Patent Application
20070276094
The present invention relates generally to thermoplastic polyolefin compositions having improved adhesion to polymer foams and/or coatings and more specifically to thermoplastic polyolefin compositions for rotational molding having such improved adhesion.
Thermoplastic polyolefin compositions are actively pursued as alternative materials for fabricated articles made of polyvinyl chloride, thermoplastic polyurethane, and/or recycled polymers. In the automotive field, thermoplastic polyolefin compositions have been used for the fabrication of articles such as interior sheathing, including instrument panel skins, door panels, air bag covers and seat covers. Many of these articles have surface appearances and designs with complex surface characteristics, such as contours and geometric technical grains.
Rotational molding processes involving a rotating mold have been found to be useful in the production of a variety of molded articles. Slush molding is a type of rotational molding wherein less than the entire interior surface of the rotating mold is heated. That is, in a slush molding process, a preheated mold is in continuous contact with a reservoir holding unheated polymer powder. As the polymer powder contacts the heated mold surface, it melts and fills all aspects of the mold. The relevant portion of the mold surface must therefore be heated to a temperature sufficient to obtain a desirable melt viscosity in the polymer to be molded.
Slush molding process have been found to be particularly advantageous for the production of molded articles with complex surface characteristics.
Unfortunately, the balance of material properties desired for a slush molding process has been difficult to achieve with current thermoplastic polyolefin compositions. Typical thermoplastic polyolefin compositions are often processed for prolonged time periods at extremely high temperatures to form a fused skin in a slush molding process. The material composition of a typical thermoplastic polyolefin composition may degrade during processing which in turn may alter the material properties, such at the material strength and uniform fusion of the composition. As a result, slush molded articles produced using traditional thermoplastic polyolefin compositions may have unacceptable surface appearance and mechanical properties.
To achieve suitability for slush molding without material property degradation, thermoplastic polyolefin compositions with a very low melt viscosity during the molding process are desired. Herein we refer to melt viscosity at any given temperature as that property measured at low shear rates, such as that defined by zero shear rate viscosity. The melt viscosity of the thermoplastic polyolefin compositions for use in slush molding will generally be, but are not limited to, melt viscosities in the range of 50 Pa.s to 250 Pa.s over the processing temperature range of 180° C. to 260° C. as measured at low shear rate such as that applied by a parallel plate rheometer.
There is thus a need in the art for a thermoplastic polyolefin composition having a low melt viscosity at the molding temperature for use in slush molding. There is a further need for a thermoplastic polyolefin composition having improved material properties, such as uniform melt fusion, during the slush molding process. There is also a further need for a process for preparing such a composition for use in manufacturing automotive and non-automotive articles with improved surface characteristics and appearance.
However, in addition to suitability for slush molding processes, desirable thermoplastic olefin compositions must also be capable of adhering to subsequently applied coatings and/or polymer-based foams.
For example, in some cases, the slush molded sheets may be subsequently subjected to additional processing steps such as painting and/or the application of a polymer foam. In one embodiment, a ‘skin’ having a grained outer surface is first produced by a slush molding process. The non-grained inner surface of the skin is then filled with a foam such as a polyurethane foam. Such processes may be used to produce textured or grained instrument panels. In other cases, the outer grained or textured surface may be painted or coated.
In either case, the molded thermoplastic polyolefin skin must exhibit desirable adhesion to applied foams and/or coatings. However, the prior art has struggled to provide thermoplastic polyolefin compositions suitable for slush molding processes that exhibit desirable adhesion to applied coatings and/or foams.
Thus, the surfaces of thermoplastic polymer alloy composition sheets have traditionally been treated prior to applying paint or adhering to understructures such as foams, especially polyurethane foams. Various methods have been used to increase the surface activity of thermoplastic polyolefin compositions, especially those having substantial amounts of polypropylene.
For example, primers or adhesion promoters such as chlorinated polyolefins have been used to improve the adherence of thermoplastic polyolefin compositions. However, the chlorination process is highly corrosive, typically requiring glass-lined reactors. Further, the reaction generally requires relatively high residence times, thereby resulting in higher manufacturing costs. In addition, at least two additional process steps are required to apply the liquid primer and hot air oven drying on both sides of the molded skin with the thermoplastic polyolefin composition. Other secondary treatment processes intended to improve adhesion to TPO include plasma, corona and flame treatment.
In some cases, processing of a molded skin or sheet continues with the application of a primer on a bottom or interior surface of the sheet or skin, heat curing, applying a primer on a top or exterior surface of the skin, heat curing again, applying a top coat (e.g., paint) and heat curing again. After this multiple step process, the resultant sheets or skins can be used to form articles of manufacture such as interior vehicle sheathing. A primer on the bottom surface of the sheet is typically needed to promote adhesion to the understructure, especially urethane foam understructures.
There is thus a need in the art for a thermoplastic polyolefin composition having improved adhesive properties in order to minimize or obviate the need for a separate surface primer activating step and which satisfies the above noted parameters for slush molding processes.
Disclosed is a thermoplastic polyolefin composition having improved adhesion to applied polymeric foams or coating is disclosed, methods of making the same, methods of making molded composites, and articles made therefrom.
In one embodiment, the disclosed composition comprise a polypropylene (a), a hydrogenated copolymer (b) of a vinyl aromatic compound and an alkylene compound, the hydrogenated copolymer (b) comprising (i) from 1 to no more than 30% by weight of vinyl aromatic residues, based on the weight of the hydrogenated copolymer (b), and (ii) at least 55% by weight of alkylene residues that are C4 or higher, based on total alkylene content of the hydrogenated copolymer (b) prior to hydrogenation (c) a functionalized polyolefin, and (d) a monoamine terminated polyalkylene oxide.
Also disclosed is a method of making a thermoplastic olefin composition having improved adhesion to applied foams or coatings. In one embodiment, the method comprises combining a polypropylene (a), a hydrogenated copolymer (b) of a vinyl aromatic compound and an alkylene compound, the copolymer (b) comprising (i) from 1 to no more than 30% by weight of vinyl aromatic residues, based on the weight of the hydrogenated copolymer (b), and (ii) at least 55% by weight of alkylene residues that are C4 or higher, based on total alkylene content of the copolymer (b) prior to hydrogenation, (c) a functionalized polyolefin, and (d) a monoamine terminated polyalkylene oxide, wherein the functionalized polyolefin (c) and monoamine terminated polyalkylene oxide (d) form an adduct that is thermodynamically miscible with the elastomer (b) at adduct:elastomer ratios of from 0.1:9.9 to 9.9:0.1.
Also disclosed is a method of making a molded composite. In one embodiment, the method comprises applying the composition of claim 1 to a mold to make a molded skin, and applying a polymer based composition to at least one surface of the skin, wherein the polymer based composition adheres to the molded skin without the use of adhesion enhancing techniques selected from the group consisting of adhesion primers, plasma surface treatments, flame surface treatments, or corona discharge surface treatments.
In another embodiment, articles of manufacture prepared with the present compositions are provided.
These and other features and advantages will be apparent from the following brief description of the drawings, detailed description, and appended claims and drawings.
Referring now to the drawings that are meant to be exemplary, not limiting:
Described herein are thermoplastic polyolefin compositions and processes for preparing the same. The present invention also relates to articles of manufacture prepared from the compositions.
In one embodiment, the thermoplastic polyolefin compositions are flexible thermoplastic polymer compositions having flex modulus values less than about 10,000 pounds per square inch (psi), preferably about 1,000 psi to about 7,000 psi, more preferably about 1,000 psi to about 3,000 psi all at 75° F./25° C.
In one embodiment, a thermoplastic polyolefin composition having improved adhesion to applied foams or coatings is disclosed, the composition comprising a polypropylene (a), a hydrogenated vinyl aromatic alkylene copolymer (b) comprising (i) from 1 to no more than 30% by weight of vinyl aromatic residues, based on the weight of the copolymer, and (ii) from 55 to 98% by weight of alkylene resides that are C4 or higher, based on the weight of the total alkylene content of the copolymer (b) prior to hydrogenation, (c) a functionalized polyolefin, and (d) a monoamine terminated polyalkylene oxide.
In another embodiment, the disclosed polyolefin composition will further comprise from 0 to 30 weight % of a block copolymer (e).
In another exemplary embodiment, the functionalized polyolefin (c) and monoamine terminated polyalkylene oxide (d) form an adduct that is thermodynamically miscible with the copolymer (b) at adduct:copolymer ratios of from 0.1:9.9 to 9.9:0.1.
In yet another exemplary embodiment, the disclosed thermoplastic polyolefin composition comprises a processing oil in an amount of from 0 to 15 weight %, based on the weight of the thermoplastic polyolefin composition.
In one embodiment, the disclosed thermoplastic polyolefin composition comprises (a) from 20 to 50% by weight of polypropylene, (b) from 5to 60% by weight of the hydrogenated vinyl aromatic alkylene copolymer (b), (c) from 1 to 30% by weight of the functionalized polyolefin, and (d) from 1 to 10% by weight of the monoamine terminated polyalkylene oxide.
Suitable polypropylene for use as polypropylene (a) includes, but is not limited to, crystalline polypropylene and is intended to include in addition to the homopolymer those polymers that also contain other olefin monomers, for example ethylene, butene, octene and the like. In one embodiment, such other olefin monomers may be present in minor amounts of from 5 to 15 weight %, based on the weight of the polypropylene. In one embodiment, suitable polypropylene polymers (a) have melt flow indices in the range of about 60 to about 1200 grams/10 minutes (g/10 min.) measured at 230° C. employing a 2.16 kilogram (kg) weight.
In one embodiment, the disclosed thermoplastic polyolefin compositions comprise about 20 wt. % to about 50 wt. % polypropylene (a) based on the total weight of all polymeric components. The term “all polymeric components” as used herein refers to components (a), (b), (c), (d) and optional polymer component (e). In another embodiment, the disclosed thermoplastic polyolefin compositions comprise about 20 wt. % to about 40 wt. % polypropylene based on the total weight of all polymer components. In one exemplary embodiment, the disclosed thermoplastic polyolefin compositions comprise about 25 wt. % to about 35 wt. % polypropylene based on the total weight of all polymeric components.
The disclosed thermoplastic polyolefin composition further comprises a hydrogenated copolymer (b) resulting from the hydrogenation of a copolymer (b′) resulting from the copolymerization of an alkenyl or vinyl aromatic compound and an alkylene compound. The copolymer (b′) is characterized by having (i) from 1 to no more than 30% by weight of vinyl aromatic residues, based on the weight of copolymer (b′), and (ii) from 55 to 98% by weight of alkylene residues that are C4 or higher, based on total alkylene content of the copolymer (b′).
The copolymer (b′) may be comprised of either random or block. In one exemplary embodiment, the copolymer (b′) and thus hydrogenated copolymer (b) will be a random copolymer.
The alkenyl or vinyl aromatic compound is represented by formula:
wherein R2 and R3 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C2-C8 alkenyl group, or the like; R4 and R8 each independently represent a hydrogen atom, a C1-C8 alkyl group, a chlorine atom, a bromine atom, or the like; and R5-R7 each independently represent a hydrogen atom, a C1-C8 alkyl group, a C2-C8 alkenyl group, or the like, or R4 and R5 are taken together with the central aromatic ring to form a naphthyl group, or R5 and R6 are taken together with the central aromatic ring to form a naphthyl group.
Specific examples, of the alkenyl aromatic compounds include styrene, p-methylstyrene, alpha-methylstyrene, vinylxylenes, vinyltoluenes, vinylnaphthalenes, divinylbenzenes, bromostyrenes, chlorostyrenes, and the like, and combinations comprising at least one of the foregoing alkenyl aromatic compounds. Of these, styrene, alpha-methylstyrene, p-methylstyrene, vinyltoluenes, and vinylxylenes are preferred, with styrene being more preferred.
Suitable alkylene compounds include diene and polyalkyenes. In one embodiment, the alkylene compound used in the preparation of the copolymer (b′) and thus hydrogenated copolymer (b) will be a diene. Especially suitable alkylenes are those alkylenes that result in repeating units comprising alkylene groups having four or more carbons prior to any hydrogenation of the resulting copolymer. In one exemplary embodiment, the alkylene compound will be a conjugated diene. Specific examples of suitable alkylenes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like. In one embodiment, the alkylene will at least one of 1,3-butadiene and 2-methyl-1,3-butadiene, butadiene, with 1,3-butadiene being used in one especially exemplary embodiment.
It is an aspect of the disclosed thermoplastic polyolefin composition that the content of the repeating unit derived from the alkenyl aromatic compound in the copolymer (b′) and thus hydrogenated copolymer (b) will be limited from 1 to no more than 30% by weight, based on the total weight of the hydrogenated copolymer (b). In one embodiment, the content of the repeating unit derived from the alkenyl aromatic compound in the hydrogenated copolymer (b) will be from 1 to 30% by weight, based on the total weight of the hydrogenated copolymer (b). In another embodiment, the content of the repeating unit derived from the alkenyl aromatic compound in the hydrogenated copolymer will be from 5 to 20% by weight, based on the total weight of the hydrogenated copolymer (b). In one exemplary embodiment, the content of the repeating unit derived from the alkenyl aromatic compound in the copolymer (b′) and thus the hydrogenated copolymer (b) will be from 5 to 15% by weight, based on the total weight of the hydrogenated copolymer (b).
It is also an aspect of the disclosed thermoplastic polyolefin composition that the content of the alkylene repeating unit derived from the alkylene compound in copolymer (b′) be at least 55% by weight, based on the total weight of copolymer (b′). In one embodiment, the content of the repeating unit derived from the alkylene compound in the hydrogenated copolymer (b) will be from 60 to 95% by weight, based on the total weight of the copolymer (b′), i.e., hydrogenated copolymer (b) prior to hydrogenation. In another embodiment, the content of the repeating unit derived from the alkylene compound in the hydrogenated copolymer will be from 65 to 90% by weight, based on the total weight of the copolymer (b′). In one exemplary embodiment, the content of the repeating unit derived from the conjugated diene in the copolymer (b′) will be from 70 to 90% by weight, based on the total weight of copolymer (b′).
It will be appreciated that in the most exemplary embodiment, the resulting hydrogenated copolymer (b) will result from the hydrogenation of an ethylene-butene styrene copolymer (b′) having an alkylene residue content wherein at least 60% of the alkylene residues comprise four or more carbons, based on the total alkylene content of copolymer (b′).
The hydrogenated copolymer (b) preferably has a number average molecular weight of about 5,000 to about 500,000 AMU, as determined by gel permeation chromatography (GPC) using polystyrene standards. Within this range, the number average molecular weight may preferably be at least about 10,000 AMU, more preferably at least about 30,000 AMU, yet more preferably at least about 45,000 AMU. Also within this range, the number average molecular weight may preferably be up to about 300,000 AMU, more preferably up to about 200,000 AMU, yet more preferably up to about 150,000 AMU.
In one embodiment, the hydrogenation copolymer (b) will have a glass transition temperature (Tg) below 0 degrees C. From the standpoint of low-temperature impact strength of the resulting resin composition, in another embodiment, the copolymer (b) will have a Tg greater than −90 degrees C. In one exemplary embodiment, the hydrogenated copolymer (b) will have a glass transition temperature (Tg) of between −20 to −60 degrees C. The glass transition temperature of the hydrogenated copolymer (b) can be measured by the aforesaid DSC method or from the visco-elastic behavior toward temperature change as observed with a mechanical spectrometer.
In one embodiment of the disclosed thermoplastic polyolefin composition, the hydrogenated copolymer (b) is selected so as to be thermodynamically miscible with an adduct of the functionalized polyolefin (c) and monoamine terminated polyalkylene oxide (d) at adduct:copolymer (b) ratios of from 0.1:9.9 to 9.9:0.1. The term ‘thermodynamically miscible’ as used herein refers to two components that are mixed on a molecular level so as to be a one phase homogenous composition independent of shear forces.
Illustrative examples of commercially available suitable hydrogenated copolymers (b) include Dynaron® 1321P, available from Japan Synthetic Rubber Corp of Japan and Kraton® 6932, available from Kraton Corp.
In one embodiment, the disclosed thermoplastic polyolefin compositions comprise about 5 wt. % to about 60 wt. % of the hydrogenated copolymer (b) based on the total weight of all polymeric components. In another embodiment, the disclosed thermoplastic polyolefin compositions comprise about 20 wt. % to about 60 wt. % of the hydrogenated copolymer (b) based on the total weight of all polymeric components. In one exemplary embodiment, the disclosed thermoplastic polyolefin compositions comprise about 40 wt. % to about 60 wt. % the hydrogenated copolymer (b) based on the total weight of all polymeric components.
The disclosed thermoplastic polyolefin compositions further comprise a functionalized polyolefin (c), and a polyetheramine (d). Those of skill in the art will appreciated that the functionalized polyolefin (c) and polyetheramine (d) form an adduct as discussed above.
Functionalized polyolefin (c) is a polyolefin onto which a monomer has been grafted.
Any functionalized polyolefin can be employed in the disclosed thermoplastic polyolefin compositions which may react with the polyetheramine and which is generally compatible with a given polyolefin after reaction with the polyetheramine.
The usual method of grafting a monomer onto a polyolefin is by free radical reaction. In the practice of this invention, the functionalized polyolefin is not a copolymer of, for example, maleic anhydride and propylene, where the maleic anhydride moiety is predominantly in the backbone of the copolymer.
Representative examples of suitable polyolefins to which a monomer may be grafted include homopolymers and copolymers of various olefins such as ethylene, propylene, butylene, pentene, hexylene, heptene and octene.
Suitable monomers for preparing functionalized polyolefin (c) are, for example, olefinically unsaturated monocarboxylic acids of less than 12 carbon atoms, e.g., acrylic acid or methacrylic acid, and the corresponding tert-butyl esters, e.g., tert-butyl(meth)acrylate, olefinically unsaturated dicarboxylic acids of less than 12 carbon atoms, e.g., fumaric acid, maleic acid, and itaconic acid and the corresponding mono-and/or di-tert-butyl esters, e.g., mono- or di-tert-butyl fumarate and mono- or di-tert-butyl maleate, olefinically unsaturated dicarboxylic anhydrides of less than 12 carbon atoms, e.g., maleic anhydride, sulfo- or sulfonyl-containing olefinically unsaturated monomers of less than 12 carbon atoms, e.g., p-styrenesulfonic acid, 2-(meth)acrylamide-2-methylpropenesulfonic acid or 2sulfonyl(meth)acrylate, oxazolinyl-containing olefinically unsaturated monomers of less than 12 carbon atoms, e.g., vinyloxazolines and vinyloxazoline derivatives, and epoxy-containing olefinically unsaturated monomers of less than 12 carbon atoms, e.g., glycidyl (meth)acrylate or allyl glycidyl ether.
In one exemplary embodiment, the monomer used for preparing the functionalized polyolefin (c) will be maleic anhydride while the polyolefin will be polypropylene. Hence, in one exemplary embodiment, the functionalized polyolefin (c) will be maleated polypropylene.
Maleated polypropylene is commercially available, being manufactured by a number of producers. For example, a suitable maleated polypropylene is available from Eastman Chemical under the name EPOLENE E-43.
The functionalized polyolefin (c) used in the practice of this invention may have a wide variety of number average molecular weights. In the practice of the disclosed thermoplastic composition, any functionalized polyolefin (c) can be used which reacts with polyetheramines (d) to provide an adduct.
In one embodiment, the functionalized polyolefin (c) may have a number average molecular weight greater than about 3,000 and preferably less than about 50,000. It should be appreciated that the polyolefin can be bonded to one or two monomers when the polyolefin is linear, while more than two monomers might be included when the polyolefin is branched. Typically, one or two monomers are present.
The polyetheramines (d) used herein include monoamines, diamines and triamines, having a molecular weight of from about 150 to about 12,000, such chemicals including but not limited to hydroxyl, amine, and aminoalcohol functionalized polyether materials.
In one embodiment, the polyetheramines (d) will have a molecular weight of from about 200 to about 4,000. In another embodiment, the polyetheramine (d) will have a molecular weight in the range from about 400 to about 2000.
In another embodiment, the polyetheramine (d) will contain ethylene oxide units and propylene oxide units in a molar ratio of about 10:1 to about 3:1. In one embodiment, such polyether monoamines have a molecular weight in the range from about 2000 to about 2200. In a more exemplary embodiment, the polyetheramine (d) will contain ethylene oxide units and propylene oxide units in a molar ratio of about 7:1.
As disclosed herein, the use of monoamines and diamines are especially desirable. In one exemplary embodiment, the polyetheramine (d) will be a monoamine terminated polyoxyalkylene.
Suitable polyether blocks of the polyetheramine include polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly(1,2-butylene glycol), and poly(tetramethylene glycol). The glycols can be aminated using well known methods to produce the polyetheramines. Generally, the glycols are prepared from ethylene oxide, propylene oxide or combination thereof using well-known methods such as by a methoxy or hydroxy initiated reaction. When both ethylene oxide and propylene oxide are used, the oxides can be reacted simultaneously when a random polyether is desired, or reacted sequentially when a block polyether is desired.
In one embodiment, the polyetheramines (d) are prepared form ethylene oxide, propylene oxide or combinations thereof. Generally, when the polyetheramine (d) is prepared from ethylene oxide, propylene oxide or combinations thereof, the amount of ethylene oxide on a molar basis is greater than about 5 percent of the polyetheramine, preferably greater than about 75 percent and more preferably greater than about 90 percent. In one embodiment of this invention, polyols and amines including polyalkylene polyamines and alkanol amines or any amine that is not a polyetheramine as disclosed herein may be absent from the composition. Similarly, functional groups other than ether linkages and amine groups may be absent from the polyetheramine (d).
The polyetheramines (d) can be prepared using well known amination techniques such as described in U.S. Pat. No. 3,654,370; U.S. Pat. No. 4,152,353; U.S. Pat. No. 4,618,717; U.S. Pat. No. 4,766,245; U.S. Pat. No. 4,960,942; U.S. Pat. No. 4,973,761; U.S. Pat. No. 5,003,107; U.S. Pat. No. 5,352,835; U.S. Pat. No. 5,422,042; and U.S. Pat. No. 5,457,147. Generally, the polyetheramines (d) are made by aminating a polyol, such as a polyether polyol with ammonia in the presence of a catalyst such as a nickel containing catalyst such as a Ni/Cu/Cr catalyst.
Suitable monoamines include JEFFAME.™. M-1000, JEFFAMINE.™. M-2070, and JEFFAMINE.™. M-2005. Suitable diamines include JEFFAMINE.™. ED-6000, JEFFAMINE.™. ED-4000, JEFFAMINE.™. ED-2001 including XTJ-502 and XTJ-418, JEFFAMINE.™. D-2000, JEFFAMINE.™. D-4000, JEFFAMINE.™. ED-900, JEFFAMINE.™. ED-600, and JEFFAMINE.™. D-400. Suitable triamines include JEFFAMINE.™. ET-3000, JEFFAMINE.™. T-3000 and JEFFAMINE.™. T-5000.
In one exemplary embodiment, the polyetheramine (d) will be at least one of JEFFAMINE XTJ-418.
The functionalized polyolefin (c) and the polyetheramine (d) may be added to the thermoplastic polyolefin composition either during or after the preparation of the thermoplastic polyolefin composition. Moreover, the functionalized polyolefin (c) and the polyetheramine (d) may be added to the thermoplastic polyolefin composition either separately or as previously mixed combination. Thus the mixing of the functionalized polyolefin (c) and polyetheramine (d) to form the adduct may occur before or during the preparation of the disclosed thermoplastic polyolefin composition. It will therefore be appreciated that the reaction of the functionalized polyolefin (c) and the polyetheramine (d) to form the adduct may be carried out in a customary mixing apparatus including batch mixers, continuous mixers, kneaders, and extruders. For most applications, the mixing apparatus will be an extruder.
The thermoplastic polyolefin compositions may also comprise from 0 to up to about 30 wt. % of an optional polymer component (e).
In one embodiment, the optional polymer component (e) may be an ethylene copolymer elastomer, such as ethylene-based rubber. Suitable ethylene copolymer elastomers include, but are not limited to, ethylene-propylene, ethylene-butene, ethylene-octene, ethylene-pentene, ethylene-hexene copolymers and the like, as well as combinations comprising at least one of the forgoing ethylene copolymer elastomers, having glass transition temperatures of about down to −70° C. or less. In one embodiment, the optional polymer component (e) may be present as an ethylene copolymer elastomer in an amount of from 0 to 30% by weight of all polymeric components, while in another embodiment, the optional polymer component (e) may be present as an ethylene copolymer elastomer in an amount of from 15 to 25% by weight of all polymeric components
Other suitable ethylene copolymer elastomers include ethylene-propylene non-conjugated diene copolymer (EPDM). The non-conjugated dienes contain about 6 to about 22 carbon atoms and have at least one readily polymerized double bond. The ethylene-propylene copolymer elastomer contains abut 60 wt. % to about 80 wt. %, usually about 65 wt. % to about 75 wt. % ethylene, based on the total weight of the EPDM. The amount of non-conjugated diene is generally about 1 wt. % to about 7 wt. %, usually about 2 wt. % to about 5 wt. %, based on the total weight of the EPDM. In one embodiment, the ethylene-propylene copolymer elastomer is EPDM copolymer. Suitable EPDM copolymers include, but are not limited to, ethylene-propylene-1,4 hexadiene, ethylene-propylene dicyclopentadiene, ethylene-propylene norbornene, ethylene-propylene-methylene-2-norbornene, and ethylene-propylene-1,4-hexadiene/norbornadiene copolymer.
In another embodiment, the thermoplastic polyolefin compositions may further comprise about 0 wt. % to about 60 wt. % of a styrenic block copolymer as an optional polymer component (e). It will be appreciated that this optional styrenic is different from hydrogenated copolymer (b) and is not subject to its particular requirements.
In one exemplary embodiment, the disclosed thermoplastic polyolefin compositions will comprise from 0 to 15 weight % of a processing oil (f), based on the total weight of all polymeric components. In another exemplary embodiment, the disclosed thermoplastic polyolefin compositions will comprise from 5 to 10 weight % of a processing oil (f), based on the total weight of all polymeric components.
Illustrative examples of suitable processing oils (f) are those compatible processing oils that include hydrocarbon based oils comprising mainly paraffinic components. Suitable process oils have an average molecular weight (calculated from the kinematic viscosity per ASTM D2502) in the range of about 100 to about 1000. The molecular weight of the process oil should be selected to avoid migration from the composition in normal service use conditions. Commercially available examples of suitable processing oils (f) include Paralux processing oil and Hydrobrite™ processing oil, respectively commercially available from Chevron Oil and Crompton, Calitoria, N.J. In one embodiment, the processing oil (f) will be a nonaromatic processing oil.
The thermoplastic polyolefin compositions may further optionally comprise up to about 5 wt. % polymer additive(s). Suitable polymer additives include polymer surface modifier to improve scratch resistance, such as fatty acid amides like oleamide and erucamide, and siloxane. The thermoplastic polyolefin compositions may be comprised of up to about 5 wt. %, preferably and 0.3% to about 1 wt. %, of polymer surface modifier.
In an additional embodiment, the thermoplastic polyolefin compositions further comprise from 0 to up to 10 wt. %, preferably about 3 wt. % to about 7 wt. %, of a powder flow additive, such as inorganic particulate. Suitable powder flow additive includes hydrated silicate such as talc and montmorillonite clay. The particle size range of the silicate should be in the range of about 1 to about 40 μm and preferably in the range of about 1 to about 20 μm.
The disclosed thermoplastic polyolefin compositions can also optionally comprise stabilizer, such as heat stabilizer, light stabilizer and the like, as well as combinations comprising at least one of the foregoing stabilizers. Heat stabilizers include phenolics, hydroxyl amines, phosphates, ands the like, as well as combinations comprising at least one of the foregoing heat stabilizers. Light stabilizers include low molecular weight (having number-average molecular weights less than about 1,000 AMU) hindered amines, high molecular weight (having number-average molecular weights greater than about 1,000 AMU) hindered amines, and the like, as well as combinations comprising at least one of the foregoing light stabilizers.
Optionally, various additives known in the art may be used as needed to impart various properties to the composition, such as heat stability, stability upon exposure to ultraviolet wavelength radiation, long-term durability, and processability. The exact amount of stabilizer is readily empirically determined by the reaction employed and the desired characteristics of the finished article, having about 1 wt. % to about 4 wt. %, preferably about 1 wt. % to about 3 wt. %, stabilizer.
In one embodiment, the disclosed thermoplastic polyolefin compositions for use in slush molding may be characterized by melt viscosities in the range of 50 Pa.s to 1000 Pa.s over the processing temperature range of 180° C. to 260° C. as measured at low shear rate such as that applied by parallel plate rheometer. In another embodiment, the disclosed thermoplastic polyolefin compositions for use in slush molding may be characterized by melt viscosities in the range of 100 Pa.s to 600 Pa.s over the processing temperature range of 180° C. to 260° C. as measured at low shear rate such as that applied by parallel plate rheometer. High Melt Flow Index (as measured according to ASTM D1238) materials with Melt Flow Index (MFI) greater than about 20 grams/10 minutes (g/10 min) measured at 230° C. employing a 2.16 kilogram (kg) weight (>20 g/10 min) are selected to obtain low melt viscosity of the composition.
In addition, the disclosed thermoplastic polyolefin compositions may also be characterized by single composition dependent glass transition temperature Tg, since the components (a) and (b) are a homogenous one-phase mixture. That is, the disclosed thermoplastic polyolefin compositions will not show phase distinct Tg points. In one embodiment, the disclosed compositions will have a Tg of from −20 to −50° C.
Table 1 provides a list of components suitable for use in the thermoplastic compositions and examples discussed herein. It will be understood that the components listed in Table 1 are given for the purpose of illustration and do not limit the invention. ExxonMobil,
The thermoplastic polyolefin compositions further optionally comprise a color pigment or a combination of color pigments. Suitable color pigments are known to those skilled in the art and the exact amount of color pigment is readily empirically determined based on the desired color characteristic of the formulation and the finished product, with about 1 wt. % to about 2 wt. % possible.
The thermoplastic polyolefin composition may be prepared by melt blending the ingredients under high shear conditions, for example, using an internal mixer, such as Banbury type mixer, or by using a twin-screw extruder with screw elements selected to provide high shear for good distributive mixing of components. The resulting compositions may be processed further into smaller particles, such as pellets, micropellets, or powder, or any suitable form. The smaller particles of the compositions are particularly useful for slush molding to achieve uniform skin formation.
In one embodiment, as shown in
In another embodiment, as shown in
Micropellets 29 of the composition may be larger spherical particles than cryoground powder 19 particles, usually measuring in the range of about 350 to about 900 μm. Slush molding can be achieved using either the cryoground powder 19, the micropellets 29 of the composition or combinations of the two for forming articles of manufacture therefrom.
The process of slush molding may be successful when the powder 19 and/or micropellets 29 possess good mechanical flow within the forming tool during the rotation cycle. This property of mechanical flow can be quantified by measuring the time to empty a cup with an orifice at the bottom and with specific volume. The improved flow can be achieved by the addition of suitable powder flow additive such as inorganic particulate. Suitable powder flow additive includes hydrated silicate such as talc and montmorillonite clay. The powder flow additive may comprise up to about 10 wt. %, preferably about 3 wt. % to about 7 wt. %, of the total weight of the thermoplastic polyolefin composition. The particle size range of the silicate should be in the range of about 1 to about 40 μm and preferably in the range of about 1 to about 20 μm. These powder flow additive may be added during the melt compounding or as a secondary process during cryogrinding or mechanical mixing of the powder 19 and/or micropellets 29 with the powder flow additive.
The embodiments of the present compositions, process and articles made therefrom, although primarily described in relation to vehicle application such as interior sheathing, including instrument panel skins, door panels, air bag covers roof liners and seat covers, can be utilized in numerous automotive and non-automotive applications.
The following examples illustrate the present invention. It is understood that these examples are given for the purpose of illustration and do not limit the invention. In the examples, all parts and percentages are by weight based on the total weight of the composition unless otherwise specified.
Example of Improved Foam Adhesion in a Slush Molded Article
TPO Skin using the Maleated Polyolefin-Long Chain Amine “Adduct”
The foam adhesion test is applied to a skin (Sample 2 of Table 3 below) on which a polyurethane based cellular foam has been cast. The test applies a series of controlled Humidity (90% RH) and Temperature Cycles (−30 to 90° C.) that are set forth below in Table 2. After each cycle a samples is tested for foam adhesion in a peel test. Failure at the foam TPO skin interface is labeled “Adhesive Failure”. This signifies insufficient adhesion between the foam and the TPO substrate. When failure is labeled “Cohesive Failure”, this signifies tearing in the foam layer with good adhesion between foam and TPO substrate. An example of test results indicating a “Pass” (Table 2) on one formulation (Table 3) is shown below in Table 2.
Example to Substantiate Surface Modification of TPO
Using Maleated Polyolefin-Long Chain Amine “Adduct”
Three separated TPO compositions were prepared by melt mixing as per Table 3. After processing into a powder the samples gave the test results as per Table 4 and the bottom of Table 3. Specific Surface Energy values were determined by inverse chromatography (IGC), using the pulse method at infinite dilution, by Surface Measurement Systems, NA, Allentown, PA. Standard IGC equipped with a flame ionization detector, was used to determine the surface energetics for the three TPO samples at 303 K, and 0% RH.
The technique measures the surface energetics of the three samples and relates the values to the adhesive properties of the TPO powders. The specific free energies of desorption were determined by measuring the retention volume of polar probe molecules (acetone, ethyl acetate, acetonitrile, ethanol, and dichloromethane) on the samples. Points representing a polar probe are located above the alkane straight line in the RTln(VN) versus α(γnD)½ plot; α is the molecular area of the probe molecule; γnD is the dispersive component of the surface energy of the liquid elutant (surface tension); VN is the measured net retention volume—dead volume; R is the gas constant and T is the temperature The distance to the straight line is equal to the specific component of the free energy. The Foam Adhesion Test was conducted as per Example 1.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in herein are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the above specific examples are reported as precisely as possible. Any numerical value, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
It will be understood that a person skilled in the art may make modifications to the particular embodiments described herein within the scope and intent of the claims. While the present invention has been described as carried out in specific embodiments thereof, it is not intended to be limited thereby, but is intended to cover the invention broadly within the scope and spirit of the claims.
This application claims priority upon U.S. patent application Ser. No. 10/983,010, filed Nov. 5, 2004, entitled “SLUSH MOLDABLE THERMOPLASTIC POLYOLEFIN FORMULATION FOR INTERIOR SKIN”.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10983010 | Nov 2004 | US |
| Child | 11769457 | Jun 2007 | US |
