Polyether monoamine with 36-44 EO units and 1-6 PO units

Abstract

A polyether monoamine containing from about 36 to about 44 ethylene oxide units and from about 1 to about 6 propylene oxide units is useful as a reactant with functionalized polypropylene such as maleated polypropylene to form a reaction product blended with polypropylene.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a novel olefin polymer composed of the reaction of a functionalized polypropylene and a polyether amine. This invention also relates to thermoplastic resin blends containing the novel olefin polymer and polypropylene. This invention also relates to polyetheramines.

2. Related Art

The in situ formation of compatibilizers 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 compatibilizer for a mixture of two or more polymers. The prior 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 resin compositions containing polypropylene are well known in the art (e.g. U.S. Pat. No. 5,208,081). U.S. Pat. No. 5,179,164 describes a polypropylene/polyamide composition suitable for producing moldings. The patent describes an ethylene copolymer useful as an adhesion promoter. Moreover, the patent indicates that maleic acid is a suitable monomer for preparing the ethylene copolymer.

In addition, maleated polypropylene is commercially available.

European patent application 0 367 832 discloses a resin composition containing an olefinic polymer having acid anhydride groups. As in U.S. Pat. No. 5,179,164, the novel compound is blended with a polyamide.

Japanese patent 46003838 reveals a maleic anhydride modified polypropylene composition containing trimethylamine and polyethylene glycol nonylphenyl ether. Japanese patent 60195120 reveals a molding containing polyethylene, maleic anhydride-grafted polyethylene, and diethylenetriamine.

However, the instant invention uses the maleic anhydride in conjunction with polyetheramines which produce unexpected improvements in resin properties.

SUMMARY OF THE INVENTION

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 anhydride component of the functionalized polypropylene to form a reaction product, for instance, a primary amine will react with a maleic anhydride to form an imide. 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 imide group.

This invention is also a polyether monoamine which contains from about 36 to about 44 ethylene oxide units and from about I to about 6 propylene oxide units. By ethylene oxide unit and propylene oxide unit it is meant the residue of ethylene oxide and propylene oxide which has been incorporated into the polyether monoamine, i.e., units corresponding to —CH 2 CH 2 O— and —CH 2 CHCH 3 O—, respectively. This invention further relates to a process for making a blend containing polypropylene and the reaction product of a functionalized polypropylene and a polyether monoamine by melting polypropylene polyether monoamine and functionalized polypropylene to form the blend. This invention is yet further directed to a blend containing polypropylene and the reaction product of polyether monoamine and functionalized polypropylene.

The compositions of the present invention are useful for preparing molded automotive body parts, including directly paintable thermoplastic polyolefins (“TPO”) 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 printable films; fibers including dyable and non-woven PP fibers; and in packaging materials for electronics components such as semiconductor chips, wherein 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 barrier 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.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The blend of polypropylene with the reaction product of maleated polypropylene and polyether amine shows improved paintability, improved impact resistance, and excellent mold flowability 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 strips and the like. Therefore, a thermoplastic resin 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 engineering plastics which are materials 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 described for example in Kunststoff-Handbuch, volume IV, Polyolefins, 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 anhydride or equivalent thereof, and propylene, such that the maleic anhydride moiety is predominantly in the backbone of the copolymer. Suitable monomers for preparing functionalized polypropylene 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 2-sulfonyl(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. The most preferred monomer for preparing functionalized polypropylene is maleic anhydride.

The functionalized polypropylene used in the practice of this invention may have a wide variety of number average molecular weights. When the functionalized polypropylene is used to make paintable 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 polyetheramines in accordance with the practice of this invention, appears to render the resulting extruded compositions more readily paintable. In other applications wherein 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 40,000 and less than about 60,000 may be employed. Generally, glass filler and polypropylene are not miscible, and their combination commonly leads to voids in the resulting compositions. The relatively higher molecular weight materials “wet” the glass to make the glass filler particles and polypropylene more combinable to thereby decrease the amount of voids in the resulting compositions.

Suitable anhydride 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 polyetheramines include monamines, diamines and triamines, having a molecular weight of from about 150 to about 12,000. Preferred polyetheramines have a molecular weight of from about 1,000 to about 3,000. Suitable monamines, shown in the Glossary, include JEFFAMINE M-1000, JEFFAMINE M-2070, and JEFFAMINE M-2005. Suitable diamines include JEFFAMINE ED-6000, JEFFAMINE ED-4000, JEFFAMINE ED-2001, 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. Preferred polyetheramines include JEFFAMINE M-2070 and JEFFAMINE ED-2001. More preferred polyetheramines of the present invention have a molecular weight in the range from about 1500 to about 2000. 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(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.

An especially preferred polyetheramine is a polyether monoamine which contains from about 36 to about 44 ethylene oxide units and from about 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:

wherein m is about 36 to about 44 and wherein n is about 1 to about 6, including polyether monoamines wherein 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 one embodiment of the present invention, the polyetheramines 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 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. The polyether amines used in the practice of this invention can be prepared using well known amination techniques such as described in U.S. Pat. Nos. 3,654,370; 4,152,353; 4,618,717; 4,766,245; 4,960,942; 4,973,761; 5,003,107; 5,352,835; 5,422,042; and 5,457,147. Generally, the polyether amines 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.

The mixing of the functionalized PP and polyetheramine and optionally also PP may be carried 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/polyetheramine structural components according to the invention, the resin 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 described for example in Methoden der organischen Chemie (Houben-Weyl), volume XIV/1, Makromolekulare Chemie (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 described hereinbelow. TPO-based compositions can be prepared in the same manner as for non-elastomer-containing compositions. TPO's are commonly sold in compounded or reactor grades. Representative examples of TPO which are currently available commercially are described below in the paragraphs preceding Examples 18-29.

It is contemplated that the polyetheramine and functionalized polypropylene, and optionally a small amount of PP or TPO, can be reacted to form a reaction product concentrate and, later, the reaction product concentrate can be blended with polypropylene or TPO. In this aspect of the invention, the polyetheramine comprises from about 10 to about 50 weight percent of the concentrate. When the reaction product of polyether amine 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 prior to introducing the admixture in the mixing apparatus. Alternatively, mixers are available which will mix the components during operation. In either case, during 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 resin 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 shrinkage and control coefficient of thermal expansion; glass (beads or 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 a glass filler, the composition can contain up to about 40% glass filler if highly stiff compositions are desired. More typically, from about 2% to about 10% glass filler in the 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 amine 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 described hereinabove.

The preferred functionalized polypropylene is a maleated polypropylene having the following structure:

wherein PP is polypropylene.

The preferred polyetheramines are monoamines and diamines. The preferred monoamines as well as the preferred triamines 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.

The preferred reaction product between the preferred functionalized polypropylene, maleated polypropylene, and the preferred polyetheramine has the following 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 hydrogen or an alkyl radical 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 % PP, from about 20 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, the compositions generally comprise from about 5 to about 40 wt a maleated PP, 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 comprise about 15 to about 30 wt % maleated PP, from about 2 to about 8 wt % polyetheramine and from about 62 to about 83 wt % PP.

The preferred customary mixing apparatus is an extruder in 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 nonreactive component of the mixing blend. The preferred temperature range is from about 190 to 260° C.

Molded articles prepared from compositions according to the present invention are generally directly paintable. Representative examples of paints commonly employed for this purpose include urethane-based and melamine-based paints. Such paints may be applied using conventional techniques. Advantageously, compositions of the present invention may be painted directly without chlorine pretreatment and optionally without primer, though a primer may be used.

In the examples, continuous compounding was carried 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 stoichiometric excess of maleic functionality on the maleated polypropylene is used relative to the amount of amine functionality on the polyetheramine.

EXAMPLES 1-6

Blends of PP, maleated PP (MAL-PP), and JEFFAMINE M-2070 produced in an extruder exhibit characteristics in percent compositions as shown in Table 1 in which the remaining percent is PP:

TABLE 1
Example	1	2	3	4	5	6
% MAL-PP	20	30
% M2070	0	2	4	0	2	4
FM, psi	284K	255K	226K	289K	256K	201K
StY, psi	8660	7980	7030	8750	7830	6170
TE, %	8	16	10	4	13	5
TSt, psi	4990	4770	4280	5000	4630	3720
NI, ft lb/in	0.161	0.220	0.386	0.123	0.139	0.220
UnI, ft lb/in	12	14	10	10	14	5
where:
FM — flexural modulus
StY — stress at yield
TE — Tensile elongation
TSt — tensile strength
NI — notched izod impact
UnI — unnotched izod impact

EXAMPLES 7-10

Table 2 reveals the effects of JEFFAMINE M-2070 (M) as compared to JEFFAMINE ED-2001 (ED) in which either is blended with from about 76 to 78 wt % of PP, and from about 20 wt % of MAL-PP in an extruder.

	TABLE 2
	Example	7	8	9	10
	J. Type	M	ED	M	ED
	% JEFF.	2		4
	FM, psi	255K	246K	226K	230K
	StY, psi	7980	7730	7030	7140
	TE, %	16	10	10	16
	TSt, psi	4770	4560	4280	4420
	NI, ft lb/in	14	15	10	18
	UnI, ft lb/in	14	15	10	18
	where:
	FM — flexural modulus
	StY — stress at yield
	TE — Tensile elongation
	TSt — tensile strength
	NI — notched izod impact
	UnI — unnotched izod impact.

EXAMPLES 11-17

Table 3 reveals the percent paint adhesion of various compositions of PP, maleated PP, and the JEFFAMINES indicated relative to a control sample wherein the blends were produced in an extruder.

TABLE 3
Exam-		MAL-		Paint	Con-
ple	PP	PP	% J. Type	Adhesion	trol
11	76%	20%	4% JEFFAMINE M1000	62%	2%
12	76%	20%	4% JEFFAMINE ED-6000	28%	4%
13	74%	20%	6% JEFFAMINE ED-6000	46%	4%
14	74%	20%	6% JEFFAMINE ED-4000	40%	4%
15	74%	20%	6% JEFFAMINE M-2070	77%	21%
16	72%	20%	8% JEFFAMINE M-2070	40%	21%
17	72%	20%	8% JEFFAMINE M-2001	68%	21%

In the following Examples 18-29, there are shown modified TPO-based (thermoplastic olefin-based) compositions including polyether amines of the present invention (in Tables 18A, 19A, 20A, 21A, 22A, 23A, 24A, 25A, 26A, and 27A), the physical properties of the compositions (in Tables 18B, 19B, 20B, 21B, 22B, 23B, 24B, 25B, 26B, and 27B) and the paint adhesion of the compositions (in Tables 18C, 19C, 20C, 21C, 22C, 23C, 24C, 25C, 26C, and 27C). In the Tables shown in Examples 18-29, 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 described 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 LB150161 ” 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/min. 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.

“NICHIBAN” 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 230° C./2.16 Kg using an 150 R1133 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 at 230° C./2.16 Kg using an ISO R1133 procedure of 6.5 dg/min. as reported by the supplier, DSM.

“VISTALON 878” is an EP rubber available from Exxon Chemical.

“W/IPA” means with isopropanol wipe prior to painting and “W/O IPA” means without isopropanol wipe painting.

In Examples 18-29, 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 amine 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/min. Izod impact properties were measured according to ASTM D256.

Dynamical mechanical spectrometry (DMS) was performed using a RHEOMETRICS RDS-II. Injection molded bars measuring 12 mm×50mm×3 mm were tested in rectangular torsion mode at 1 Hz. Strains imposed upon the samples were typically between 0.05% 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 measuring from −120° C. up through the melting of the samples, using a heating rate of 2° C./min. in a nitrogen atmosphere. Samples were tested after conditioning at 24° C. 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 scribe is used to generate 100 squares (approximately 2 mm×2 mm 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.

EXAMPLE 18

TABLE 18A
			JEFFAMINE ®
Sample	TPO 1	MAL-PP 2	M-2070	Phenol	PP
1	99.7%	—	—	0.3%
2	84.7%	—	—	0.3%	15%
3	79.7%		—	0.3%	20%
4	84.7%	15%	—	0.3%
5	79.7%	20%	—	0.3%
6	80.7%	15%	4%	0.3%
7	78.7%	15%	6%	0.3%
8	75.7%	20%	4%	0.3%
9	73.7%	20%	6%	0.3%
10	71.7%	20%	8%	0.3%
11	80.7%	15%	4%	0.3%
12	78.7%	15%	6%	0.3%
13	75.7%	20%	4%	0.3%
14	73.7%	20%	6%	0.3%
15	71.7%	20%	8%	0.3%
1 HIMONT CA53A
2 EPOLENE E-43

TABLE 18B
	1	2	3	4	5
Flexural Modulus, MPa	578	725	736	686	741
Stress at Yield, MPa	19.1	23.3	24.1	22.6	24.4
Tensile Elongation, %	667	666	622	559	417
Tensile Strength, MPa	16.2	18.9	18.8	16.1	16.7
Young's Modulus, MPa	338	432	453	423	452
Notched Izod Impact, J/m	554	493	382	100	72.9
−30° C., J/m	55.0	49.4	43.3	44.3	34.0
Unnotched Izod Impact, J/m	839	1025	931	924	997
Falling Dart Impact
Max Load, J/m	1430	1624	1652	1556	1485
Total E, J	21.6	23.7	25.6	23.1	16.0
DSC
Tm, ° C.	156	156	158	153	164
Delta H, J/g	61.8	63.5	72.0	9.7	78.2
Tc, ° C.	98.9	103	104	102	109
Delta H, J/g	69.5	79.1	80.8	74.8	81.6
	6	7	8	9	10
Flexural Modulus, MPa	643	560
Stress at Yield, MPa	21.1	17.3
Tensile Elongation, %	296	53
Tensile Strength, MPa	15.3	13.2
Young's Modulus, MPa	390	364
Notched Izod Impact, J/m	154	363
−30° C., J/m	33.2	33.7
Unnotched Izod Impact, J/m	828	651
Falling Dart Impact
Max Load, J/m	1406	1064	1247	1043	905
Total E, J	19.1	11.4	15.9	11.0	9.59
DSC
Tm, ° C.	152		151	150	150
Delta H, J/g	61.6		62.4	63.7	63.3
Tc, ° C.	101		102	103	103
Delta H, J/g	73.7		73.3	73.2	72.8
	11	12	13	14	15
Flexural Modulus, MPa	586	572	579	596	648
Stress at Yield, MPa	18.2	17.4	18.5	18.8	19.8
Tensile Elongation, %	666	666	666	666	666
Tensile Strength, MPa	14.8	14.9	13.3	13.7	14.7
Young's Modulus, MPa	348	322	323	342	342
Hardness Shore D	57	56	57	57	56
Notched Izod Impact, J/m	563	574	116	184	565
−30° C., J/m	40.9	34.9	34.4	27.0	29.0
Unnotched Izod Impact, J/m	840	780	847	772	756
Falling Dart Impact
Max Load, J/m	1541	1523	1505	1557	1539
Total E, J	22.8	23.0	20.7	21.9	23.0

TABLE 18Ci
ADHESION TEST
% Adhesion	% Adhesion
SAM-	Test			SAM-
PLE	1	Test 2	Test 3	PLE	Test 1	Test 2	Test 3
PP	0	0		PP	0	2
1	0	2		1	0	0
2	19	32		2	0	1
3	5	1		3	1	5
4	49	23	36	4	0	0
5	61	57	59	5	0	0
6	80	99	90	6	65	52	58
7	100	78	89	7	26	5	16
8	77	62	70	8	43	30	36
9	91	90	90	9	90	98	94
10	93	98	96	10	82	91	6
				11	80	94	87

TABLE 18Cii
CROSS-HATCH ADHESION TEST
         S1
(SAMPLE) W/IPA
6        100%
7        100%
9        100%
10       96%
11       100%
14       100%

TABLE 18Ciii
CROSS-HATCH ADHESION TEST
	S1	S2
(SAMPLE)	W/O IPA	W/O IPA
11	97	100
12	0	4
13	82	88
14	95	98
15	7	9

EXAMPLE 19

TABLE 19A
			JEFFAMINE ®
Sample	TPO 1	MAL-PP 2	M-2070	Phenol
1	99.7%	—	—	0.3%
2	84.7%	15%	—	0.3%
3	79.7%	20%	—	0.3%
4	69.7%	30%	—	0.3%
5	80.7%	15%	4%	0.3%
6	78.7%	15%	6%	0.3%
7	75.7%	20%	4%	0.3%
8	73.7%	20%	6%	0.3%
9	71.7%	20%	8%	0.3%
10	65.7%	30%	4%	0.3%
11	63.7%	30%	6%	0.3%
12	61.7%	30%	8%	0.3%
13	80.7%	15%	4%	0.3%
14	78.7%	15%	6%	0.3%
15	75.7%	20%	4%	0.3%
16	73.7%	20%	6%	0.3%
17	71.7%	20%	8%	0.3%
18	65.7%	30%	4%	0.3%
19	63.7%	30%	6%	0.3%
20	61.7%	30%	8%	0.3%
1 HIMONT CA53A
2 EPOLENE E-43

TABLE 19B
	1	2	3	4	5
Flexural Modulus, MPa	1234	1314	1329	1379	1351
Stress at Yield, MPa	39.1	41.6	42.5	43.9	39.9
Tensile Elongation, %	186	59	18	10	159
Tensile Strength, MPa	25.3	25.9	26.4	26.5	25.1
Young's Modulus, MPa	694	732	789	809	715
Notched Izod Impact, J/m	69.3	47.0	43.3	25.2	57.2
−30° C., J/m	33.5	19.1	17.7	16.5	18.8
Unnotched Izod Impact, J/m	1413	1095	965	694	945
Falling Dart Impact
Max Load, J/m	2096	2148	1010	344	1137
Total E, J	30.9	29.8	4.69	1.46	5.70
DSC
Tm, ° C.	166	165		164	165
Delta H, J/g	86.6	85.8		95.2	94.2
Tc, ° C.	109	109		110	109
Delta H, J/g	106	105		104	99.3
	6	7	8	9	10	11
Flexural Modulus, MPa	1128	1253	1108	1017	1280	1186
Stress at Yield, MPa	31.6	37	28.4	23	35.4	31.4
Tensile Elongation, %	11	19	8.8	8.3	8.3	6.9
Tensile Strength, MPa	20.8	24.1	20	17.6	22.8	20.4
Young's Modulus, MPa	661	708	677	624	742	701
Notched Izod Impact, J/m	72.5	50.4	47.1	42.2	26.6	17.7
−30° C., J/m	15.2	11.7	10.2	9.5	7.5	6.6
Unnotched Izod Impact, J/m	262	475	178	172	241	191
Falling Dart Impact
Max Load, J/m	630	356	329	368	219	220
Total E, J	3.53	1.63	2.66	2.37	1.2	1.23
DSC
Tm, ° C.	165	165	166	164	164	164
Delta H, J/g	93.9	97.3	95.7	91.4	97.7	93.5
Tc, ° C.	109	109	110	109	110	108
Delta H, J/g	98	101	7.1	96	101	97.3

TABLE 19C
ADHESION TEST
	% Adhesion		% Adhesion
SAM-	Test			SAM-
PLE	1	Test 2	Test 3	PLE	Test 1	Test 2	Test 3
PP 1	0	0		PP	0	2
1	0	2		1	0	0
2	19	32		2	0	1
3	5	1		3	1	5
4	49	23	36	4	0	0
5	61	57			0	0
6	80	99	90	6	65	52	58
7	100	78	89	7	26	5	16
8	77	62	70	8	43	30	36
9	91	90	90	9	90	98	94
10	93	98	96	10	82	91	6
				11	80	94	87
1 Control

	TABLE 19C
	% Adhesion		% Adhesion
Sample	Test 1	Test 2	Sample	Test 1	Test 2
13	0%	0%	13	0%	0%
14	0%	0%	14	0%	6%
15	1%	0%	15	20%	1%
16	0%	11%	16	4%	36%
17	0%	0%	17	0%	3%
18	28%	17%	18	23%	26%
19	22%	13%	19	13%	11%
20	89%	62%	20	27%	21%

EXAMPLE 20

TABLE 20A
			JEFFAMINE ®	EP
Sample	PP 1	MAL-PP 2	M-2070	RUBBER 3	Phenol
1	74.7%	5%	—	20%
2	69.7%	10%	—	20%	0.3%
3	59.7%	15%	—	25%	0.3%
4	70.7%	5%	4%	20%	0.3%
5	68.7%	5%	6%	20%	0.3%
6	66.7%	5%	8%	20%	0.3%
7	65.7%	10%	4%	20%	0.3%
8	63.7%	10%	6%	20%	0.3%
9	61.7%	10%	8%	20%	0.3%
10	55.7%	15%	4%	25%	0.3%
11	53.7%	15%	6%	25%	0.3%
12	51.7%	15%	8%	25%	0.3%
1 AMOCO 1016
2 EPOLENE E-43
3 VISTALON

TABLE 20B
	1	2	3	4	5	6
Flexural Modulus, MPa	1342	1411	1333	1359	1070	1029
Stress at Yield, MPa	38.6	40.2	36.5	36.4	29.6	28.0
Tensile Elongation, %	168	140	173	451	125	106
Tensile Strength, MPa	25.2	25.4	22.7	22.5	19.1	18.1
Young's Modulus, MPa	731	750	699	671	575	552
Hardness, Shore D	66	69	64	67	63	61
Notched Izod Impact, J/m	108	59	107	338	361	444
−30° C., J/m	17.6	16.6	18.0	23.1	28.4	43.8
Unnotched Izod Impact, J/m	1106	1199	1311	1252	867	816
Falling Dart Impact
Maximum Load, J/m	2045	2035	1826	1879	1710	1495
−30° C., J/m	3417	3351	3122	2888	920	595
Total Energy, J	30.0	29.2	26.2	25.9	18.5	14.8
−30° C., J	41.9	34.6	39.4	22.2	30.5	2.19
	7	8	9	10	11	12
Flexural Modulus, MPa	1168	1064	1006	1078	968	915
Stress at Yield, MPa	31.6	28.3	26.4	28.8	26.4	24.0
Tensile Elongation, %	188	119	122	196	184	40
Tensile Strength, MPa	19.9	18.2	17.1	18.2	17.2	15.6
Young's Modulus, MPa	595	555	523	553	527	500
Hardness, Shore D	64	63	61	62	61	60
Notched Izod Impact, J/m	273	286	256	277	240	127
−30° C., J/m	19.2	18.4	24.0	25.0	26.4	13.8
Unnotched Izod Impact, J/m	874	785	729	904	860	782
Falling Dart Impact
Maximum Load, J/m	1858	1338	1024	1606	1317	1110
−30° C., J/m	2101	385	339	1021	500	561
Total Energy, J	22.8	13.5	9.2	18.9	13.5	9.9
−30° C., J	12.4	1.58	1.74	4.31	2.50	2.69

TABLE 20C
CROSS-HATCH ADHESION TEST
	S1	S2	S1	S2
SAMPLE	W/IPA	W/IPA	W/O IPA	W/O IPA
1	19%	20%	0%	2%
2	19%	44%	11%	13%
3	50%	89%	99%	100%
4	40%	59%	37%	52%
5	29%	55%	5%	33%
6	92%	100%	4%	39%
7	82%	89%	28%	32%
8	95%	100%	68%	100%
9	97%	78%	70%	75%
10	83%	100%	99%	100%
11	99%	100%	82%	96%
12	92%	100%	100%	100%

EXAMPLE 21

TABLE 21A
			JEFFAMINE ®
Sample	TPO 1	MAL-PP 2	M-2070	Phenol
1	100%	—	—	0.3%
2	90%	10%	—	0.3%
3	85%	15%	—	0.3%
4	80%	20%	—	—
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%	0.2%
9	75.8%	20%	4%	0.2%
10	73.8%	20%	6%	0.2%
11	80.8%	15%	4%	0.2%
12	78.8%	15%	6%	0.2%
13	75.8%	20%	4%	0.2%
14	73.8%	20%	6%	0.2%
1 DEXFLEX D161
2 EPOLENE E-43

TABLE 21B
	1	2	3	4	5
Flexural Modulus,	944	985	1050	1101	857
MPa
Stress at Yield, MPa	25.1	27.4	29.3	30.7	23.9
Tensile Elongation, %	506	186	116	78	466
Tensile Strength, MPa	17.8	18.7	19.5	20.1	16.8
Young's Modulus,	551	581	629	654	491
MPa
Hardness Shore D	63	65	67	68	63
Notched Izod Impact,	576	343	84	54	475
J/m
−30° C., J/m	35.9	31.5	25.1	16.9	33.6
Unnotched Izod	1027	965	1174	1066	944
Impact, J/m
Falling Dart Impact
Max Load, J/m	1669	1678	1703	1721	1509
−30° C., J/m	2980	3140	3094	2880	2397
Total E, J	24.1	22.8	22.7	21.8	21.9
−30° C., J	36.9	38.0	29.7	17.0	28.8
	6	7	8	9	10
Flexural Modulus,	748	832	745	788	804
MPa
Stress at Yield, MPa	20.8	23.0	20.4	22.6	22.4
Tensile Elongation, %	71	100	31	26	18
Tensile Strength, MPa	14.7	16.1	14.5	16.3	15.0
Young's Modulus,	445	486	451	492	460
MPa
Hardness Shore D	61	64	451	61	60
Notched Izod Impact,	331	252	60	74	56
J/m
−30° C., J/m	37.8	22.2	144	17.2	18.3
Unnotched Izod	736	737	22.7	419	310
Impact, J/m
Falling Dart Impact 422
Max Load, J/m	1340	1408	1047	1047	704
−30° C., J/m	550	422	356	411	339
Total E, J	15.1	15.7	9.0	7.4	5.1
−30° C., J	1.31	0.82	0.62	0.70	0.53
	11	12	13	14
Flexural Modulus, MPa	892	802	945	874
Stress at Yield, MPa	26.2	23.7	27.1	25.4
Tensile Elongation, %	221	511	187	370
Tensile Strength, MPa	18.1	16.8	18.3	17.4
Young's Modulus, MPa	525	467	539	495
Hardness Shore D	63	63	64	61
Notched Izod Impact, J/m	159	511	99	118
−30° C., J/m	26.6	25.9	20.6	18.7
Unnotched Izod Impact, J/m	1020	934	1174	913
Falling Dart Impact
Max Load, J/m	1610	1603	1591	1618
−30° C., J/m	2655	1541	1517	1259
Total E, J	22.4	23.6	19.1	19.5
−30° C., J	20.8	5.45	6.24	4.88

TABLE 21C
CROSS-HATCH ADHESION TEST
	S1	S2	S1	S2
(SAMPLE)	W/IPA	W/IPA	W/O IPA	W/O IPA
PP 1	0.00	0.00	0.00
1	3	18	78	27
2	63	63	94	48
3	79	59	62	100
4	0.00	14	87	83
5	100	100	100	100
6	100	100	100	100
7	100	100	99	100
8	100	100	97	100
9	100	100	100	100
10	100	100	100	100
11	67	67	94	88
12	62	62	10	22
13	100	100	100	100
14	100	100	100	100
1 Control.

EXAMPLE 22

TABLE 22A
			JEFFAMINE ®
Sample	TFO 1	MAL-PP 2	M-2070	Phenol
1	100%	—	—	—
2	90%	10%	—	—
3	85%	15%	—	—
4	80%	20%	—	—
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%	0.2%
9	75.8%	20%	4%	0.2%
10	73.8%	20%	6%	0.2%
11	80.8%	15%	4%	0.2%
12	78.8%	15%	6%	0.2%
13	75.8%	20%	4%	0.2%
14	73.8%	20%	6%	0.2%
1 STAMYLAN P
2 EPOLENE E-43

TABLE 22B
	1	2	3	4	5	6	7
Flexural Modulus,	1053	1123	1185	1259	1100	1025	1040
MPa
Stress at Yield, MPa	32.3	35.3	36.5	38.9	32.7	30.0	31.0
Tensile Elongation, %	453	173	141	36	168	30	22
Tensile Strength, MPa	21.2	22.7	23.1	23.7	21.5	19.9	20.3
Young's Modulus,	568	647	665	696	581	571	592
MPa
Notched Izod Impact	716	607	159	118	519	482	219
J/m
−30° C., J/m	77.4	43.5	34.7	23.5	37.0	47.8	33.5
Unnotched Izod	1075	1246	1078	1124	911	853	629
Impact, J/m
Falling Dart Impact
Max Load, J/m	1987	2002	2013	2052	1853	1614	1632
−30° C., J/m	3562	3721	2804	1154	1464	461	503
Total Energy, J	31.4	31.1	30.0	28.8	25.9	17.4	18.1
−30° C., J	45.2	42.7	17.2	3.6	5.3	0.9	1.0
	8	9	10	11	12	13	14
Flexural Modulus,	995	1062	999	1107	1083	1131	1076
MPa
Stress at Yield, MPa	26.9	30.8	28.4	33.9	32.2	34.0	32.5
Tensile Elongation, %	14	15	11	218	483	80	230
Tensile Strength, MPa	18.3	19.9	18.5	21.4	20.1	21.7	20.8
Young's Modulus,	542	582	560	587	517	619	582
MPa
Notched Izod Impact,	238	109	104	495	563	145	157
J/m
−30° C., J/m	34.6	24.2	22.7	27.1	39.8	28.5	26.8
Unnotched Izod	514	464	336	1029	1008	1004	863
Impact, J/m
Falling Dart Impact
Max Load, J/m	1301	1003	1021	2017	2002	941	1878
−30° C., J/m	460	455		3633	1244	1140	1193
Total Energy, J	11.0	8.3	6.3	30.2	29.5	7.9	26.4
−30° C., J	0.7	0.7		26.8	3.6	3.2	3.5

TABLE 22C
CROSS-HATCH ADHESION TEST
DISC SAMPLE	S1	S2	S1	S2
TAPE	3M 1	3M	NICHIBAN	NICHIBAN
SAMPLE	W/IPA	W/IPA	W/O IPA	W/O IPA
1	6%	0%	0%	3%
2	1%	0%	14%	1%
3	1%	0%	7%	2%
4	0%	6%	1%	15%
5	45%	80%	83%	32%
6	96%	98%	96%	100%
7	88%	96%	82%	92%
8	89%	78%	74%	96%
9	94%	87%	100%	98%
10	99%	100%	100%	100%
11	3%	47%	20%	27%
12	7%	1%	2%	3%
13	38%	79%	35%	78%
14	85%	65%	100%	97%
1 Scotch Brand 2040

TABLE 22C
CROSS-HATCH ADHESION TEST
DISC SAMPLE	S1	S2	S1	S2
SAMPLE	W/IPA	W/IPA	W/O IPA	W/O IPA
1	4%	1%	5%	0%
2	0%	0%	7%	0%
3	4%	0%	4%	10%
4	9%	1%	17%	1%
5	26%	79%	57%	46%
6	95%	90%	93%	92%
7	95%	89%	94%	89%
8	83%	84%	97%	97%
9	85%	94%	98%	96%
10	96%	88%	99%	97%
11	83%	58%	90%	71%
12	0%	5%	8%	20%
13	86%	95%	74%	92%
14	97%	86%	92%	98%
15 1	98%	98%	100%	100%
1 Reactive extrusion product of 73% STAMYLAN P, 20% EPOLENE E-43, 6% JEFFAMINE ® M-2070, and 0.2% Phenol.

EXAMPLE 23

TABLE 23A
			JEFFAMINE ®	EP
Sample	PP 1	MAL-PP 2	M-2070	RUBBER 3	Phenol
1	69.7%	—	—	30%	0.3%
2	59.7%	10%	—	30%	0.3%
3	56.7%	13%	—	30%	0.3%
4	52.2%	17.5%	—	30%	0.3%
5	57.7%	10%	2%	30%	0.3%
6	55.7%	10%	4%	30%	0.3%
7	53.7%	10%	6%	30%	0.3%
8	54.7%	13%	2%	30%	0.3%
9	52.7%	13%	4%	30%	0.3%
10	50.7%	13%	6%	30%	0.3%
11	50.2%	17.5%	2%	30%	0.3%
12	48.2%	17.5%	4%	30%	0.3%
13	46.2%	17.5%	6%	30%	0.3%
14	57.7%	10%	2%	30%	0.3%
15	55.7%	10%	4%	30%	0.3%
16	53.7%	10%	6%	30%	0.3%
17	54.7%	13%	2%	30%	0.3%
18	52.7%	13%	4%	30%	0.3%
19	50.7%	13%	6%	30%	0.3%
20	50.2%	17.5%	2%	30%	0.3%
21	48.2%	17.5%	4%	30%	0.3%
22	46.2%	17.5%	6%	30%	0.3%
1 AMOCO 1016
2 EPOLENE E-43
3 VISTALON 878

TABLE 23B
	1	2	3	4	5	6	7	8
Flexural	1064	1095	1166	1156	1062	843	741	959
Modulus, MPa
Stress at Yield,	28.5	29.7	32.5	31.3	27.4	22.8	20.1	25.7
MPa
Tensile	483	211	181	151	252	356	107	316
Elongation, %
Tensile	19.5	19.7	20.2	19.2	18.1	15.2	13.7	16.6
Strength, MPa
Young's	583	608	608	611	551	456	412	487
Modulus,
MPa
Hardness,	64	63	65	64	61	60	59	59
Shore D
Notched Izod	576	436	252	161	510	449	450	427
Impact, J/m
−30° C., J/m	58.4	28.0	22.2	26.0	33.0	54.3	54.9	31.4
Unnotched	979	957	976	867	955	847	815	819
Izod Impact,
J/m
Falling Dart
Impact
Max Load, J/m	1711	1760	1710	1607	1565	1431	1199	1514
−30° C., J/m	3096	3236	3245	3177	3014	1487	802	2962
Total Energy, J	25.5	29.2	22.5	20.6	27.3	18.1	14.2	20.0
−30° C., J	39.1	41.5	42.6	37.4	40.1	6.8	3.6	19.6
Ductile/5	5	5	5	5	5	5	5	5
−30° C./5	5	5	5	3	5	0	0	0
	9	10	11	12	13	14	15	16
Flexural	798	746	863	792	709	991	964	907
Modulus, MPa
Stress at Yield,	22.2	20.3	23.9	21.8	19.5	26.8	25.4	23.6
MPa
Tensile	157	65	252	94	33	498	494	656
Elongation, %
Tensile	15.0	13.7	16.3	14.9	13.6	18.1	17.3	17.5
Strength, MPa
Young's	437	387	476	436	408	503	479	437
Modulus, MPa
Hardness,	61	59	61	60	60	62	59	58
Shore D
Notched Izod	439	384	258	271	205	530	575	586
Impact, J/m
−30° C., J/m	40.9	31.0	25.5	28.6	29.8	49.8	33.9	56.1
Unnotched	818	679	712	778	665	1146	1108	1012
Izod Impact,
J/m
Falling Dart
Impact
Max Load, J/m	1370	1224	1452	1258	1027	1649	1631	1554
−30° C., J/m	1224	718	1229	580	487	3098	3096	3060
Total Energy, J	16.1	14.6	18.6	13.9	11.9	24.0	23.6	23.8
−30° C., J	5.0	3.4	5.8	2.6	3.4	40.0	40.1	39.8
Ductile/5	5	5	5	5	5	5	5	5
−30° C./5	0	0	0	0	0	5	5	5
	17	18	19	20	21	22
Flexural Modulus, MPa	986	946	921	964	922	889
Stress at Yield, MPa	27.2	25.0	23.5	26.4	24.8	23.0
Tensile Elongation, %	511	578	605	87	109	202
Tensile Strength, MPa	1.67	16.0	15.7	17.7	16.7	16.2
Young's Modulus, MPa	456	439	404	518	477	475
Hardness, Shore D	62	60	58	62	62	54
Notched Izod Impact, J/m	463	549	594	209	357	551
−30° C., J/m	27.7	30.9	34.1	19.9	30.2	24.7
Unnotched Izod Impact, J/m	996	922	804	899	1011	774
Falling Dart
Impact
Max Load, J/m	1541	1602	1534	1484	1429	1418
−30° C., J/m	3199	3171	3131	2932	3215	3225
Total Energy, J	20.9	22.8	22.2	18.2	18.4	20.6
−30° C., J	41.6	41.9	41.4	24.4	40.6	41.8
Ductile/5	5	5	5	5	5	5
−30° C./5	5	5	5	1	5	5

TABLE 23C
CROSS-HATCH ADHESION TEST
	S1	S2	S1	S2
(SAMPLE)	W/IPA	W/IPA	W/O IPA	W/O IPA
PP 1	0%		0%
1	94%	72%	35%	1%
2	74%	57%	73%	45%
3	10%	25%	26%	36%
4	80%	62%	16%	24%
5	94%	97%	54%	94%
6	99%	100%	94%	97%
7	100%	100%	100%	100%
8	100%	100%	100%	100%
9	100%	100%	100%	100%
10	100%	100%	100%	100%
11	100%	100%	97%	100%
12	100%	100%	100%	100%
13	97%	95%	98%	100%
14	94%	100%	69%	79%
15	65%	59%	0%	0%
16	39%	52%	0%	0%
17	100%	100%	67%	71%
18	85%	88%	8%	2%
19	75%	43%	20%	3%
20	100%	100%	99%	100%
21	100%	100%	93%	100%
22	83%	78%	2%	2%
1 Control

EXAMPLE 24

	TABLE 24A
				JEFFAMINE ®
	Sample	TPO 1	MAL-PP 2	M-2070	Phenol
	1	100%	—	—	—
	2	90%	10%	—	—
	3	85%	15%	—	—
	4	80%	20%	—	—
	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%	0.2%
	9	75.8%	20%	4%	0.2%
	10	73.8%	20%	6%	0.2%
	11	80.8%	15%	4%	0.2%
	12	78.8%	15%	6%	0.2%
	13	75.8%	20%	4%	0.2%
	14	73.8%	20%	6%	0.2%
	1 KELTAN TP 0552-2
	2 2EPOLENE E-43

TABLE 24B
	1	2	3	4	5	6	7
Flexural Modulus,	915	971	1034	1076	799	724	780
MPa
Stress at Yield, MPa	23.1	25.5	27.6	28.4	21.5	18.4	21.1
Tensile Elongation, %	529	61	36	16	38	20	17
Tensile Strength, MPa	15.6	16.1	16.6	17.0	14.8	13.4	14.8
Young's Modulus,	504	534	570	588	459	432	461
MPa
Hardness, Shore D	61	61	63	64	58	56	58
Notched Izod Impact,	669	551	160	111	486	402	413
J/m
−30° C., J/m	700	101	71.3	56.7	96.4	75.6	70.6
Unnotched Izod	944	877	942	937	810	706	805
Impact, J/m
Falling Dart Impact
Max Load, J/m	1695	1732	1399	1747	1522	1178	1453
−30° C., J/m	2912	3013	3110	2932	1389	529	839
Total Energy, J	27.8	26.9	21.0	22.2	19.0	14.4	17.8
−30° C., J	40.5	40.6	29.9	18.6	5.4	4.2	4.3
Ductile/5	5	5	5	5	5	5	5
−30° C./5	5	5	1	0	0	0	0
	8	9	10	11	12	13	14
Flexural Modulus,	718	812	760	863	798	871	845
MPa
Stress at Yield, MPa	19.0	21.7	19.9	22.8	21.6	23.4	22.9
Tensile Elongation, %	12	11	11	82	478	65	92
Tensile Strength,	13.7	15.0	13.9	15.7	15.6	16.3	16.1
MPa
Young's Modulus,	441	487	462	473	463	486	478
MPa
Hardness, Shore D	56	59	58	62	59	61	61
Notched Izod Impact,	438	128	200	519	620	147	166
J/m
−30° C., J/m	42.3	38.4	29.1	61.7	44.1	50.8	37.7
Unnotched Izod	570	574	374	850	855	905	828
Impact, J/m
Falling Dart Impact
Max Load, J/m	1155	1284	924	1544	1579	1516	1544
−30° C., J/m	454	545	487	2989	2300	2287	1526
Total Energy, J	13.2	10.7	6.7	19.9	24.4	16.3	21.1
−30° C., J	3.4	2.9	3.6	22.3	12.0	10.8	10.4
Ductile/5	5	0	0	5	5	0	5
−30° C./5	0	0	0	0	0	0	0

TABLE 24C
CROSS-HATCH ADHESION TEST
	S1	S2	S1	S2
(SAMPLE)	W/IPA	W/IPA	W/O IPA	W/O IPA
PP 1	0%		0%
1	96%	88%	86%	90%
2	72%	75%	53%	24%
3	69%	41%	43%	10%
4	41%	15%	40%	3%
5	100%	100%	100%	100%
6	100%	100%	100%	100%
7	100%	100%	100%	100%
8	100%	100%	100%	100%
9	100%	100%	100%	100%
10	100%	100%	99%	100%
11	100%	100%	100%	100%
12	98%	100%	78%	3%
13	100%	88%	100%	100%
14	100%	100%	100%	100%
15 2	100%	100%
1 Control
2 Reactive extrusion product of 73% STAMYLAN P, 20% EPOLENE E-43, 6% JEFFAMINE ® M-2070, and 0.2% Phenol.

EXAMPLE 25

TABLE 25A
Sample	PP 1	MAL-PP 2	AMINE 3	EP RUBBER 4	Phenol
1	74.7%	5%	—	20%	0.3%
2	69.7%	10%	—	20%	0.3%
3	59.7%	15%	—	25%	0.3%
4	70.7%	5%	4%	20%	0.3%
5	68.7%	5%	6%	20%	0.3%
6	66.7%	5%	8%	20%	0.3%
7	65.7%	10%	4%	20%	0.3%
8	63.7%	10%	6%	20%	0.3%
9	61.7%	10%	8%	20%	0.3%
10	55.7%	15%	4%	25%	0.3%
11	53.7%	15%	6%	25%	0.3%
12	51.7%	15%	8%	25%	0.3%
1 AMOCO 1016
2 EPOLENE E-43
3 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
4 VISTALON 878

	TABLE 25B
	1	2	3	4	5	6	7	8	9	10	11	12
Flexural Modulus, MPa	1233	1218	1134	1197	1098	994	1161	1029	970	976	922	910
Stress at Yield, MPa	35.1	35.2	31.7	33.0	30.9	28.6	32.1	29.2	28.5	26.8	25.6	25.3
Tensile Elongation, %	189	182	148	159	262	116	374	240	118	376	474	185
Tensile Stength, MPa	23.7	23.6	21.3	22.0	20.3	18.4	20.5	18.9	18.3	17.7	16.0	17.0
Young's Modulus, MPa	642	648	612	618	580	527	570	552	521	505	469	486
Hardness, Shore D	64	65	63	65	63	62	64	61	60	61	60	60
Notched Izod Impact, J/m	128	82	100	282	451	470	366	383	315	391	425	341
−30° C., J/m	15.2	16.2	17.2	16.0	15.6	23.1	17.9	16.8	19.2	20.2	19.8	17.6
Unnotched Izod Impact, J/m	1056	1237	1144	1091	969	981	893	781	854	857	799	827
Falling Dart Impact
Max Load, J/m	1915	1848	1728	1788	1753	1408	1787	1449	1046	1546	1252	995
−30° C., J/m	3480	3496	3325	2495	2191	479	3079	588	542	1668	676	492
Total Energy, J	27.0	25.2	22.2	22.9	22.5	14.2	23.5	14.8	10.2	18.4	13.2	10.0
−30° C., J	43.5	40.0	42.2	20.4	9.6	2.0	20.8	2.6	2.6	7.0	2.6	2.2
Ductile/5	5	5	5	5	5	5	5	5	5	5	5	5
−30° C./5	5	4	5	2	0	0	0	0	0	0	0	0

TABLE 25C
CROSS-HATCH ADHESION TEST
DISC
SAMPLE	S1		S2	S1	S2
TAPE	3M 1		3M	NICHIBAN	NICHIBAN
SAMPLE	W/O IPA		W/O IPA	W/O IPA	W/O IPA
PP 2	0%			1%
1	8%	4%	1%	12%	49%
2	1%	2%	4%	39%	43%
3	87%	90%	91%	97%	100%
4	49%	53%	57%	87%	95%
5	98%	98%	97%	100%	100%
6	99%	100%	100%	100%	100%
7	100%	100%	99%	100%	100%
8	98%	99%	100%	100%	100%
9	100%	100%	100%	100%	100%
10	100%		100%	100%	100%
11	100%		100%	100%	100%
12	100%		100%	100%	100%
1 Scotch Brand 2040
2 Control

EXAMPLE 26

	TABLE 26A
				JEFFAMINE ®
	Sample	TPO 1	MAL-PP 2	M-2070	Phenol
	1	100%	—	—	—
	2	90%	10%	—	—
	3	85%	15%	—	—
	4	80%	20%	—	—
	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%	0.2%
	9	75.8%	20%	4%	0.2%
	10	73.8%	20%	6%	0.2%
	11	80.8%	15%	4%	0.2%
	12	78.8%	15%	6%	0.2%
	13	75.8%	20%	4%	0.2%
	14	73.8%	20%	6%	0.2%
	1 KELTAN TP 2632
	2 EPOLENE E-43

TABLE 26B
	1	2	3	4	5	6	7
Flexural Modulus,	1648	1838	1863	1895	1537	1314	1415
MPa
Stress at Yield, MPa	26.9	32.7	33.9	34.2	27.5	23.8	25.7
Tensile Elongation, %	93	6	4	2	9	9	6
Tensile Strength, MPa	15.9	18.7	19.0	18.9	17.0	15.4	15.9
Young's Modulus,	876	1007	1065	1080	881	779	802
MPa
Hardness, Shore D	63	64	64	64	62	57	60
Notched Izod Impact,	518	56	98	23	126	204	63
J/m
−30° C., J/m	146	36	24	14	27	32	19
Unnotched Izod	1147	923	691	327	920	508	417
Impact, J/m
Falling Dart Impact
Max Load, J/m	1496	1644	1628	1222	1408	1044	916
−30° C., J/m	2499	2662	2371	799	1040	597	566
Total Energy, J	22.0	21.1	20.1	9.72	16.7	10.1	8.45
−30° C., J	34.7	21.6	13.1	5.14	3.61	3.15	2.96
Ductile/5	5	5	5	0	3	5	0
−30° C./5	5	0	0	0	0	0	0
	8	9	10	11	12	13	14
Flexural Modulus,	1285	1439	1261	1356	1173	1479	1323
MPa
Stress at Yield, MPa	22.8	25.8	22.6	27.6	26.1	28.7	27.0
Tensile Elongation, %	6	4	5	8	10	4	6
Tensile Strength, MPa	15.0	16.4	14.9	17.7	17.4	17.4	17.0
Young's Modulus,	767	887	777	738	663	862	743
MPa
Hardness, Shore D	59	60	60	62	60	61	59
Notched Izod Impact,	58	27	31	55	92	32	40
J/m
−30° C., J/m	16	13	12	22	22	15	18
Unnotched Izod	313	334	222	691	812	632	771
Impact, J/m
Falling Dart Impact
Max Load, J/m	719	492	334	1548	1555	929	1207
−30° C., J/m	518	487	472	1923	1161	616	812
Total Energy, J	5.92	4.02	2.71	18.9	19.0	7.08	10.8
−30° C., J	3.07	2.63	2.82	7.76	5.34	3.85	4.02
Ductile/5	0	0	0	4	5	0	0
−30° C./5	0	0	0	0	0	0	0

TABLE 26C
CROSS-HATCH ADHESION TEST
DISC SAMPLE	S1	S2	S1	S2
TAPE	3M 1	3M	NICHIBAN	NICHIBAN
SAMPLE	W/IPA	W/IPA	W/O IPA	W/O IPA
PP 2	0%		0%
1	77%	84%	65%	92%
2	32%	0%	22%	5%
3	1%	4%	8%	8%
4	0%	0%	7%	13%
5	100%	100%	99%	96%
6	100%	100%	100%	100%
7	100%	100%	95%	82%
8	100%	100%	88%	100%
9	99%	98%	100%	100%
10	100%	100%	100%	100%
11	100%	96%	100%	93%
12	74%	19%	57%	77%
13	83%	62%	100%	64%
14	91%	84%	91%	93%
1 Scotch Brand 2040
2 Control

EXAMPLE 27

TABLE 27A
Sample	TPO 1	MAL-PP 2	AMINE 3	Phenol	PP 4
1	99.7%	—	—	0.3%
2	84.7%	—	—	0.3%	15%
3	79.7%	—	—	0.3%	20%
4	89.7%	10%	—	0.3%
5	84.7%	15%	—	0.3%
6	79.7%	20%	—	0.3%
7	85.7%	10%	4%	0.3%
8	83.7%	10%	6%	0.3%
9	80.7%	15%	4%	0.3%
10	78.7%	15%	6%	0.3%
11	75.7%	20%	4%	0.3%
12	73.7%	20%	6%	0.3%
13	71.7%	20%	8%	0.3%
1 HIMONT CA53A
2 EPOLENE E-43
3 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, and which is referred to as “XTJ-418” within Huntsman Corporation.
4 AMOCO 1016

TABLE 27B
	1	2	3	4	5	6	7
Flexural Modulus,	510	646	705	588	664	734	546
MPa
Stress at Yield, MPa	15.8	19.8	21.4	18.7	20.6	22.7	17.2
Tensile Elongation, %	666	666	666	666	666	484	531
Tensile Strength, MPa	14.6	17.0	18.1	14.6	14.6	15.5	12.3
Young's Modulus,	284	368	394	340	375	414	310
MPa
Hardness, Shore D	58	60	60	59	61	62	57
Notched Izod Impact,	589	582	597	529	398	94	499
J/m
−30° C., J/m	65	47	38	38	37	37	40
Unnotched Izod	722	867	841	727	882	958	704
Impact, J/m
Falling Dart Impact
Max Load, J/m	1428	1589	1632	1486	1513	1529	1334
−30° C., J/m	3007	3335	3506	3290	3278	2610	889
Total Energy, J	20.6	22.6	23.4	20.9	20.6	21.1	16.0
−30° C., J	39.4	39.3	44.6	43.0	38.5	18.0	3.7
Ductile/5	5	5	5	5	5	5	5
−30° C./5	5	4	5	5	4	0	0
	8	9	10	11	12	13
Flexural Modulus, MPa	502	529	618	603	591	653
Stress at Yield, MPa	16.4	16.9	18.6	18.8	18.5	19.6
Tensile Elongation, %	208	245	170	138	37	43
Tensile Strength, MPa	11.7	12.2	13.0	13.5	13.5	13.8
Young's Modulus, MPa	299	309	355	348	354	381
Hardness, Shore D	52	58	57	52	57	59
Notched Izod Impact, J/m	443	437	445	310	162	90
−30° C., J/m	46	35	36	28	25	22
Unnotched Izod Impact, J/m	601	642	834	871	732	789
Falling Dart Impact
Max Load, J/m	1180	1255	1207	1263	1205	908
−30° C., J/m	760	2344	1505	1018	911	688
Total Energy, J	12.9	14.1	14.2	14.4	13.2	7.0
−30° C., J	3.2	12	6.3	3.3	3.1	3.1
Ductile/5	5	5	5	5	5	0
−30° C./5	0	0	0	0	0	0

TABLE 27C
CROSS-HATCH ADHESION TEST
DISC SAMPLE	S1	S2	S1	S2
TAPE	3M 1	3M	NICHIBAN	NICHIBAN
SAMPLE	W/O IPA	W/O IPA	W/O IPA	W/O IPA
PP 2	5%		2%
1	29%	67%	74%	92%
2	66%	76%	81%	84%
3	61%	73%	78%	61%
4	100%	98%	100%	98%
5	96%	100%	100%	99%
6	85%	94%	91%	96%
7	100%	100%	100%	100%
8	100%	100%	100%	100%
9	100%	100%	100%	100%
10	100%	100%	100%	100%
11	100%	100%	100%	100%
12	100%	100%	100%	100%
13	100%	100%	100%	100%
1 Scotch Brand 2040
2 Control

Examples 18-27 demonstrate that TPO modified with the reaction product of maleated PP and polyether amines of this invention provides a composition that is directly paintable. This paintability is surprising and unexpected in that the TPO's used to make automotive body parts, such as bumper fascias, are not directly readily paintable to a commercially acceptable level. Heretofore, in order to render automotive TPO based molded body parts paintable, the parts were treated with an adhesion promoter comprised of low molecular weight chlorinated polyethylene and a solvent, which results in a toxic waste stream that must be properly disposed of, and which adds to the cost of the parts. Alternatively, the parts could be heat treated using plasma irradiation, or otherwise partially burning the surface of the parts. This procedure is also expensive and may be, moreover, prone to variability in result owing to batch to batch variances from procedure and errors by the operator.

Compositions prepared in accordance with the practice of the present invention generally may be directly painted, with or without a primer, such that the paint adhesion is greater than about 75 percent based on the testing procedure described above for Examples 18-27, preferably greater than about 85 percent, more preferably greater than about 90 percent, and most preferably greater than about 95 percent.

Compositions prepared in accordance with the present invention may be used to prepare molded articles of manufacture using conventional, well known, molding techniques under standard conditions. For instance, standard injection molding techniques can be employed. Certain compositions (blends) of the present invention have surprisingly been found to have improved flowability characteristics during injection molding of TPO-based compositions such that less pressure may be used when injecting the melted compositions into a mold, as compared to compositions in which polyetheramine is absent. The desired shape of the molded article may vary depending on end use of the article. For instance, rubber containing compositions of the present invention may be injection molded to manufacture automotive body parts such as bumper fascias.

EXAMPLE 28

A polyol was prepared by ethoxylation of methanol (ethylene oxide/methanol mole ratio of about 43:1), followed by propoxylation with approximately three moles of propylene oxide to yield a polyol that analyzed as 0.474 meq/g total acetylatables (2110 g/equivalent). To a tubular reactor containing 594 g of an amination catalyst, there was simultaneously fed 1.0 lb/hr of the polyol, 1.25 lb/hr of ammonia, 42 lb/hr (STP) hydrogen. The reactor was maintained at 208° C. and 2000 psig. The effluent was collected and stripped of ammonia, water and light materials and analyzed as follows: 0.473 meq/g total acetylatables, 0.454 meq/g total amine, and 0.450 meq/g primary amine. The polyether monoamine so formed contained about 43 ethylene oxide units and had an equivalent weight of about 2110. This polyether monoamine is referred to herein as “XTJ-418.”

EXAMPLE 29

Blends containing the polyether monoamine of Example 28 were prepared having the components and properties as denoted in Tables 29A and 29B. In Table 29A, compositions containing polypropylene, maleated PP (HIMONT CA53A) and amines were employed. In Table 29B, TPO-based compositions are used. In the Tables 29A-29B, the JEFFAMINE M-2070 designates a polyether monoamine containing 10 propylene oxide units and 32 ethylene oxide units. The data points for JEFFAMINE M-2070 are intended to be for comparative purposes, as contrasted with the data for XTJ-418.

TABLE 29A
PP-BASED COMPOSITIONS
Maleated-PP (%)	20	20	20	20	20	20	30	30	30	30	30
XTJ-418 (%)	4		6		8		4		6		8
JEFFAMINE		4		6		8		4		6
M-2070 (%)
Paint Adhesion (%)	14	42	56	53	80	40	65	50	52	43	92

TABLE 29B
TPO-BASED COMPOSITIONS
Maleated-PP (%)	10	10	15	15	15	20	20	20	20	20	20	20
XTJ-418 (%)	4	6	4		6		4		6		8
JEFFAMINE M-2070				4		6		4		6		8
(%)
Paint Adhesion (%)	100	100	100	90	100	89	100	70	100	90	100	96

Example 29 demonstrates the superior paint adhesion achieved using the polyether monoamine of Example 28. It should be appreciated that XTJ-418 results in adhesion of up to 80% in Table 29A, whereas the adhesion for JEFFAMINE M-2070 did not produce adhesion above 53%. Furthermore, it should be appreciated that in the automotive industry, adhesion of less than 100% is considered unacceptable for commercial purposes.

GLOSSARY

JEFFAMINE M-1000

JEFFAMINE M-2070 and JEFFAMINE M-2005

where R═H or CH 3 , m is from about 3 to 32, and n is from about 10 to 32.

JEFFAMINE D-2000, JEFFAMINE D-4000 and JEFFAMINE D-400

where x is about 33 for D-2000, x is about 68 for D-4000 and x is about 5.6 for D-400.

JEFFAMINE ED-600. JEFFAMINE ED-900. JEFFAMINE ED-2001. JEFFAMINE ED-4000, and JEFFAMINE ED-6000

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-20-1, 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 JEFFAMINE T-5000

where x+y+z=50 for T-3000 and x+y+z=83 for T-5000.

JEFFAMINE ET-3000

where x+y+z=57 and a+b+c=4.

Claims

1. A polyether monoamine which contains from about 36 to about 44 ethylene oxide units and from about 1 to about 6 propylene oxide units.

2. The polyether monoamine of claim 1 wherein the polyether monoamine has a molecular weight of about 2000 to about 2200.

3. The polyether monoamine of claim 1 wherein the polyether monoamine contains about 40 to about 43 ethylene oxide units and from about 2.4 to about 3 propylene oxide units.

4. The polyether monoamine of claim 1, wherein the polyether monoamine is of the formula: wherein m is about 36 to about 44, and wherein n is about 1 to about 6.

5. The polyether monoamine of claim 4, wherein m is about 40 to about 43 and n is from about 2.4 to about 6.

6. The polyether monoamine of claim 4, having a molecular weight of about 2000 to about 2200.

7. The polyether monoamine of claim 5, having a molecular weight of about 2000 to about 2200.