POLYETHER AMINE MODIFICATION OF POLYPROPYLENE

Abstract: A compound comprising a blend of polypropylene with the reaction of a functionalized polypropylene and polyether amine in which the polyetheramine is grafted into the functionalized polypropylene in a customary mixing apparatus is disclosed. The blend may include a thermoplastic vulcanizate ("TPV"). A process for producing the reaction product of the functionalized polypropylene and the polyether amine by melting with polypropylene in a customary mixing apparatus is also disclosed. Blends of the present invention are advantageously useful to prepare paintable automotive body parts.

Description: POLYETHER AMINE MODIFICATION OF POL. YPROP YT .EN This invention relates to a novel olefin polymer composed of the reaction of a functionalized polypropylene and a polyetheramine This invenUon also relates to thermoplastic res blends containing the novel olefin polymer and polypropylene. The in situ formation of compatibi zers for polyblends is rapidly gaining popularity In the last few years, more and more cases have been reported where advantage is taken of the presence of reactive groups to form a graft or a block or a random copolymer, which could act as a compatibihzer for a mixture of two or more polymers The pπor art, Process Requirements of the Reactive Compatibilization of Nylon 6/Polypropylene Blends by S.S. Dagli, M. Xanthos and J.A Biensenberger Polymer Processing Institute at Stevens Institute of Technology, Hoboken, N.J. 07030 reveals an acrylic acid grafted modified polypropylene used with a blend of nylon-6 and polypropylene Thermoplastic resm compositions containing polypropylene are well known m the art (e.g. U.S Patent 5,208,081 ). U.S. Patent 5, 179, 164 descπbes a polypropylene/polyamide composition suitable for producing moldings. The patent descπbes an ethylene copolymer useful as an adhesion promoter Moreover, the patent indicates that maleic acid is a suitable monomer for prepaπng the ethylene copolymer In addition, maleated polypropylene is commercially available. European patent application 0 367 832 discloses a resm composition containing an olefinic polymer having acid anhydπde groups. Λs in U.S. Patent 5,179,164, the novel compound is blended with a polyamide. Japanese patent 46003838 reveals a maleic anhydπde modified polypropylene composition containing tπethylamme and polyethylene glycol nonylphenyl ether Japanese patent 60195120 reveals a molding containing polyethylene, maleic anhydnde-grafted polyethylene, and diethylenetπamine. However, the instant invention uses the maleic anhydπde in conjunction with polyetheram es which produce unexpected improvements in resin properties. This invention is a compound comprising a blend of polypropylene ("PP") with the reaction product of a functionalized polypropylene and polyetheramine in which the polyether amine is grafted onto the functionalized polypropylene in a customary mixing apparatus By grafted it is meant that the amine functionality of the polyetheramine reacts with the anhydπde component of the polypropylene to form a reaction product, for instance, a pπmary amine will react with a maleic anhydπde to form an lmide This invention is also a process for producing the reaction product of the functionalized polypropylene and the polyether amine by melting with polypropylene in a customary mixing apparatus In this regard, the compound blend of this invention may be prepared by reactive extrusion by feeding a polyetheramine, a functionalized polypropylene and polypropylene into an extruder at temperatures such that the polyetheramine reacts with the functionalized polypropylene to form a reaction product containing, for example, an lmide group In another respect, this invention is a composition compπsing polypropylene, a crosshnked thermoplastic polyolefϊn vulcanizate, and the reaction product of a functionalized polypropylene and a polyether amine. The compositions of the present invention are useful for prepaπng molded automotive body parts, including directly pamtable thermoplastic polyolefms ("TPO") based, and thermoplastic polyolefin vulcanizates ("TPV") based, automotive body parts It is also contemplated that the compositions are useful for making molded parts that contain filler such as glass It is yet further contemplated that the compositions of the present invention may be useful in the preparation of films, including packaging films, to eliminate tie layers and to improve pπntabihty and barπer properties; fibers including dyeable and non-woven PP fibers; and in packaging matenals for electronics components such as semiconductor chips, wherem the packaging materials may provide electrostatic dissipation which would thereby protect the chips from damage It is yet further contemplated that the composition of the present invention may be useful to improve the barπer properties for polyethylene and to modify polyethylene as a tie layer in multilayer films It is further contemplated that the composition of the present invention may be useful as an additive as polypropylene based reinforcement fibers for concrete. The blend of polypropylene with the reaction product of maleated polypropylene and polyether amine shows improved paintabihty, improved impact resistance, and excellent mold flowabihty over blends of polypropylene and maleated polypropylene. Plastics are increasingly being employed in the production of motor vehicles Impact-modified PP has proved to be particularly suitable for applications such as bumpers, spoilers, fenders, side bump stπps and the like. Therefore, a thermoplastic resm blend having the improved properties of the instant invention has significant potential commercial usefulness. These resin compositions, according to the present invention, are useful as engmeeπng plastics which are matenals for structural members in the fields of transport machines (automobiles, ships and the like), apparatus, tools, electronic appliances, electric appliances, sporting goods, leisure goods and the like; and for connectors, tubes and the like Suitable polypropylenes are known from polymer chemistry, are descπbed for example m Kunststoff-Handbuch, volume IV, Polyolefms, edited by R Vieweg, A Schley and A. Schwarz Carol Hanser Verlag, Munich, 1969, and are commercially available, so that no details need be given Functionalized PP is PP onto which a monomer has been grafted The usual method of such grafting is by free radical reaction. In the practice of this invention, the maleated polypropylene is not a copolymer of maleic anhydπde or equivalent thereof, and propylene, such that the maleic anhydπde moiety is predominantly m the backbone of the copolymer Suitable monomers for prepaπng functionalized polypropylene are, for example, olefinically unsaturated monocarboxyhc acids of less than 12 carbon atoms, e.g., acrylic acid or methacryhc 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., fiimanc acid, maleic acid, and ltacomc 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 anhydπde, sulfo- or sulfonyl- contaimng olefinically unsaturated monomers of less than 12 carbon atoms, e.g., p-styrenesulfomc acid, 2-(meth)acrylamιde-2-methylpropenesulfonιc acid or 2-sulfonyl(meth)acrylate, oxazolmyl -containing olefinically unsaturated monomers of less than 12 carbon atoms, e.g., vmyloxazolmes and vinyloxazohne deπvatives, and epoxy-containing olefinically unsaturated monomers of less than 12 carbon atoms, e.g., glycidyl (meth)acrylate or allyl glycidyl ether The most preferred monomer for prepaπng functionalized polypropylene is maleic anhydπde. The functionalized polypropylene used in the practice of this invention may have a wide vaπety of number average molecular weights. When the functionalized polypropylene is used to make pamtable articles, such as automotive body parts, the functionalized polypropylene preferably has a number average molecular weight greater than about 3,000 and preferably less than about 20,000, more preferably less than about 10,000 A representative example of a maleated polypropylene that is currently commercially available is under the name EPOLENE E-43, available from Eastman Chemical Such relatively low molecular weight functionalized polypropylenes, when reacted with polyetherammes in accordance with the practice of this invention, appears to render the resulting extruded compositions more readily pamtable. In other applications where the functionalized polypropylene is employed, such as when a glass filler is added to increase stiffness and strength, a higher average number molecular weight greater than about 20,000 may be employed. Suitable anhydπde functionalized polypropylene include the following structures- wherein PP is polypropylene. In these structures, it should be appreciated that the polypropylene can be bonded to one or two monomers when the polypropylene is linear, while more than two monomers might be included when the propylene is branched Typically, one or two monomers are present. Suitable polyetherammes include monamines, diamines and tπammes, having a molecular weight of from about 150 to about 12,000 Preferred polyetherammes have a molecular weight of from about 1,000 to about 3,000. Suitable monamines include JEFF AMINE™ 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 TXJ-418, JEFFAMINE™ D-2000, JEFFAMINE™ D-4000, JEFFAMINE™ ED-900, JEFFAMINE™ ED-600, and JEFFAMINE™ D-400. Suitable tπamines include JEFFAMINE™ ET-3000, JEFFAMINE™ T-3000 and JEFFAMINE™ T-5000. Preferred polyetherammes include JEFFAMINE™ M-2070 and JEFFAMINE™ ED-2001. See the glossary for structures of these polyetherammes. More preferred polyetherammes of the present invention have a molecular weight in the range from about 1500 to about 2000. One especially preferred polyetheramine is a polyether monoamine which contains from about 36 to about 44 ethylene oxide units and from 1 to about 6 propylene oxide units. In one embodiment, such polyether monoamines have a molecular weight of about 2000 to about 2200 In another embodiment, the polyether monoamine contains about 40 to about 43 ethylene oxide units and from about 2.4 to about 3 propylene oxide units Certain polyether monoamines are of formula. CH 3 O(CH 2 CH 2 O) m -(CH 2 CHO), r CH 2 CHNH 2 CH, CH, wherein m is about 36 to about 44 and wherein n is about 1 to about 6, including polyether monoamines wherem m is about 40 to about 43 and n is about 2.4 to about 3, as well as compounds of the formula having a molecular weight of about 2000 to about 2200. In the practice of this invention, monoamines and diamines are preferred. Suitable polyether blocks for the polyetheramine include polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly(l,2-butylene glycol), and poly(tetramethylene glycol). The glycols can be aminated using well known methods to produce the polyetherammes 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 of the present invention, the polyetherammes are prepared from ethylene oxide, propylene oxide or combinations thereof. Generally, when the polyetheramine is prepared from ethylene oxide, propylene oxide or combinations thereof, the amount of ethylene oxide on a molar basis is greater than about 50 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 polyam es and alkanol amines or any am e 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. The polyether amines used m the practice of this invention can be prepared using well known am ation techniques such as descπbed in U.S. 3,654,370, U.S 4,152,353; U.S. 4,618,717; U.S. 4,766,245, U.S. 4,960,942, U.S. 4,973,761; U.S. 5,003,107; U.S. 5,352,835; U.S. 5,422,042; and U.S 5,457,147 Generally, the polyether amines are made by aminatmg 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 The mixing of the functionalized PP and polyetheramine and optionally also PP may be earned out in a customary mixing apparatus including batch mixers, continuous mixers, kneaders, and extruders. For most applications, the preferred mixing apparatus is an extruder. Besides the PP/functionalized-PP/polyethera ine structural components according to the invention, the resm composition may, to improve the impact strength, contain impact modifiers, advantageously impact-modifying elastomers Impact-modifying elastomers for the instant invention are known to a skilled worker. Examples are rubbers based on ethylene, propylene, butadiene, and acrylates, e.g. methacrylates, or mixtures thereof. Other examples include EP and EPDM rubbers, with EP rubber (ethylene propylene rubber) being preferred in applications where automotive body parts are being prepared. A representative example of a currently commercially available EP rubber is sold under the name VISTALON 878 by Exxon Chemical. Suitable impact-modifying elastomers are descπbed for example m Methoden der organischen Chemie (Houben-Weyl), volume XTV/1, Makromolekulare Che ie (Georg-Thieme-Verlag, Stuttgart, 1961), pages 390 to 406, and in the monograph by C.B. Bucknal, Toughened Plastics (Applied Publishers, London, 1977) A composition containing polypropylene and elastomers, such as EP rubber, is commonly referred to as a "TPO," which stands for thermoplastic polyolefin. TPO's are commonly used in the manufacture of molded automotive body parts, such as bumper fascias. Such molded parts may also contain other components such as fillers, as descπbed hereinbelow. TPO-based compositions can be prepared in the same manner as for non-elastomer-containmg compositions TPO's are commonly sold in compounded or reactor grades. Representative examples of TPO which are currently available commercially are descπbed below in the paragraphs preceding Examples 18-27. o A composition containing polypropylene and vulcanized elastomers (vulcanized rubber), including thermoplastic polyolefin vulcanizates, is commonly referred to as a "TPV " TPV's are commonly used in the manufacture of molded automotive body parts, such as gπps and handles These molded parts may contain other components such as fillers, as described below TPV-based compositions may be prepared in the same manner as for non-elastomer-contaming compositions. A representative example of a commercially available TPV is descnbed below with reference to Examples 28 and 29. It is contemplated that the polyetheramine and functionalized polypropylene, and optionally a small amount of PP, TPV or TPO, can be reacted to form a reaction product concentrate and, later, the reaction product concentrate can be blended with polypropylene or TPO or TPV In this aspect of the invention, the polyetheramine compnses from about 10 to about 50 weight percent of the concentrate When the reaction product of polyether amme and maleated PP is prepared neat, the reaction product can be blended or compounded with polypropylene or TPO and any other components of the desired composition to the desired levels using a mixing apparatus such as an extruder It should be understood that PP may be commonly used to dilute the reaction. Depending on the type of mixer, the reaction product, polypropylene and any other components can be thoroughly mixed as solids pπor to introducing the admixture in the mixing apparatus. Alternatively, mixers are available which will mix the components duπng operation In either case, duπng operation of the mixer, the components are heated to melt the solids, with the melted components being thereafter mixed to form the final composition. In addition to the structural components of PP, functionalized-PP, and polyetheramine and any impact modifier contained in a resin composition according to the instant invention, the resm may also contain reinforcing agents and/or additives The reinforcing agents used may be reinforcing fillers, for example, carbon or carbon fibers; clay, chalk, talc, and mica to control shπnkage and control coefficient of thermal expansion; glass (beads, fibers or mats such as of woven fibers) to increase stiffness Further, the fillers may be finished with adhesion promoters and/or sizing agents In addition, phosphite or hindered phenol or both can be added as a stabilizer (as a free radical scavenger). When compositions include glass beads or fibers, the composition can contain up to about 40% glass filler if highly stiff compositions are desired. When compositions include glass mats, the composition can contain up to about 80% glass. More typically, from about 2% to about 10% glass filler e composition is employed. Advantageously, the compositions of the present invention that contain glass filler generally are substantially free of voids that typically develop in compositions containing polypropylene and glass While not wishing to be bound by theory, it is believed that the reaction product of polyether amme and maleated polypropylene serves to "wet" the glass to thereby make the glass and polypropylene more combinable (more miscible). In this aspect of the invention, it is preferred to employ maleated polypropylene having an average molecular weight of about 40,000 to about 60,000, as is descπbed heremabove. Generally, glass filler and polypropylene are not miscible, and their combination commonly leads to voids m the resulting compositions The relatively higher molecular weight matenals "wet" the glass to make the glass filler particles and polypropylene more combinable to thereby decrease the amount of voids in the resulting compositions. The preferred functionalized polypropylene is a maleated polypropylene having the following structure: wherem PP is polypropylene. The preferred polyetherammes are monoamines and diamines. The preferred monoamines as well as the preferred tnamines have a molecular weight of from about 200 to about 4000 The preferred diamines have a molecular weight of from about 148 to about 6000. More preferred monoamines and diamines have a molecular weight of from about 1,000 to about 3,000 In one embodiment, the preferred polyetheramine is a polyether monoamine which contains from about 36 to about 44 ethylene oxide units and from 1 to about 6 propylene oxide units In one embodiment, such polyether monoamines have a molecular weight of from about 2000 to about 2200. In a particular embodiment, the polyether monoamine contains from about 40 to about 44 ethylene oxide units and about 2.4 to about 3 propylene oxide units Such polyether monoamines may have the formula CH 3 O(CH 2 CH 2 O) m -(CH 2 CHO),,-CH 2 CHNH 2 CH 3 CH 3 wherein m is from about 36 to about 44, and wherein n is about 1 to about 6. Huntsman Corporation refers to one such polyether monoamine as XTJ-418. The preferred reaction product between the preferred functionalized polypropylene, maleated polypropylene, and the preferred polyetheramine has the following formula. wherem a is from about 5 to 50,000, for b:c from about 0: 100 to 100:0, x is from about 1 to 3, and R is hydrogen or an alkyl moiety having a functionality of x (i.e., if x is 2, R is a divalent), the alkyl radical having 1 to 10 carbon atoms. Suitable thermoplastic resin compositions may contain from about 66 to about 80 wt% TPO or TPV, from about 5 to about 30 wt % maleated PP and from about 2 to about 10 wt% polyetheramine When the compositions include elastomers, such as in TPO-based compositions used to make automotive body parts, or TPV based compositions, the compositions generally compπse from about 5 to about 40 wt% maleated TPO or TPV, from about 2 to about 10 wt% polyetheramine and from about 50 to about 93 wt% PP, such percentages based on the weights of these components of the composition Preferred compositions that include elastomers, or which are TPV-based, compπse about 15 to about 30 wt% maleated PP, from about 2 to about 8 wt% polyetheramine and from about 62 to about 83 wt% TPO or TPV The preferred customary mixing apparatus is an extruder m which the polyetheramine is grafted onto the maleated polypropylene at from about 175 to 300°C in the course of a residence time of from about 25 to 300 seconds. For typical compositions of this invention, degradation begins to occur above this temperature range and below this range the compositions generally do not melt. Polypropylene is a non-reactive component of the mixing blend. The preferred temperature range is from about 190 to 260°C Excess moisture in the blended composition may cause surface blemishes upon molding, but the moisture can be removed by the normal drying processes, including the use of heated, dry air Molded articles prepared from compositions according to the present invention are generally directly pamtable. Representative examples of paints commonly employed for this purpose include urethane-based and melamme-based pamts. Such paints may be applied using conventional techniques Advantageously, compositions of the present invention may be painted directly without solvent borne chlonnated polyethylene pretreatment and optionally without pπmer, though a pπmer may be used. In the examples, continuous compounding was earned out in a Werner & Pfleiderer 30 mm twin screw extruder (ZSK30), having a nine barrel configuration, three kneading zones and one vent section, in which the feed sequence was a combined feed in which all the components fed at the same location (hopper of the extruder). The following examples which illustrate the nature of the instant invention are not intended to be limitative. In the examples, a stoichiometnc excess of maleic functionality on the maleated polypropylene is used relative to the amount of amine functionality on the polyetheramine. EXAMPLES 1-2 In the Tables shown in Examples 1-2, the following phrases have the indicated meanings: "HIMONT CA53A" is a reactor grade TPO containing polypropylene ("PP") and ethylene propylene rubber ("EP rubber") obtained from Himont, which may be descπbed as having medium melt flow. "Phenol" is ETHANOX 330 which is a hindered phenol stabilizer obtained from Albemarle. "EPOLENE E-43" is a maleated PP obtained from Eastman Chemical, having about 4 wt% maleation as determined from proton nmr. "HIMONT LB 150161" is a reactor grade TPO having a high melt flow. "AMOCO 1016" is a PP having a melt flow rate at 230°C of about 5 g/mm. as indicated by the supplier, Amoco Chemical. "DEXFLEX D-161" is a compounded TPO of PP and EP rubber which is described as having medium melt flow by the supplier, D&S Plastics International "NICHTBAN" refers to the tradename of a tape obtained from a Japanese company. "STAMYLAN P" is an impact EP copolymer containing 5-10% ethylene in the backbone obtained from DSM having a melt flow at 230EC/2.16 Kg using an 150 Rl 133 procedure of 4.7 dg/min. as reported by the supplier, Dutch State Mines ("DSM"). "KELTAN TP-0552-2" is a TPO having a melt flow of 6.5 at 230EC/2.16 Kg using an ISO Rl 133 procedure of 6.5 dg/min. as reported by the supplier, DSM. "VISTALON 878" is an EP rubber available from Exxon Chemical. "W/TPA" means with isopropanol wipe pπor to painting and "W/O IPA" means without isopropanol wipe painting. In the Examples, the sample compositions were injection molded to prepare type I tensile bars, which were used in the adhesion tests. The following procedures were used in these examples. A hand mixed blend of polypropylene, maleated polypropylene, polyether amme and an antioxidant is produced and added to the feed hopper. The extruder heater bands are set to the following profile feed throat 200°C, 220°C, 220°C, 220°C, 220°C, 220°C die face The blend is fed into the feed throat of a Werner Pfleiderer ZSK30 twin screw extruder The compounded product is cooled in a water bath and pelletized Test specimens were injection molded using an ENGEL 55 ton injection molding machine using the following conditions Heating Zones. Next to Nozzle Nozzle Feed Zone Feed Zone 199°C 196°C 196°C 196°C Mold Temperature 27°C Physical test specimens were allowed to equilibrate at 24°C and at 50% relative humidity for 48 hours Tensile measurements were made according to ASTM D638 on an INSTRON frame using a crosshead speed of 10 cm/min Flexural properties were measured according to ASTM D790 using a crosshead speed of 1.25 cm/mm. Izod impact properties were measured according to ASTM D256 Dynamical mechanical spectrometry (DMS) was performed using a RHEOMETRICS RDS-II Injection molded bars measuπng 12mm x 50mm x 3mm were tested m rectangular torsion mode at 1 hz Strains imposed upon the samples were typically between 005% and 0 2% Measurements were shown to be strain insensitive over the region investigated The storage and the loss moduli as well as tan delta were measuπng from -120°C up through the melting of the samples, using a heating rate of 2°C/mιn in a nitrogen atmosphere Samples were tested after conditioning at 24EC and 50% relative humidity for 24 hours Paint adhesion testing involved painting four inch injection molded discs with a white, two component urethane automotive paint supplied by RED SPOT PAINTS The paint is applied with a high volume, low pressure BINKS spray gun The painted disks are based for 30 minutes at 80°C The specimens are conditioned 24 hours and then tested using a crosshatch/tape adhesion test where a multibladed scnbe is used to generate 100 squares (approximately 2mm x 2mm per square) on the disks A piece of tape (Scotch Brand 2040, 3M) is then applied over the squares and then the tape is pulled from the disk The percentages denoted in the tables reflect the number of painted squares remaining after pulling the tape from the disk. In the following Examples 1-2, there are shown modified TPV-based (thermoplastic polyolefin vulcanizate-based) compositions that include polyether amines of the present invention (Tables 1 and 2, and the physical properties of the compositions (Tables 28B and 29B, including paint adhesion) In Examples 1 -2, and Tables 1 , 1 B, 2A, and 2B, the TPV employed was SANTOPRENE 101-87, available from Advance Elastomer Systems. SANTOPRENE 101-87 is believed to contain PP and dynamically vulcanized rubber. In Example 2, the amine employed was a polyether monoamine containing 40 ethylene oxide units and 2.4 propylene oxide units, generally of the formula shown in the Glossary for JEFFAMINE™ M-2070, which is referred to within Huntsman Corporation as "XTJ-418". EXAMPLE 1 TABLE 1A Sample TPV EPOLENE E-43 AMINE ETHANOX 330 1 100% ~ — - 2 89.8% 10% — 0.2% 3 85.8% 10% 4% 0.2% 4 83.8% 10% 6% 0.2% 5 80.8% 15% 4% 0.2% 6 78.8% 15% 6% 0.2% 7 75.8% 20% 4% 0.2% 8 73.8% 20% 6% 0.2% 9 71.8% 20% 8% 0.2% TABLE IB 1 2 3 4 5 6 7 8 9 Flexural Modulus, MpA 196 294 252 272 282 316 321 345 366 Stress at Yield, MPa 7.1 9.5 8.5 8.8 9.1 9.8 10.2 10.8 10.8 Tensile Elongation, % 666 666 666 666 644 666 479 467 118 Tensile Strength, MPa 12.0 12.3 1 1. 11.6 11.4 1 1.4 10.4 10.4 7.9 6 Hardness Shore D 41 45 43 44 45 47 47 48 49 Notched Izod Impact, 268 388 380 357 402 377 354 198 120 J/m -30°C, J/m 606 114 103 81 58 49 25 30 19 Falling Dart Impact Max Load, J/m 824 915 854 836 870 865 878 892 813 -30°C, J/m 152 1749 182 1655 157 1597 1042 1194 782 9 7 0 Total E, J 19.4 20.2 18. 18.5 17.7 18.4 15.5 16.2 8.7 9 -30°C, J 26.2 25.9 22. 20.6 9.0 11.1 4.5 5.8 3.0 0 Ductile/5 5 5 5 5 5 5 5 5 5 -30°C 5 5 5 5 0 0 0 0 0 MFI, gm/lO mm. 0.3 4.0 5.1 23 40 47 63 90 154 Paint Adhesion w LPA, 30 49 72 100 72 92 92 96 100 % w/o LPA, % 46 23 70 100 66 72 69 78 100 EXAMPLE 2 TABLE 2A Sample TPV EPOLENE E-43 JEFFAMINE™ ETHANOX 330 M-2070 1 100% ... ... ... 2 89 8% 10% ... 0 2% 3 84 8% 15% ... 0 2% 4 79 8% 20% ... 02% 5 85 8% 10% 4% 0 2% 6 83 8% 10% 6% 0 2% 7 80 8% 15% 4% 0 2% 8 78 8% 15% 6% 02% 9 75 8% 20% 4% 0 2% 10 73 8% 20% 6% 0 2% 1 1 71 8% 20% 8% 0 2% JEFFAMINE™ ED-2003 12 80 8% 15% 4% 0 2% 13 78 8% 15% 6% 0 2% 14 75 8% 20% 4% 0 2% 15 73 8% 20% 6% 0 2% 16 71 8% 20% 8% 0 2% TABLE 2B 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Flexural Modulus, MPa 208 290 368 417 273 251 282 272 329 310 313 263 227 292 295 280 Stress at Yield, MPa 73 95 115 126 90 86 93 89 104 98 99 89 81 95 99 97 J Tensile Elongation, % 666 666 658 545 666 666 666 663 561 580 379 666 666 666 666 666 Tensile Strength, MPa 123 129 127 116 117 115 123 115 111 106 98 118 122 118 113 n 4 Hardness, Shore D 41 46 49 51 44 43 45 44 47 46 47 46 44 46 47 46 Notched Izod Impact, J/m 353 400 438 393 378 381 379 403 250 321 150 404 378 423 373 380 -30 σ C, J/m 655 153 46 24 70 12 71 48 15 25 23 44 58 24 24 27 Maximum Load, J/m 973 906 961 966 895 889 894 832 881 854 850 906 922 921 895 935 -30°C, J/m 1741 1658 1817 1538 1857 1731 1909 1865 854 1100 796 2068 1662 689 387 574 Total Energy, J 210 210 202 175 198 192 190 177 158 166 153 193 189 185 154 191 -30°C 266 283 202 74 238 211 211 139 44 51 40 150 74 21 25 13 Ductile/5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 -30°C 5 5 4 0 4 4 5 0 0 0 0 0 0 0 0 0 MFI, gm/IOmin 06 08 81 14 43 19 44 74 111 95 11 09 24 19 38 Paint Adhesion w/IPA, % 4 0 14 4 16 35 14 72 80 98 96 2 1 32 92 70 w/o IPA, % 1 1 20 8 14 16 6 78 98 92 92 10 1 36 91 62 Examples 1-2 demonstrate the improved properties of TPV-based compositions that have been modified with the reaction product of maleated PP and polyether amines, providing composition that are directly pamtable This paintabi ty is surprising and unexpected in that TPV's used to make automotive parts, are not directly readily pamtable to a commercially acceptable level Instead, TPV- based compositions had to be treated, as descπbed above for TPO-based compositions TPV-based compositions prepared m accordance with the practice of this invention generally may be directly painted, with or without pπmer, such that the paint adhesion is greater than about 75 percent based on the testing procedure used for Examples 1 -2, preferably greater than about 85 percent, more preferably greater than about 90 percent, and most preferably greater than about 95 percent Performance improvements can be gained by incorporating polyetherammes into polyolefms such as polypropylene, polyethylene and copolymers of ethylene, propylene, alpha-olefms, and mixtures thereof, as well as polyolefms containing conjugated and unconjugated dienes, for textile and nonwoven applications Polyetherammes can be incorporated into polyolefms by reacting the polyetheramine with a functionalized polyolefin One example of such technology is the reaction of polyetheramine with maleated polypropylene in the presence of polypropylene Such a reaction can be completed in an extruder or similar thermoplastic mixing device An adduct of the reaction product of the maleated polypropylene/polyether amme can be produced m a reactor and then subsequently added to polypropylene or polyolefin for further processing The incorporation of polyetherammes into polyolefms will improve the dyeabihty of the polyolefin The polar polyether segment is a site for the complexation of polar solvent or water based dyes Typical polar dyes are not compatible with nonpolar polyolefms and would quickly bleed out of the fiber or filament The polyetherammes will improve the washabihty of a polyolefin based textile fabric or nonwoven mat The nonpolar polyolefin tends to hold on to dirt due to the hydrophobic nature of both The polyetheramine will allow detergents to penetrate the fabπc or matrix so the detergents can loosen and wash away the dirt and oils The incorporation of polyether amines will increase the adsorption and wickabihty of polyolefin textiles and nonwovens One example is the melt blown, nonwoven absorbent in baby diapers Making the surface of the nonwoven filament more hydrophihc by incorporating the polar polyetheramine into the polyolefin will greatly increase the diaper's moisture absorption characteπstics Suitable thermoplastic resin compositions useful in the manufacture of fibers and nonwovens should contain an effective amount of polyetheramine. In one embodiment of the present invention, the thermoplastic resm composition may contain up to about 12 wt % polyetheramine and up to about 30 wt % maleated polypropylene. In particular, the thermoplastic resm composition may contain up to 8 wt % polyetheramine and up to 20 wt % maleated polypropylene. In a preferred embodiment, the thermoplastic resin composition may contain from about 0.1 to about 5 wt % polyetheramine and from about 0.2 to about 15 wt % maleated polypropylene. In an especially preferred embodiment, the thermoplastic resm composition may contain from about 1 to about 4 wt % polyetheramine and from about 2 to about 12 wt % maleated polypropylene. Applications of the fibers and filaments from the polyether modified polyolefms include, with limitation: woven garments (outerwear and underwear); carpet; furniture and automobile upholstery; nonwoven absorbents used in diapers, sanitary pads, incontinence pads, spill abatement, and medical absorbent pads; nonwoven garments, including disposable medical garments; felts; pressed sheets; geo- textiles; filters (bipolar); and packaging materials, including envelopes. GLOSSARY ■TEFFAMTNFJ M-1000 CH 3 CH 3 CH 3 0(C 2 H 4 0) 18 6 (CH 2 CHO) 1 6 CH 2 CHNH 2 JEFFAMINE™ M -2070 and EFFAMTNE™ M-2005 CH 3 0(CH 2 CH ) m -(CH 2 CHO) n -CH 2 CHNH 2 R CH 3 where R=H or CH 3 , is from about 3 to 32, and n is from about 10 to 32 .IEFFAMINE™ D-2000. .TEFFAMINE™ D-4000 and JEFFAMINE™ D-400 H 2 NCHCH ^[OCH 2 CH] χ -NH 2 CH 3 CH 3 where x is about 33 for D-2000, x is about 68 for D-4000 and x is about 5.6 for D-400. .TEFFAMINE™ ED-600. .IEFFAMINE™ ED-900. JEFFAMINE™ ED-2001. JEFFAMINE™ ED-4000. and .IEFFAMINE™ ED-6000 CH 3 CH 3 CH 3 H 2 NCHCH ^-(OCHCH 2 ) a --(OCH 2 CH 2 ) b -(OCH 2 CH) C -NH 2 where b is about 8.5 and a + c is about 2.5 for ED-600, b is about 15.5 and a + c is about 2.5 for ED- 900, b is about 40.5 and a + c is about 2.5 for ED-2001, b is about 86.0 and a + c is about 2.5 for ED- 4000, and b is about 132.0 and a + c is about 3.0 for ED-6000. JEFFAMINE™ T-3000 and .TEFFAMINE™ T-5000 H 2 CO[CH 2 CHO] χ CH 2 CHNH 2 I <?H 3 CH 3 H 2 CO[CH 2 CHO] y CH 2 CHNH 2 I c H 3 CH 3 H 2 CO[CH 2 CHO] Z CH 2 CHNH 2 where x + y + z = 50 for T-3000 and x + y + z = 83 for T-5000. lo JEFFAMINE™ ET-3000 H 2 2 H 2 C0[CH 2 CH 2 0] y [CH 2 CHO] b CH 2 CHNH 2 I CH :3 H3 H 2 CO[CH 2 CH 2 0] z [CH 2 CHO] c CH 2 CHNH 2 where x + y + z = 57 and a + b + c = 4.

Claims: CLAIMS: 1. A composition compπsing polypropylene, a polyolefin vulcanizate, and the reaction product of a functionalized polypropylene and a polyether amine 2. The compound of claim 1, wherein the functionalized polypropylene is deπved from the free radical reaction of polypropylene and an olefinically unsaturated carboxyhc acid 3. The compound of Claim 2 wherein the olefinically unsaturated carboxyhc acid is a monocarboxylic acid compπsed of acrylic acid or methacry c acid, and the corresponding esters. 4. The compound of Claim 2 wherem the olefinically unsaturated carboxyhc acid is a dicarboxylic acid compπsed of fumaπc acid, maleic acid, and ltacomc acid. 5. The compound of Claim 1 wherein the functionalized polypropylene is deπved from the reaction of polypropylene and mono- and/or di- esters of olefinically unsaturated dicarboxylic acids compπsing mono- or di- fumarate and mono- or di- maleate. 6. The compound of Claim 1 wherein the functionalized polypropylene is derived from the reaction of polypropylene and an olefinically unsaturated carboxyhc anhydπde. 7. The compound of Claim 1 wherem the functionalized polypropylene is deπved from the reaction of polypropylene and sulfo- or sulfonyl-containmg olefinically unsaturated monomers compπsing p-styrenesulfonic acid, 2-(meth)acrylamιde-2-methylpropenesulfomc acid and 2-sulfonyl- (meth)acrylate. 8. The compound of Claim 1 wherem the functionalized polypropylene is deπved from the reacUon of polypropylene and oxazolmyl-containing olefinically unsaturated monomers compπsing vinyloxazo nes and vinyloxazohne deπvatives. 9. The compound of Claim 1 wherein the functionalized polypropylene is deπved from the reaction of polypropylene and epoxy-contaimng olefinically unsaturated monomers, selected from the group compπsing glycidyl (meth)acrylate and allyl glycidyl ether. 10. The compound of Claim 1 wherem the polyether amine is selected from the group consisting of monoamines, diammes and tπammes and has a molecular weight of from about 148 to 12,000. 11. The composition according to claim 10, wherein the polyetheramine is a monoamine or diamine and having a molecular weight of from about 150 to about 12,000. 12. The composition according to claim 1, wherein the polyetheramine is prepared from ethylene oxide and propylene oxide with the amount of ethylene oxide m the polyetheramine being greater than about 50 percent. 13. The composition according to claim 1, wherein the composition compπses from about 5 to about 40 weight percent functionalized polypropylene, from about 2 to about 10 weight percent of polyether amine, and 50 to about 93 weight percent of polypropylene and elastomer. 14 A composition useful as a mateπal for making pamtable automotive body parts, comprising' polypropylene; polyolefin vulcanizate; and the reaction product of maleated polypropylene and a polyether amine 15. The compound of Claim 14 wherein the reaction product of maleated polypropylene and the polyether amine has the formula: wherein a is from about 5 to 50,000, for b:c from about 0:100 to 100:0, x is from about 1 to 3, and R is an alkyl moiety 16. The compound of Claim 14 wherein the maleated polypropylene is selected from the group consisting of the structures having the formulae wherein PP is polypropylene: 17. The compound of Claim 14 wherein the polyether is selected from the group consisting of polyethylene glycol, polypropylene glycol and copolymers of polyethylene glycol and polypropylene glycol. 18. The compound of Claim 14 wherein the polyetheramine has the following structure: CH 3 0(CH 2 CH 2 0) m -(CH 2 CHO) n -CH 2 CHNH 2 R CH 3 where R=H, CH 3 , m is from about 3 to 32, and n is from about 10 to 32. 19 The compound of Claim 14 wherein the polyetheramine has the following structures CH 3 CH 3 CH 3 H 2 NCHCH 2~(OCHCH 2 ) a -(OCH 2 CH 2 ) b -(OCH 2 CH) C -NH 2 where b is about 40.5 and a + c is about 2.5, b is about 86.0 and a + c is about 2 5, and b is about 1320 and a + c is about 2 to 10. 20 The compound of Claim 14 wherem the polyetheramine has the following formula 21. The compound of Claim 14 wherein the polyether amme is selected from the group consisting of monoamines, diammes and tnamines and has a molecular weight of from about 148 to 12,000. 22. The compound of claim 21 wherein the polyether amine is a monoamine selected from the group having a molecular weight from about 200 to 4000 23. The compound of Claim 22 wherem the monoamine has the following structure: CH 3 CH CH 3 0(C 2 H 4 0) 18 6 (CH 2 C I HO) 1 . 5 CH 2 C 1HNH 2 24. The compound of Claim 22 wherein the monoamine has the following structure: CH 0(CH 2 CH 2 0)-(CH 2 CHO) -CH 2 CHNH 2 R CH where R = H or CH, m is from about 3 to 32, and n is from about 10 to 32. 25. The compound of Claim 21 wherein the polyether amine is a diamine selected from the group having a molecular weight of from about 148 to 6000. 26. The compound of Claim 25 wherein the diamme is selected from the group consisUng of compounds of the following structure: CH 3 CH 3 CH 3 H 2 NCHCH 2~(OCHCH 2 ) a ~(OCH 2 CH 2 ) b -(OCH 2 CH) C -NH 2 where b is about 8.5 and a + c is about 2.5, b is about 15.5 and a + c is about 2.5, b is about 40.5 and a + c is about 2.5, b is about 86.0 and a + c is about 2.5, and b is about 132.0 and a + c is about 2 to 10. 27. The compound of Claim 21 wherein the diamine is selected from the group consisting of compounds of the following structure. H 2 NCHCH ^[OCH QH] X -NH 2 CH 3 CH 3 where x is about 33, x is about 68, and x is about 5.6. 28. The compound of Claim 21 wherein the polyether amine is a tπamme having the molecular weight of from about 200 to 4000. 29. The compound of Claim 28 wherein the tπamme is selected from the group consisting of compounds having the following structure: H 2 CO[CH 2 CHO] X CH 2 CHNH 2 H 2 CO[CH 2 CHO] y CH 2 CHNH 2 I 9 H 3 9 H 3 H 2 CO[CH 2 CHO] Z CH 2 CHNH 2 where x + y + z = 50 and x + y + z = 83. 30. The compound of Claim 28 wherein the triamine has the following structure: H 2 2 H 2 2 H 2 CO[CH 2 CH 2 0] Z [CH 2 CHO] C CH 2 CHNH 2 where x + y + z = 57 and a + b + c = 3 to 15. 31. The composition according to claim 14, wherein the functionalized polypropylene has a number average molecular weight of about 3,000 to about 20,000. 32. The composition according to claim 14, wherein the polyetheramine has a molecular weight in the range from about 1,500 to about 2,000 and is a monoamine or a diamine. 33. The composition according to claim 14, wherein the polyetheramine is prepared from ethylene oxide and propylene oxide with the amount of ethylene oxide in the polyetheramine being greater than about 50 percent. 34. The composition according to claim 32, wherein the polyetheramine is a monoamine and wherein the polyetheramine is prepared from ethylene oxide and propylene oxide wherein the amount of ethylene oxide in the polyetheramine on a molar basis is greater than about 75 percent. 35. T e composition according to claim 34, wherein the amount of ethylene oxide is greater than about 90 percent. 36. The composition according to claim 14, wherein the maleated polypropylene has a number average molecular weight of from about 3,000 to about 20,000. 37. The composition according to claim 14, wherein the composition compπses maleated polypropylene m an amount in the range from about 5 to about 40 weight percent and polyetheramine in an amount in the range from about 2 to about 10 weight percent 38. The composition according to claim 14, wherein the polyetheramine is a monoamine or diamme having a molecular weight in the range from about 1,000 to about 3,000 and wherein the polyetheramine is prepared from propylene oxide, ethylene oxide or combination thereof 39. The composition according to claim 14, wherem the polyetheramine is prepared from ethylene oxide, propylene oxide or combination thereof. 40. The composition according to claim 14, in the absence of an am e other than a polyetheramine and in the absence of a copolymer of an olefin and maleic anhydπde. 41. The composition according to claim 14, wherem the paint adhesion of the composition is greater than 95 percent. 42. The composition according to claim 14, further compnsing a glass filler in an amount up to about 40 weight percent. 43. A process for prepaπng a composition useful for making molded automotive body parts, compπsing: feeding polypropylene, crosslinked thermoplastic polyolefin, maleated polypropylene, and polyether amme to a mixing apparatus at a temperature in the range from about 175°C to about 300°C under conditions such that a reaction product of the maleated polypropylene and the polyether amme is formed. 44. The process of Claim 43 wherein the reaction product of maleated polypropylene and the polyether amine has the formula. wherem a is from about 5 to 50,000, for b:c from about 0:100 to 100:0, x is from about 1 to 3, and R is an alkyl moiety. 45. The process of Claim 43 wherein the maleated polypropylene is selected from the group consisting of the structures having the formulae wherein PP is polypropylene: 46. The process of Claim 43 wherein the polyether is selected from the group consisting of polyethylene glycol, polypropylene glycol and copolymers of polyethylene glycol and polypropylene glycol. 47. The process of Claim 43 wherein the polyetheramine has the following structure: CH 3 0(CH 2 CH 2 0) m -(CH 2 CHO) n -CH 2 CHNH 2 R CH 3 where R=H, CH 3 , m is from about 3 to 32, and n is from about 10 to 32 48. The process of Claim 43 wherem the polyetheramine has the following structures CH 3 CH 3 CH 3 H 2 NCHCH ^-(OCHCH 2 ) a -(OCH 2 CH 2 ) b -(OCH 2 CH) C -NH 2 where b is about 40.5 and a + c is about 2.5, b is about 86.0 and a + c is about 2.5, and b is about 132.0 and a + c is about 2 to 10. 49 The process of Claim 43 wherein the polyetheramine has the following formula- CH CH 3 i CH 3 0(C 2 H 4 0) 18 6 (CH 2 CHO) 1 . 5 CH 2 CHNH 2 50 The process of Claim 43 wherein the polyether amine is selected from the group consisting of monoamines, diamines and tnamines and has a molecular weight of from about 148 to 12,000 51. The process of claim 50 wherem the polyether amine is a monoamine selected from the group having a molecular weight from about 200 to 4000. 52. The process of Claim 51 wherem the monoamine has the following structure: CH 3 0(C 2 H 4 0) 18 6 (CH 2 53. The process of Claim 51 wherein the monoamine has the following structure : CH 2 0(CH 2 CH 2 0) m -(CH 2 CHO) n -CH 2 CHNH 2 R CH 3 where R = H or CH, m is from about 3 to 32, and n is from about 10 to 32. 54. The process of Claim 50 wherein the polyether amme is a diamine selected from the group having a molecular weight of from about 148 to 6000. 55. The process of Claim 54 wherein the diamme is selected from the group consisting of compounds of the following structure: H 2 NCHCH 2~(OCHCH 2 ) a -(OCH 2 CH 2 ) b -(OCH 2 CH) C -NH 2 where b is about 8.5 and a + c is about 2.5, b is about 15.5 and a + c is about 2.5, b is about 40.5 and a + c is about 2.5, b is about 86.0 and a + c is about 2.5, and b is about 132.0 and a + c is about 2 to 10. 56. The process of Claim 50 wherein the diamme is selected from the group consisting of compounds of the following structure. H 2 NCHCH ^[OCH 2 CH] X -NH 2 CH 3 CH 3 where x is about 33, x is about 68, and x is about 5.6 57. The process of Claim 50 wherein the polyether amine is a tnamme having the molecular weight of from about 200 to 4000. 58 The process of Claim 57 wherein the tπamine is selected from the group consisting of compounds having the following structure: H 2 H 2 H 2 CO[CH 2 CHO] Z CH 2 CHNH 2 where x + y + z = 50 and x + y + z = 83. 59 The process of Claim 57 wherem the tnamme has the following structure CH 3 CΗ 3 H 2 CO[CH 2 CH 2 0] χ [CH 2 CHO] a CH 2 CHNH 2 CH - CH H 2 CO[CH 2 CH 2 0] y [CH 2 CHO] b CH 2 CHNH 2 I 9 Hs ? H 3 H 2 CO[CH 2 CH 2 0] Z [CH 2 CHO] C CH 2 CHNH 2 where x + y + z = 57 and a + b + c = 3 to 15. 60 The process according to claim 43, wherein the functionalized polypropylene has a number average molecular weight of about 3,000 to about 20,000 61 The process according to claim 43, wherein the polyetheramine has a molecular weight m the range from about 1 ,500 to about 2,000 and is a monoamine or a diamme 62. The process according to claim 43, wherein the polyetheramine is prepared from ethylene oxide and propylene oxide with the amount of ethylene oxide in the polyetheramine being greater than about 50 percent. 63. The process according to claim 62, wherem the polyetheramine is a monoamine and wherein the polyetheramine is prepared from ethylene oxide and propylene oxide wherem the amount of ethylene oxide m the polyetheramine on a molar basis is greater than about 75 percent. 64. The process accordmg to claim 63, wherem the amount of ethylene oxide is greater than about 90 percent 65. The process according to claim 43, wherem the maleated polypropylene has a number average molecular weight of from about 3,000 to about 20,000 66 The process according to claim 43, wherein the composition compnses maleated polypropylene in an amount in the range from about 5 to about 40 weight percent and polyetheramine in an amount in the range from about 2 to about 10 weight percent 67. The process according to claim 43, wherem the polyetheramine is a monoamine or diamme having a molecular weight in the range from about 1,000 to about 3,000 and wherem the polyetheramine is prepared from propylene oxide, ethylene oxide or combination thereof 68. The process according to claim 43, wherein the polyetheramine is prepared from ethylene oxide, propylene oxide or combination thereof 69 The process accordmg to claim 43, in the absence of an amine other than a polyetheramine and m the absence of a copolymer of an olefin and maleic anhydnde. 70 The process according to claim 43, wherein the paint adhesion of the composition is greater than 95 percent 71 The process according to claim 43, further compnsing a glass filler in an amount up to about 40 weight percent 72 The process of claim 43, further compnsing prepaπng a molded automotive body part by injection molding a blend made m accordance with the feeding step, and painting the molded automotive body part. 73. An article of manufacture made in accordance with claim 72

Inventors: CLARK RICHARD J, DOMINGUEZ RICHARD JOSEPH GILBE, EVANS RANDALL KEITH, CLARK, RICHARD, J., DOMINGUEZ, RICHARD, JOSEPH, GILBERT, EVANS, RANDALL, KEITH
Applicants: CLARK RICHARD J, DOMINGUEZ RICHARD JOSEPH GILBE, EVANS RANDALL KEITH, HUNTSMAN SPEC CHEM CORP, CLARK, RICHARD, J., DOMINGUEZ, RICHARD, JOSEPH, GILBERT, EVANS, RANDALL, KEITH, HUNTSMAN PETROCHEMICAL CORPORATION
Application year: 1997
Main classification: C08L23
IPC codes: C08F8, C08G65, C08G81, C08L23, C08L51, C08L71