerization from the reaction mass, so the temperature and pressure of the reaction can be controlled appropriately.
- the propylene polymer is in the isotactic form, although other forms can also be used (for example, syndiotactic or atactic).
- the propylene polymer used for the present invention is a propylene homopolymer or a propylene copolymer of propylene ana an alpha-olefin, preferably a C 2 , or C 4 to C 20 alpha-olefin, for example, a random or block copolymer or preferably an impact propylene copolymer.
- Examples of the C 2 , and C 4 to C 20 alpha-olefins for constituting the propylene copolymer include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1- hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyI-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyt-1-pentene, 3-methyl-1- hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-
- the alpha-olefin is present in an amount of not more than 15 weight percent, preferably not more than 12 weight percent, even more preferably not more than 9 weight percent and most preferably not more than 7 weight percent.
- Impact propylene copolymers are commercially available and are well known within the skill in the art, for instance, as described by E.P. Moore, Jr in Polypropylene Handbook, Hanser Publishers, 1996, page 220-221 and U.S. Patents 3,893,989 and 4,113,802.
- impact propylene copolymer is used herein to refer to heterophasic propylene copolymers where polypropylene is the continuous phase and an elastomeric phase is dispersed therein.
- the impact propylene copolymer may be polypropylene and an elastomer physically blended, preferably the impact propylene copolymers result from an in-reactor process.
- the impact propylene copolymers are formed in a dual or multi-stage process, which optionally involves a single reactor with at least two process stages taking place therein, or optionally multiple reactors.
- the continuous phase of the impact propylene copolymer typically will be a propylene homopolymer or a random propylene copolymer, more typically a propylene homopolymer.
- the continuous phase of the impact propylene copolymer may be made using Ziegler-Natta catalyst, constrained geometry catalyst, metallocene catalyst, or any other suitable catalyst system.
- the catalyst(s) yield stereo-regular polymers, preferably isotactic.
- the crystallinity of the propylene polymer is preferably equal to or greater than 50 percent, more preferably equal to or greater than 62 percent, even more preferably equal to or greater than 75 percent, even more preferably equal to or greater than 90 percent, even more preferably equal to or greater than 95 percent, and most preferably equal to or greater than 98 percent.
- the methods for determining percent crystallinity using a differential scanning calorimetry are known to one skilled in the art.
- the propylene polymer making up the continuous phase is a high crystalline propylene homopolymer having equal to or less than 1.5 weight percent atactic propylene polymer as determined by xylene solubles, more preferably having equal to or less than 1.2 weight percent atactic propylene polymer, even more preferably having equal to or less than 1 weight percent atactic propylene polymer, and most preferably having equal to or less than 0.7 weight percent atactic propylene polymer wherein weight percent is based on the total weight of the propylene polymer.
- the elastomeric phase comprises propylene and one or more alpha olefins, preferably ethylene.
- the elastomeric phase may be made using constrained geometry catalyst, Ziegler-Natta catalyst, metallocene catalyst, or any other suitable catalyst.
- the continuous phase of the impact propylene copolymer is a propylene homopolymer and the elastomeric phase is comprised of a copolymer or terpolymer containing monomer units derived from ethylene
- the impact propylene copolymer preferably contains an amount equal to or greater than 5 weight percent, more preferably equal to or greater than 7 weight percent, most preferably equal to or greater than 9 weight percent -CH 2 CH 2 - units derived from ethylene monomer based on the total weight of the impact propylene copolymer.
- such an impact propylene copolymer contains less than 30 weight percent, more preferably less than 25 weight percent, most preferably less than 20 weight percent -CH 2 CH 2 - units derived from ethylene monomer based on the total weight of the impact propylene copolymer.
- the impact propylene copolymers used for the invention have an elastomeric phase in an amount equal to or greater than 10 weight percent, preferably equal to or greater than 15 weight percent, more preferably equal to or greater than 20 weight percent based on the total weight of the impact propylene copolymer.
- the elastomeric phase is less or equal to 70 weight percent, more preferably less than or equal to 40 weight percent, most preferably less than or equal to 25 weight percent based on the total weight of the impact propylene copolymer.
- the propylene polymer is employed in amounts equal to or greater than 30 parts by weight, preferably equal to or greater then 40 parts by weight, more preferably equal to or greater than 50 parts by weight, even more preferably equal to or greater than 60 parts by weight and most preferably equal to or greater than 70 parts by weight based on the weight of the coupled propylene polymer composition.
- the propylene polymer is used in amounts less than or equal to 100 parts by weight, preferably less than or equal to 95 parts by weight, more preferably less than or equal to 90 parts by weight, even more preferably less than or equal to 85 parts by weight and most preferably less than or equal to 80 parts by weight based on the weight of the coupled propylene polymer composition.
- the propylene polymer is reacted with a polyfunctional compound which is capable of insertion reactions into carbon-hydrogen bonds.
- a polyfunctional compound which is capable of insertion reactions into carbon-hydrogen bonds.
- Compounds having at least two functional groups capable of insertion into the carbon-hydrogen bonds of CH, CH 2 , or CH 3 groups, both aliphatic and aromatic, of a polymer chain are referred to herein as coupling agents.
- Those skilled in the art are familiar with carbon-hydrogen insertion reactions and functional groups capable of such reactions, for instance carbenes and nitrenes.
- Examples of chemical compounds that contain a reactive group capable of forming a carbene group include, for example, diazo alkanes, geminally-substituted methylene groups, and metallocarbenes.
- Examples of chemical compounds that contain reactive groups capable of forming nitrene groups include, but are not limited to, for example, alkyl and aryl azides (R-N 3 ), acyl azides (R-C(O)N 3 ), azidoformates (R-O-C(O)-N 3 ), sulfony! azides (R-SO 2 -N 3 ), phosphoryl azides ((RO) 2 -(PO)-N 3 ), phosphinic azides (R 2 -P(O)-N 3 ) and silyl azides (R 3 -Si-N 3 ). It may be necessary to activate a coupling agent with heat, sonic energy, radiation or other chemical activating energy, for the coupling agent to be effective for coupling propylene polymer chains.
- the preferred coupling agent is a sulfonyl azide, more preferably a bis(sulfonyl azide).
- sulfonyl azides include such compounds as 1 , 5-pentane bis(sulfonyl azide), 1 ,8-octane bis(sulfonyl azide), 1 ,10- decane bis(sulfonyl azide), 1 , 10-octadecane bis(sulfonyl azide), 1-octyl-2,4,6-benzene tris(sulfonyl azide), 4,4'-diphenyl ether bis(sulfonyl azide), 1,6-bis(4'-sulfonazidophenyl)hexane, 2,7-naphthalene bis(sulfonyl azide), and mixed sulfonyl azides of
- Preferred sulfonyl azides include 4, 4' oxy-bis-(sulfonylazido)benzene, 2,7- naphthalene bis(sulfonyl azido), 4,4'-bis(sulfonyl azido)biphenyl, 4,4'-diphenyl ether bis(sulfonyl azide) and bis(4-sulfonyl azidophenyl)methane, and mixtures thereof.
- Sulfonyl azides are commercially available or are conveniently prepared by the reaction of sodium azide with the corresponding sulfonyl chloride, although oxidation of sulfonyl hydrazines with various reagents (nitrous acid, dinitrogen tetroxide, nitrosonium tetrafluoroborate) has been used.
- an effective amount of coupling agent is dependent on the coupling agent selected and the average molecular weight of the propylene polymer. Typically, the lower the molecular weight of the propylene polymer, the more coupling agent needed.
- an effective amount of coupling agent is an amount sufficient to result in adequate melt strength for thermoforming, but less than a cross-linking amount, that is an amount sufficient to result in less than 10 weight percent gel in the coupled propylene polymer as measured by ASTM D2765- procedure A.
- an effective amount is equal to or greater than about 50 parts per million (ppm), preferably equal to or greater than 75 ppm, more preferably equal to or greater than 100 ppm and most preferably equal to or greater than 150 ppm by weight based on the weight of the propylene polymer.
- the amount of bis (sulfonyl azide) is limited to equal to or less than 2000 ppm, preferably equal to or less than 1500 ppm and more preferably equal to or less than 1300 ppm by weight based on the weight of the propylene polymer.
- the propylene polymer compositions of the present invention may comprise an elastomer.
- Elastomers are defined as materials which experience large reversible deformations under relatively low stress. Elastomers are typically characterized as having structural irregularities, non-polar structures, or flexible units in the polymer chain.
- an elastomeric polymer can be stretched to at least twice its relaxed length with stress and after release of the stress returns to approximately the original dimensions and shape.
- elastomers include natural rubber, polyolefin elastomers (POE), chlorinated polyethylene (CPE), silicone rubber, styrene/butadiene (SB) copolymers, styrene/butadiene/styrene (SBS) terpolymers, styrene/ethylene/butadiene/styrene (SEBS) terpolymers and hydrogenated SBS or SEBS.
- Preferred elastomers are polyolefin elastomers.
- Suitable polyolefin elastomers for use in the present invention comprise one or more C 2 to C 20 alpha-olefins in polymerized form, having a glass transition temperature (T 9 ) less than 25°C, preferably less than O 0 C.
- T 9 is the temperature or temperature range at which a polymeric material shows an abrupt change in its physical properties, including, for example, mechanical strength.
- T 9 can be determined by differential scanning calorimetry.
- polymers from which the present polyolefin elastomers are selected include polyethylene and copolymers of aipha-olefins, such as ethylene and propylene (EPM), ethylene and 1-butene, ethylene and 1-hexene or ethylene and 1-octene copolymers, and terpolymers of ethylene, propylene and a diene comonomer such as hexadiene or ethylidene norbomene (EPDM) and ethylene, propylene and a C 4 to C 20 alpha-olefin.
- EPM ethylene and propylene
- EPDM ethylidene norbomene
- a preferred polyolefin elastomer is one or more substantially linear ethylene polymer or one or more linear ethylene polymer (S/LEP), or a mixture of one or more of each. Both substantially linear ethylene polymers and linear ethylene polymers are well known.
- the elastomer is employed in amounts of equal to or greater than 5 parts by weight, preferably equal to or greater than 10 parts by weight, more preferably equal to or greater than 15 parts by weight and most preferably equal to or greater than 20 parts by weight based on the weight of the coupled propylene polymer composition.
- the elastomer is used in amounts less than or equal to 70 parts by weight, preferably less than or equal to 60 parts by weight, more preferably less than or equal to 50 parts by weight, even more preferably less than or equal to 40 parts by weight and most preferably 30 parts by weight based on the weight of the coupled propylene polymer composition.
- thermoplastic polymer may be blended with the coupled propylene polymer provided the desired thermoforming properties in the resulting coupled propylene polymer composition are achieved.
- additional thermoplastic polymers include any of the coupled or uncoupled propylene polymers described above for this invention including high crystalline polypropylene, high crystalline propylene copolymers with from 0.5 percent to 1 percent ethylene, or more preferably from 0.5 percent to 2 percent ethylene, or mini-random propylene/ethylene copolymers; functionalized polypropylene, such as maleated polypropylene or polypropylene with carboxylic acid moieties; polyethylene, such as high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylenes (ULDPE) and very low density polyethylene (VLDPE); interpolymers of ethylene with a vinyl aromatic, such as styrene; ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl
- the additional thermoplastic polymer is employed in amounts equal to or greater than 5 parts by weight, preferably equal to or greater than 10 parts by weight, more preferably equal to or greater than 15 parts by weight and most preferably equal to or greater than 20 parts by weight based on the weight of the coupled propylene polymer composition.
- the additional polymer is used in amounts less than or equal to 70 parts by weight, preferably less than or equal to 60 parts by weight, more preferably less than or equal to 50 parts by weight, even more preferably less than or equal to 40 parts by weight and most preferably 30 parts by weight based on the weight of the coupled propylene polymer composition.
- the propylene polymer compositions of the present invention may further comprise mineral fillers such as calcium carbonate, talc, clay, mica, wollastonite, hollow glass beads, titaninum oxide, silica, carbon black, glass fiber or potassium titanate.
- Preferred fillers are talc, wollastonite, clay, cation exchanging layered silicate material or mixtures thereof.
- Talcs, wollastonites, and clays are generally known fillers for various polymeric resins. See for example US-A-5,091 ,461 and US-A-3,424,703; EP 639,613 A1 ; and EP 391 ,413, where these materials and their suitability as filler for polymeric resins are generally described.
- Examples of preferred cation exchanging layered silicate materials include biophilite, kaolinite, dickalite or talc clays; smectite clays; vermiculite clays; mica; brittle mica; fluoromica; Sepiolite; Magadiite; Kenyaite; Octosilicate; Kanemite; and Makatite.
- Preferred cation exchanging layered silicate materials are smectite clays, including montmorillonite, bidelite, saponite and hectorite.
- the desired amount of filler will depend on the filler, the propylene polymer and the application, but usually, the filler is employed in an amount equal to or greater than 0.01 parts by weight, preferably equal to or greater than 0.1 parts by weight, more preferably equal to or greater than 1 parts by weight, even more preferably equal to or greater than 5 parts by weight, and most preferably equal to or greater than 10 parts by weight based on the total weight of the coupled propylene polymer composition.
- an amount of filler equal to or less than 50 parts by weight, preferably equal to or less then 40 parts by weight, more preferably equal to or less than 30 parts by weight, more preferably equal to or less than 25 parts by weight, more preferably up to and including 20 parts by weight, and most preferably up to and including 15 parts by weight based the weight of the coupled propylene polymer composition.
- nucleating agents and/or clarifying agents may preferably be utilized with the practice of the invention.
- nucleating agents include metal salts of an aromatic or aliphatic carboxylic acid, such as aluminum benzoate, sodium benzoate, aluminum p-t-butylbenzoate, sodium adipate, sodium thiophenecarboxylate and sodium pyrrolecarboxylate.
- Metal salts of an organic phosphoric acid are also preferred as the nucleating agent. Additional nucleating agents and their use are fully described in US-A-6,153,715 which is incorporated herein by reference.
- additives are optionally incorporated in the coupled propylene polymer composition such as, pigments, antioxidants, acid scavengers, ultraviolet absorbers, neutralizers, slip agents, antiblock agents, antistatic agents, waxes, flame retardants, processing aids, extrusion aids, and other additives within the skill in the art used in combination or alone. Effective amounts are known in the art and depend on parameters of the composition and conditions to which they are exposed.
- the coupling reaction is implemented via reactive extrusion or any other method which is capable of mixing the coupling agent with the propylene polymer and adding sufficient energy to cause a coupling reaction between the coupling agent and the propylene polymer.
- the process is carried out in a single vessel such as a melt mixer or a polymer extruder, such as described in U.S. Patent Application 09/133,576 filed August 13, 1998 which is incorporated by reference herein in its entity.
- extruder is intended to include its broadest meaning and includes such devices as a device which extrudes pellets as well as an extruder which produces sheet. An extruder which produces a multilayer sheet by coextrusion is also with in the scope of the present invention.
- the reaction vessel preferably has at least two zones capable of different temperatures into which a reaction mixture would pass, the first zone advantageously being at a temperature at least the softening temperature of the propylene polymer and preferably less than the decomposition temperature of the sulfonyl azide and the second zone being at a temperature, sometimes referred to as melt process temperature, sufficient for decomposition of the sulfonyl azide.
- the first zone is preferably at a temperature sufficiently high to soften the propylene polymer and allow it to combine with the sulfonyl azide through distributive mixing, preferably to a substantially uniform admixture.
- the propylene polymer admixture comprising the sulfonyl azide is exposed to a profile of temperature in the first zone ranging from 50 0 C to 220 0 C, preferably 160°C to 200 0 C and the melt process temperature in the second zone is from 200 0 C to 285°C, preferably from 220 0 C to 255 0 C.
- Sheet manufactured from compositions of the present invention preferably have a flexural modulus according to ISO 178 of equal to or greater than about 220,000 pounds per square inch (psi), a notched Izod impact strength according to ISO 180/1 A at O 0 C of equal to or greater than about 4 foot-pound per inch (ft-lb/in.) and at 23°C of equal to or greater than about 10 ft-lb/in., a heat deflection temperature according to ISO 75 of equal to or greater than about 100 0 C, a 60 degree gloss according to ISO 2813 of equal to or greater than about 80, or combinations thereof.
- the sheet of the present invention comprises one or more layer wherein at least one layer comprises the coupled propylene polymer composition of the present invention.
- Coupled propylene polymer compositions of the present invention are thermoplastic and formed into single or multilayer sheet by any conventional process, preferably by sheet extrusion.
- the thickness of the sheet is only limited by the equipment used to make it and form it into, an article.
- the sheet of the present invention is preferably equal to or greater than 0.1 mm, more preferably equal to or greater than 0.5 mm and most preferably equal to or greater than 1 mm in thickness.
- the sheet of the present invention is preferably equal to or less than 20 mm, more preferably equal to or less than 18 mm and most preferably equal to or less than 15 mm in thickness.
- the coupled propylene polymer composition of the present invention may comprise one or more of the layers.
- the propylene polymer composition of the present invention is the base layer and/or the cap layer and/or any layer between the base layer and the cap layer.
- the base, or thickest, layer is preferably equal to or greater than 0.5 mm and most preferably equal to or greater than 1 mm in thickness.
- the base layer of a multilayer sheet of the present invention is preferably equal to or less than 20 mm, more preferably equal to or less than 18 mm and most preferably equal to or less than 15 mm in thickness.
- Any subsequent layers in a multilayer sheet are independently preferably equal to or greater than 0.1 mm, more preferably equal to or greater than 0.2 mm and most preferably equal to or greater than 0.5 mm. Any subsequent layers in a multilayer sheet are independently preferably equal to or less than 2 mm, more preferably equal to or less than 1.8 mm and most preferably equal to or less than 1.5 mm.
- the layer(s) not comprising the coupled propylene polymer of the present invention are not limited in composition other than they must be thermoplastic polymer(s) compatible with, in other words will not delaminate from, the layer(s) comprising the coupled propylene polymer composition.
- compatible thermoplastic polymer(s) may be transparent translucent and/or opaque.
- polypropylene such as maleated polypropylene or polypropylene with carboxylic acid moieties
- polyolefins such as HDPE, LDPE, LLDPE, ULDPE, VLDPE
- interpolymers of ethylene with a vinyl aromatic such as styrene, EVA, EEA, EAA, PE-g-MAH, polystyrene
- polycyclohexylethane polyesters, such as polyethylene terephthalate; syndiotatic polypropylene; syndiotactic polystyrene; polyamides; and mixtures thereof, polyethylene, polyethylene copolymer with a C 3 to C 20 alpha olefin, polypropylene, or mixtures thereof.
- the compatible thermoplastic polymer(s) may contain fillers and/or additives commonly used in such polymers such as pigments, UV stabilizers, impact modifiers, slip agents, and the like.
- the multilayer sheet may further comprise tie layers or adhesive layers between the polymer layers comprising the sheet.
- the layer(s) not comprising the coupled propylene polymer of the present invention may also comprise scrap, regrind, and/or recycled material.
- the formed article of the present invention may be manufactured by thermoforming a sheet comprising the abovementioned coupled propylene polymer composition through the use of conventional machinery employing conventional conditions.
- thermoforming techniques there are a number of thermoforming techniques in use, but all are basically variations of two simple processes in which a heated sheet is moved by (1) air in the form of an applied vacuum and/or pressurized air, or (2) mechanical draw assists which force the sheet into a mold to produce the desired contoured or shaped article. In many cases the two processes are combined to result in a wide variety of procedures to make thermoformed articles.
- thermoforming methods within the scope of the present invention include, but are not limited to, straight forming, drape forming, snapback forming, reverse- draw forming, plug-assist forming, plug-assist/reverse draw forming, air-slip forming/plug-assist, air- slip forming, matched tool forming, twin-sheet forming, and the like.
- the thermoforming process includes heating a sheet until it softens or starts to sag, after which one or more of vacuum, air pressure, and/or mechanical draw assist is applied and the heated sheet is drawn into a female mold, sometimes referred to as die, drawn over a male mold, or the two molds are used together to form an article, the formed article is cooled, removed from the mold, and trimmed as necessary.
- the sheet temperature for thermoforming a sheet of the coupled propylene polymer of the present invention is less than or equal to 19O 0 C, preferably less than or equal to 180 0 C and more preferably less than or equal to 175 0 C. Further, the sheet temperature for thermoforming a sheet of the coupled propylene polymer of the present invention is greater than or equal to 160°C, preferably greater than or equal to 165°C and more preferably greater than or equal to 170 0 C.
- sheet made form the coupled propylene polymers of the present invention have a draw ratio of at least 3:1, preferably 2.5:1 and most preferably 2:1.
- a 50:50 talc: propylene polymer concentrate (referred to hereinafter as TALC: PP CONCENTRATE”) is compounded on a Farrel Continuous Mixer (FCM) CP-250 having a mixing section and an extruding section.
- FCM Farrel Continuous Mixer
- the propylene polymer used is a high crystalline propylene polymer having a density of about 0.9 grams per cubic centimeter (g/cc) and a melt flow rate (MFR) of about 1.5 grams per 10 minutes (g/10 min.) determined at 230 0 C under an applied load of 2.16 kilograms (kg) and is available as INSPIRETM D207.01 Performance Polymer available from The Dow Chemical Company and is hereinafter referred to as "PP-1".
- the talc is commercially available as JETFILTM 700C from Luzenac America having a median particle size of 1.5 microns and is hereinafter referred to as "TALC".
- the extrudate from the continuous mixer is fed directly into the throat of the single screw extruder having a screw length/diameter of 11 : 1 , a compression ratio of 3: 1 and 100 RPM.
- the extruder section operated under the following temperatures: Barrel rear 180 0 C, forward 200°C; Adapter: 220°C and Die: 220°C.
- the extrudate from the single screw extruder is cooled in the form of strands and comminuted in a strand chopper as pellets.
- the talc: PP concentrate pellets are blended with additional components to prepare Examples 1 to 9.
- the components of Examples 1 to 9 are dry blended then extruded into 145 mil sheet on a Welex monolayer/co-extrusion sheet line having two extruders.
- Extruder B contains a standard polypropylene 3.5 inch polypropylene screw with a length to diameter (L/D) ratio of 30:1 followed by a gear melt pump.
- Extruder A is a two inch co-extruder with a L/D of 24:1 designed to make thin cap layers on one or both sides of the sheet from extruder B.
- Both extruders feed a multi ⁇ layer feed block capable of making 1 , 2, or 3 (A/B, B/A, OR A/B/A) layer co-extruded structures.
- the line is fitted with a Welex 34 inch R-100 die, a sheet take-off, and a fixed shaft winder.
- Extrusion conditions are controlled by a Welex Ultima III Process Control.
- Zone 1 to 5 temperatures are about 396°F, 450°F, 382°F, 445°F, and 445 0 F
- Vent zone temperature is about 108 0 F
- Melt temperature is about 478 0 F
- Main head pressure is about 295 pounds per square inch (psi)
- Output rate is about 318 pounds per hour
- Die feed block and zone temperatures are all about 450 0 F.
- the 145 mil sheet measures 30 inches wide and is cut into lengths of 25 inches.
- the resulting sheet is thermoformed on an AAA melt phase cut sheet thermoformer with two side heating.
- a male mold in the shape of a truncated pyramid having a rectangular base measuring about 8 inches by 10 inches at the base, 6 inches by 8 inches at the top, and about 4 inches deep is used.
- the draw ratio is about 3:1 and the thermoformed part has an average thickness of from about 50 to about 70 mil.
- the sheet is heated to a semi-molten state in the oven using top and bottom ceramic heaters for 145 seconds at 50% heat until a surface temperature of 340 0 F to 350 0 F is measure by an infrared (IR) gun.
- IR infrared
- Vacuum is applied for 1.0 - 1.5 seconds from the top or until forming a bubble slightly smaller than the male mold.
- the mold is then pushed from the bottom into the molten bubble to produce the final forming of the sheet.
- the vacuum is switched to the mold side to force the molten sheet against the mold surface and conform to its shape.
- the formed part is extracted from the mold and cooled at about 80 - 100 0 C per minute until the part is solid enough to be extracted.
- PP 2 is a high crystalline propylene polymer having a density of about 0.9 g/cc, a MFR of about 3.0 g/10 min. determined at 230°C under an applied load of 2.16 kg and is available as INSPIRE D404.01 Performance Polymer available from The Dow Chemical Company;
- PP 3 is an impact propylene copolymer comprising about 18 percent (%) ethylene/octene rubber having a density of about 0.9 g/cc, a MFR of about 1.9 g/10 min. determined at 23O 0 C under an applied load of 2.16 kg and is available as INSPIRE D117.00 Performance Polymer available from The Dow Chemical Company;
- PP 4" is a coupled impact copolymer polypropylene wherein an impact propylene copolymer comprising about 14 % ethylene/propylene rubber is used as the base resin.
- the copolymer has a density of about 0.9 g/cc and a MFR of about 1.2 g/10 min. determined at 230°C under an applied load of 2.16 kg.
- the base resin about 2960 parts per million (ppm) IRGANOXTM 1010 (phenolic antioxidant commercially available from Ciba Geigy), 600 ppm IRGAFOSTM 168 (phosphate antioxidant commercially available form Ciba Geigy), and about 200 parts per million 4, 4' oxy-bis-(sulfonylazido)benzene are feed into a Werner and Pfleiderer ZSK40 twin screw extruder at a feed rate of 250 pounds per hour, a screw speed of 300 rpm and with a target temperature profile of 180/190/200/200/210/220/230/240/230/240/240°C (from feed inlet to die).
- the extrudate is comminuted to pellets as the coupled impact copolymer propylene.
- PP-4 has a crystallinity of about 62 weight percent as determined on a TA Instrument 2910
- a small sample (milligram size) of the propylene polymer is sealed into an aluminum DSC pan.
- the sample is placed into a DSC cell with a 25 centimeter per minute nitrogen purge and cooled to about -100°C.
- a standard thermal history is established for the sample by heating at 10 0 C per minute to 225°C.
- the sample is then cooled to about -100 0 C and reheated at 10 0 C per minute to 225°C.
- the observed heat of fusion ( ⁇ H Obse rv ed ) for the second scan is recorded.
- the observed heat of fusion is related to the degree of crystallinity in weight percent based on the weight of the polypropylene sample by the following equation:
- Crystallinity, % x 100- where the heat of fusion for isotactic polypropylene ( ⁇ H isotaotio pp), as reported in B. Wunderlich, Macromolecular Physics, Volume 3, Crystal Melting, Academic Press, New Your, 1980, p 48, is 165 Joules per gram [JIg) of polymer.
- the standard thermal history is established by allowing the sample to cool from 225°C to room temperature and then cooling the sample from room temperature to -100 0 C with liquid nitrogen; and
- S/LEP is a substantially linear ethylene/octene copolymer available as
- AFFINITYTM EG 8150 from The Dow Chemical Company having a density of approximately 0.868 g/cm 3 , a melt flow rate of 0.5 g/10 min. determined according to ASTM D 1238 at 190°C and an applied load of 2.16 kg, and a CBDI of greater than 50.
- “Flexural Properties” are determined in accordance with ASTM D 790. Testing is performed using a Series 9 Automated Testing System, Model 4501 mechanical tester. Flexural Modulus results are reported in 10 5 pounds per square inch (10 5 psi) and Flexural Strength results are reported in psi;
- HDUL heat distortion under load was determined on a Ceast HDT 300 Vicat machine in accordance to ASTM D 648-82(88) where test specimens were_unannealed and tested under an applied pressure of 66 psi;
- Notched Izod is determined according to ASTM D 256 at 23°C and 0 0 C. The specimens are notched with a notcher to give a 0.100 inch ⁇ 0.002 inch radius notch. A standard Izod impact testing unit equipped with a cold temperature chamber and a 10 foot-pound (ft-lb) free falling hammer is used. Results are reported in foot-pounds per inch (ft-lb/in).
- Examples 10 to 16 are co-extruded sheet comprising a core layer and a cap layer having a total thickness of 4mm.
- the base stock for the core layers of Examples 10 to 16 is prepared on the FCM CP-250 described hereinabove.
- the components are dry blended prior to melt blending in the FCM CP-250.
- the following are the compounding conditions for the mixing section: Barrel temperature profile: 100 0 C, 220 0 C and 220 0 C; Screw speed is 350 RPM, Rate is 300 Ib/hr.; and Melt temperature 210 0 C.
- the extrudate from the continuous mixer is fed directly into the throat of the single screw extruder having a screw length/diameter of 11 :1 , a compression ratio of 3:1 and 35 RPM.
- the extruder section operated under the following temperatures: Barrel rear 220 0 C, forward 220°C; Adapter: 220°C and Die: 220 0 C.
- the extrudate from the single screw extruder is cooled in the form of strands and comminuted in a strand chopper into pellets.
- the components for the cap layer for Examples 10 to 16 are first dry blended then melt blended in a Wemer-Pfleiderer ZSK 40mm twin screw vented extruder with barrel temperatures from 208°C at the hopper to 22O 0 C, a melt temperature of 217°C and a rate of 225 Ib/hr.
- the extrudate from the twin screw extruder is cooled in the form of strands and comminuted in a strand chopper into pellets.
- the core layer pellets and cap layer pellets are dried at 71 °C for four hours before co- extruding into sheet.
- the core layer is extruded using a 2.5 inch HPM single screw extruder with a general purpose 3.5:1 compression ratio screw.
- the barrel temperatures are set starting at 181 0 C at the hopper and increasing to 230 0 C at the extruder exit.
- the cap layer is extruded using a 1.25 inch Killion single screw extruder with a standard polyolefin screw.
- the barrel temperatures are set starting at 203 0 C at the hopper and increasing to 220°C at the extruder exit. Both extruders feed a co-extrusion feed-block set for a two layer laminate configuration.
- Feed-block temperatures are controlled at 245°C.
- a 28 inch coat-hanger type design sheet die is used and with a 0.165 inch die gap.
- a 28 inch width Sterling horizontal three roll stack operating with a roll gap of 0.160 in is used for take-off.
- Roll temperatures are controlled at: Front roll, 72°C; Middle roll, 100°C, and Back roll, 94 0 C.
- Examples 10 to 16 The formulation content of Examples 10 to 16 is given in Table 2 below in parts by weight of the total composition.
- Black is a carbon black concentrate comprising 64% carbon black in a propylene homopolymer having a MFR of 12 g/10 min. available from Modem Dispersion, Inc. as MDI Black Concentrate PP-535.
- Physical properties are measured on test specimens prepared from the co-extruded sheet. The following physical property tests are run on Examples 10 to 16 and the results of these tests are shown in Table 1 :
- VICAT softening point is measured according to ASTM D 1525 and results are reported in 0 F.
- the resulting co-extruded sheet from Examples 10 to 16 is thermoformed on a manual feed AAA thermoformer with two side heating equipped with a lower platen mounted plug mold and a top platen mounted vacuum box to allow pre-billow, vacuum snapback forming.
- a block shaped male mold having a nominal 230mm width by 165mm depth by 100mm height is used. All vertical sides have about a 10 draft and all edges and corners have a 6mm radius.
- Sheet heating cycle dwell times range from about 145 seconds to 170 seconds. Draw rations of about 2.5:1 are achieved.
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Abstract
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BRPI0515239-9A BRPI0515239A (en) | 2001-10-01 | 2005-08-03 | thermoformed article and process for thermoforming a coupled propylene polymer composition into an article |
AU2005280475A AU2005280475A1 (en) | 2004-08-27 | 2005-08-03 | Thermoformable propylene polymer compositions |
EP05782544A EP1784452A1 (en) | 2004-08-27 | 2005-08-03 | Thermoformable propylene polymer compositions |
MX2007002261A MX2007002261A (en) | 2004-08-27 | 2005-08-03 | Thermoformable propylene polymer compositions. |
JP2007529891A JP2008511721A (en) | 2004-08-27 | 2005-08-03 | Thermoformable propylene polymer composition |
CA002576807A CA2576807A1 (en) | 2004-08-27 | 2005-08-03 | Thermoformable propylene polymer compositions |
NO20071046A NO20071046L (en) | 2004-08-27 | 2007-02-23 | Thermoformable compositions of propylene polymer |
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US10/928,580 US20050070673A1 (en) | 2001-10-01 | 2004-08-27 | Thermoformable propylene polymer compositions |
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Also Published As
Publication number | Publication date |
---|---|
AU2005280475A1 (en) | 2006-03-09 |
JP2008511721A (en) | 2008-04-17 |
KR20070053718A (en) | 2007-05-25 |
CN101006131A (en) | 2007-07-25 |
MX2007002261A (en) | 2007-04-20 |
ZA200701665B (en) | 2008-05-28 |
CA2576807A1 (en) | 2006-03-09 |
EP1784452A1 (en) | 2007-05-16 |
NO20071046L (en) | 2007-03-21 |
US20050070673A1 (en) | 2005-03-31 |
US20070278717A1 (en) | 2007-12-06 |
RU2007111114A (en) | 2008-10-10 |
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