CA2228684C - Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers - Google Patents
Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Abstract
Directly paintable polymer compositions contain (1) a thermoplastic olefin, (2) a malefic anhydride-grafted propylene homopolymer or random copolymer, (3) a malefic anhydride-grafted olefin polymer material, (4) a functionalized polymer that reacts with the malefic anhydride groups of the grafted polymers, and, optionally, (5) a malefic anhydride-grafted ethylene polymer. The amount of (2) + (3) or (2) + (3) + (5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin.
Description
Case 14001 This invention relates to thermoplastic olefin compositions containing malefic anhydride-modified polymers and functionalized polymeric additives.
Thermoplastic olefins (TPOs) are uncrosslinked blends of olefin polymers and polyolefin elastomers. They can be made by physically blending in an internal mixer, or S by polymerizing in a reactor. These materials are not paintable or coatable, because the paints or coatings consist of polar materials like urethanes, acrylics, epoxies, or melamines that have very poor adhesion to nonpolar materials like polyolefins.
Typically an adhesion promoter is used as the tie layer between the TPO
substrate and the paint coating. This extra step adds to the cost of the product, and the coating is not very durable.
European Patent Application 662,496 discloses a paintable or printable polymer composition consisting of a polyolefin or polyolefin/rubber blend and 0.1 to 10% by weight of at least one polymeric additive that is the reaction product of (a) a polyolefin or polyester modified by an unsaturated acid, ester or anhydride, and (b) an amine-, hydroxy-, or alkoxy-terminated polyoxyethylene, polyoxypropylene, or a copolymer of the two, e.g., the reaction product of a malefic anhydride-modified polypropylene wax and a methoxy-capped polyethylene oxide) glycol.
European Patent Application 634;424 discloses a blend of polypropylene with the reaction product of maleated polypropylene and a polyether amine. The blend displays improved paintability, improved impact resistance, and excellent mold flowability compared to blends of polypropylene and the reaction product of polypropylene and maleated polypropylene. However, the compositions disclosed in EP 662,496 and EP
634,424 are both lacking in durability.
The composition of this invention comprises, by weight:
(1) 100 parts of a thermoplastic olefin comprising:
(a) about 10% to about 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4_g a-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60% of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing about 1% to about 10% of a dime, which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20% of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92% ethylene; and (d) about 5% to about 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 min;
Thermoplastic olefins (TPOs) are uncrosslinked blends of olefin polymers and polyolefin elastomers. They can be made by physically blending in an internal mixer, or S by polymerizing in a reactor. These materials are not paintable or coatable, because the paints or coatings consist of polar materials like urethanes, acrylics, epoxies, or melamines that have very poor adhesion to nonpolar materials like polyolefins.
Typically an adhesion promoter is used as the tie layer between the TPO
substrate and the paint coating. This extra step adds to the cost of the product, and the coating is not very durable.
European Patent Application 662,496 discloses a paintable or printable polymer composition consisting of a polyolefin or polyolefin/rubber blend and 0.1 to 10% by weight of at least one polymeric additive that is the reaction product of (a) a polyolefin or polyester modified by an unsaturated acid, ester or anhydride, and (b) an amine-, hydroxy-, or alkoxy-terminated polyoxyethylene, polyoxypropylene, or a copolymer of the two, e.g., the reaction product of a malefic anhydride-modified polypropylene wax and a methoxy-capped polyethylene oxide) glycol.
European Patent Application 634;424 discloses a blend of polypropylene with the reaction product of maleated polypropylene and a polyether amine. The blend displays improved paintability, improved impact resistance, and excellent mold flowability compared to blends of polypropylene and the reaction product of polypropylene and maleated polypropylene. However, the compositions disclosed in EP 662,496 and EP
634,424 are both lacking in durability.
The composition of this invention comprises, by weight:
(1) 100 parts of a thermoplastic olefin comprising:
(a) about 10% to about 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4_g a-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60% of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing about 1% to about 10% of a dime, which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20% of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92% ethylene; and (d) about 5% to about 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 min;
(2) about 8 parts to about 14 parts of a malefic anhydride-modified propylene homopolymer or ethylene/propylene random copolymer having a malefic anhydride content of about 2% to about 5% and a molecular weight M~ of about 2500 to about 25,000, per hundred parts of the thermoplastic olefin;
(3) about 5 parts to about 14 parts per hundred parts of the thermoplastic olefin of a malefic anhydride-grafted olefin polymer material having a malefic anhydride content of at least 0.3% but less than 3%, selected from the group consisting of:
(a) a malefic anhydride-grafted polyolefin rubber comprising an ethylene-propylene or ethylene-butene copolymer rubber, optionally containing about 0.5% to about 10% of a dime, which contains about 30% to about 70% ethylene, 2md (b) a malefic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of (i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CHZ=CHR a-olefin, where R is a CZ_g straight or branched alkyl group, and (c) propylene and an a-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an a-olefin as defined above in (i)(b), containing about 1% to about 10% of the a-olefin and over 50% up to 98% of both ethylene and the a-olefin; and (c) ethylene and an a-olefin as defined in (i)(b), containing over 50% up to 98% of the a-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40%
_~.~ ~..- ..-.-.__., ___ _ . ~__-. _,-~..°' -~ °.' ~""" . .._ , :~~.~..~:.~,~.rr-,p:".,.N..~~ ,__ v :-w~.~Lw_~.: :: _ _ .. _ . _ . . . . .. ..
_ ethylene; (b) ethylene, propylene, and an a.-olefin as defined in (i)(b), wherein the a-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and oc-olefin present is from 20% to less than 45%; and (c) ethylene and an a-olefin as defined in (i)(b), containing from 20% to less than 45% of the a-olefin, and optionally containing about 0.5% to about 10% of a dime, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or C4_g a-olefin or combination thereof in fractions (ii) + (iii) is less than 50%;
(a) a malefic anhydride-grafted polyolefin rubber comprising an ethylene-propylene or ethylene-butene copolymer rubber, optionally containing about 0.5% to about 10% of a dime, which contains about 30% to about 70% ethylene, 2md (b) a malefic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of (i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CHZ=CHR a-olefin, where R is a CZ_g straight or branched alkyl group, and (c) propylene and an a-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an a-olefin as defined above in (i)(b), containing about 1% to about 10% of the a-olefin and over 50% up to 98% of both ethylene and the a-olefin; and (c) ethylene and an a-olefin as defined in (i)(b), containing over 50% up to 98% of the a-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40%
_~.~ ~..- ..-.-.__., ___ _ . ~__-. _,-~..°' -~ °.' ~""" . .._ , :~~.~..~:.~,~.rr-,p:".,.N..~~ ,__ v :-w~.~Lw_~.: :: _ _ .. _ . _ . . . . .. ..
_ ethylene; (b) ethylene, propylene, and an a.-olefin as defined in (i)(b), wherein the a-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and oc-olefin present is from 20% to less than 45%; and (c) ethylene and an a-olefin as defined in (i)(b), containing from 20% to less than 45% of the a-olefin, and optionally containing about 0.5% to about 10% of a dime, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or C4_g a-olefin or combination thereof in fractions (ii) + (iii) is less than 50%;
(4) a fiznctionalized polymer that reacts with the anhydride groups of (2), (3), and, 1 S if present, (5), selected from the group consisting of (a) about 2.7 to about 6 parts of an amine-terminated polyalkylene glycol per hundred parts of the thermoplastic olefin;
(b) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and (c) about 2 to about 6 parts of a mixture of (a) + (b) per hundred parts of the thermoplastic olefin, wherein the ratio of (a) to (b) is about 0.1 to about 0.9; and, optionally, (5) about 4 parts to about 15 parts per hundred parts of the thermoplastic olefin of a malefic anhydride-grafted ethylene polymer having a malefic anhydride content of about 2% to about 13% and a molecular weight Mn of about 500 to about 3000, CA 02228684 1998-02-04~
wherein (2) + (3), or (2) + (3) + (5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin, and when the malefic anhydride-grafted polyethylene is present, (3) + (5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
Injection molded parts such as automobile bumpers made from this composition are directly paintable with polar paints or coatings without the need for a layer of adhesion promoter between the thermoplastic olefin surface and the paint.
Component (1) of the composition of this invention is a thermoplastic olefin comprising, by weight, (a) about 10% to about 60%, preferably about 20% to about 50%, of a propylene homopolymer having an isotactic index greater than 90, preferably between 95 and 98, or a crystalline propylene copolymer with ethylene and/or a C4_g oc-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60%, preferably about 30% to about SO%, of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing about 1% to about 10% of a diene, which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20%, preferably about 7% to about 1 S%, of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92%
ethylene; and (d) about 5% to about 20%, preferably about 7% to about 15%, of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 min, preferably about 15 to about SO g/10 min. Ethylene homopolymer is preferred. However, copolymers containing 8% or less ofan a-olefn comonomer can also be used.
The thermoplastic olefin is typically prepared by sequential polymerization in at least three stages. Fraction (a) can be made in the first reactor, fractions (b) and (c~ in the second reactor, and fraction (d) in the third. reactor. Alternatively, fraction (d) can be made in the second reactor and fractions (b) and ,(c) in the third reactor.
The polymerization conditions and the polymerization catalyst are described in more detail in U.S. Patent 5,302,454. Alternative7.y, the four fractions can be prepared separately and then blended together.
Sequential ZO polymerization is preferred.
The Ca.s a-olefins useful in the preparation of the thermoplastic olefin include, for example, butene-1; pentene-1; hexene-I; 4-methylpentene-1, and octene-1.
The diene, when present, is typically a butadiene; I,4-hexadiene; I,5-hexadiene, or ethylidenenorbornene.
The thermoplastic olefn is present in an amount of 100 parts by weight.
Component (2) is a malefic anhydride=grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of about 0.5%
to about 4%, preferably about l% to about 3%. Propylene homopolymer is preferred.
The polymer has a malefic anhydride content of about 2% to about 5%, preferably about 20 3% to about 4%, and preferably has a molecular weight M" of about 2500 to about 25,000, most preferably about 3000 to about 10,000. Component (2) is present in an amount of about 8 to about 14 parts, preferably about 10 to about 12 parts, per hundred parts of the thermoplastic olefin.
Component (3) is a malefic anhydride-grafted olefin polymer material selected from the group consisting of (a) a malefic anhydride-grafted poiyolefin rubber comprising an ethylenelpropylene or ethylene<butene copolymer rubber, optionally containing about 0.5 % to b CA 02228684Y 1998-02-04 .._,. ..... ...._,....
about 10% of a dime, preferably about 2% to about 6%, which contains about 30% to about 70%; preferably about 40% to about 60%, ethylene, and (b~ a malefic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of (i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CHZ=CHR a-olefin, where R is a C2.8 straight or branched alkyl group, and (c) propylene and an a-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an a-olefin as defined above in (i)(b), containing about 1% to about 10% ofthe a-olefin and over 50% up to 98% of both ethylene and the a-olefin; and (c) ethylene and an a-olefin as defined in (i)(b), containing over 50% up to 98% of the a-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene; (b) ethylene, propylene, and an a-olefin as defined in (i)(b), wherein the a-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and a-olefin present is from 20% to less than 45%; and (c) CA 02.2286.84. ,1.998-02-p4~" ...... __ __. .__.___ ethylene and an oc-olefin as defined in (i)(b), containing from 20% to less than 45% of the a-olefin, and optionally containing about 0.5% to about 10% of a dime, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or Ca-a a-olefin or combination thereof in fractions (ii) + (iii) is less than 50%.
Fraction (i) is preferably present in an amount of about 10% to about 40%, most preferably about 20% to about 35%. When (i) is a propylene homopolymer, the isotactic index is preferably about 85 to about 98. When (i) is a copolymer, the amount of propylene in the copolymer is preferably about 90% to about 99%.
Fraction (ii) is preferably present in an amount of about 7% to about 15%.
Typically the crystallinity is about 20% to about 60% by DSC. Generally, the ethylene or oc-olefin content or the combination of ethylene and the oc-olefin when both are used is over 55% up to 98%, preferably about 80% to about 95%.
Fraction (iii) is preferably present in an amount of about SO% to about 70%.
The ethylene or the a-olefin content or ethylene and the a-olefin content of component (iii) is preferably about 20% to about 38%, most preferably about 25% to about 38%.
Component (3)(a) can be made with a Ziegler-Natta catalyst, a metallocene catalyst, or a mixed catalyst, and can be amorphous or contain from about 1%
to about 10% crystallinity as measured by DSC.
Component (3)(b) has at least one melt peak, determined by DSC, present at temperatures higher than 120°C, and at least one peak, relative to the vitreous transition, present at temperatures from -10°C and -35°C. In addition, these materials have a flexural modulus of less than 150 MPa, generally 20 to 100 MPa; a tensile strength at yield of 10 to 20 MPa; elongation at break over 400%; a tension set, at 75% strain, of 20%
to 50%; a Shore D hardness of 20 to 35; a haze value of less than 40%, preferably less than 35%, and does not break (no brittle 'smpaet failure) when an Izod impact test is conducted at -50°C.
Suitable a-olefins of the formula CH2=CHR include, for example, butene-I;
pentene-1; 4-methylpentene-1; hexene-1, and octene-I.
When a diene is present in Component (3)(a), it is typically 1,4-hexadiene, ethylidenenorbornene, or dicyclopentadiene. When a dime is present in Component (3)(b), it is typically a butadiene; I,4-hexadiene; 1,5-hexadiene; or ethylidenenorbornene.
Component 3(b) can be prepared by a polymerization process comprising at least two stages, where in the first stage the propylene, or propylene and ethylene or the a-olefin, or propylene, ethylene and the a-olefin are polymerized to form component (i), and in the following stages the mixtures of ethylene and propylene or a-olefin, or propylene, ethylene and a-olefin, and optionally a dime, are polymerized to form components (ii) and (iii).
The polymerization can be conducted in the liquid phase, gas phase, or liquid-gas phase using separate reactors, all of which can be done either by batch or continuously. For example, it is possible to carry out the polymerization of component (i) using liquid propylene as a diIuent, and the polymerization of components (ii) and (iii) in the gas phase, without intermediate stages except for the partial degassing of the propylene. The preparation of the propylene polymer material is described in more .
detail in U.S. 5,212,246.
The olefin polymer material (3) is present in an amount of about 5 to about I4 parts, preferably about 8 to about 12 parts, per hundred parts of the thermoplastic olefin. The olefin polymer material has a malefic anhydride content of at least 0.3%, but less than 3%, preferably less than 1%, and most preferably less than 0.8%.
Levels of malefic anhydride equal to or greater than 3% give gels, poor adhesion;, and poor durability.
_.CA 02228684 1998-02-04 Component (4) is a fimctionalized polymer that can react with the malefic anhydride groups in components (2), (3), and, if present, (S) selected from the group consisting of (a) an amine-terminated polyalkylene glycol such as polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly(1,2-butylene glycol), and poly(tetramethylene glycol), and (b) a hydroxylated polymer selected from the group consisting of (i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene. Amine-terminated polyethylene oxide is preferred.
Component (4)(a), when present, is used in an amount of about 2.7 to about 6 parts, preferably about 2.8 to about 4 parts, per hundred parts of the thermoplastic olefin, and Component (4)(b), when present, is used in an amount of about 2 to about 6 parts, preferably about 3 to about 5 parts, per hundred parts of the thermoplastic olefin.
A mixture of (a) + (b) can also be used in an amount of about 2 to about 6 parts peT
hundred parts of the thermoplastic olefin, where the ratio of (a) to (b) is about 0.1 to about 0.9.
Optional component (5) is a malefic anhydride-grafted ethylene polymer having a malefic anhydride content of about 2% to about 13%, preferably about 3% to about 6%.
Ethylene homopolymer is preferred. However, copolymers containing 10% or less of an a,-olefin comonomer can also be used. The ethylene polymer preferably has a molecular weight M" of about 500 to about 3000, most preferably about 650 to about 2500; a melting point of about 90°C to about 129°C, most preferably about 92° to about 126°C, and a viscosity of about 20 to about 1000, most preferably about 100 to about 500, SUS at 1~9°C (ASTM D-88). When component (5) is used, it is present in an amount of about 4 to about 15 parts, preferably about 5 to about 10 parts, per hundred parts of the thermoplastic olefin, and the amount of (3) + (5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
The total amount of (2) + (3), or (2) + (3) + (5) is at least 16 parts but less than 27 parts, preferably about 18 to'about 22 parts, per hundred parts of the thermoplastic olefin.
If non-polymeric additives such as conductive carbon black are used, they should be added after the functionalized polymer has reacted with the malefic anhydride-grafted polymers. Alternatively, an adduct of the functionalized polymer and malefic anhydride-grafted poIyolefin can be prepared separately, then blended with the thermoplastic olefin.
The composition of the present invention can also contain other conventional I O additives, for example, antioxidants; stabilizers; extender oils such as paraffinic and naphthenic oils; fillers such as CaC03, talc, and zinc oxide, or flame retardants.
The compounding or melt blending of the components of the composition cart be carried out on an open roll, in an internal mixer (Banbury ar Haake mixers), and single-screw or twin-screw extruders.
Optionally the malefic anhydride-grafted polymers can be preblended, or they can be prereacted with component (4) prior to blending with the thermoplastic olefin. The former method is preferred, however.
In the following examples and comparative examples, the samples for testing were prepared by dry blending the ingredients and reactive mixing in a twin screw extruder at 20 a temperature of 450°F and pelletizing the resultant material. The pellets were injection molded into disks that were painted with about a 1.2 to 2 mil thick coating using Du 'Pont 872 white paint and cured at 250°F for thirty minutes. A lattice pattern of squares with each square about'/4 inch in size was scribed on the painted disk at the end opposite the gate area of the disk. Adhesive tape (3 M~'898) was pressed onto the paint and pulled off to test the amount of paint removed or the paint adhesion. The % failure was recorded as the % of the squares removed by the tape after one pull. The durability was determined by using a Taber abrader with a type C scuffing head assembly and a one pound load. The painted disk was placed in an oven at 70°C for one hour, removed .Trade-mark and placed on the platform of the abrader. The scu~ng head was placed in contact with the painted surface and the disk was rotated fox a specified number of c;ycIes. The amount of paint removed from the complete circumference subtended by the scuffing head was recorded as the % failure.
The criteria set for acceptable paint adhesion was less than 10% failure (paint removed) by the adhesive tape and less than 20% of the paint removed by the Taber abrader after 25 cycles and 30% or less removed after SO cycles.
In this specification all parts and percentages are by weight unless otherwise noted.
Examples l -7 Examples 1-7 show the paint adhesion and durability of compositions containing a thermoplastic olefin (TPO), various amounts of malefic anhydride-grafted olefin polymer material (MA-g-OPM), malefic anhydride-grafted polypropylene (MA-g-PP), and amine-terminated polyethylene oxide (ATPEO), with and without malefic anhydride-grafted polyethylene (MA-g-PE). The results are shown in Table I.
In the table, the thermoplastic olefin contains 55% propylene homopolymer,'3%
semi-crystalline ethylene/propylene copolymer that has a propylene coni:ent of~l0%
and is insoluble in xylene at room temperature, 30% amorphous ethylene/propylene copolymer rubber that has an ethylene content of 50% and is soluble in xylene at room temperature, and 12% ethylene homopolymer having a melt index of about 50 g/10 min.
The MA-grafted OPM (I) was Exxeloi VA-1803 ethylenelpropylene rubber containing 0.7% grafted malefic anhydride, commercially available from Exxon Chemical Company.
The MA-grafted OPM (2) was Royaltuf*465A ethylene/propyienehnon-conjugated diene terpolymer rubber containing 0.4% grafted malefic anhydride, having a Mooney viscosity (ML 1 + 4 @ 125°C) of 60 and an ethylene/propylene ratio of 75/25, commercially available from Uniroyal Chemical Co. Inc..
The MA-grafted polypropylene was Epolene*E-43 malefic anhydride-modified polypropylene wax, commercially available from Eastman Chemical Company.
Trade=mark IZ
The MA-graded polyethylene was Ceramer 67 maIeic anhydride-grafted polyethylene wax, commerdally available from Petrolite Corporation.
The ATPEO was XTJ-418 monaamine-terminated polyethylene oxide, commercially available from Huntsman Corporation.
The antioxidant was IrganoX B 225, a blend of I part Irgano~C ~I010 2,2-bas[[3-(3,5-bas(1,1-dimethylethyl)-4-hydroxypheayl]-1-oxopropoxy)methyl]-i,.3-propanediyl-3,5-bas(1,1-dimethylethyl)-4-hydroxybenzene propanoate stabilizer and 1 part Irgafos*
168 tris(2,4-di-t-butylphenyl) phosphate, commercially available from Ciba-Geigy.
Table 1 Ex. Ex. Ex. Ex. Ex. Ex. Ex.
1 2 3 4 5 6 ?
MA-g- 5 5. 10 10 5 10 ~ 10 OPM (1) MA-g- 5 5 - - - -OPM (2 MA- -PP 10 IO 10 10 10 10 ' 10 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Paint 3 0 G 0 0 9 0 Adhesion, .
%
Failure Durability, Failure 25 cies 10 0 8 15 0 15 15 50 C cles 20 0 8 20 12 15 25 lo Examples 1, 3, 4, 6 and 7 show that the combination of MA-grafted polypropylene and MA-grafted ethylene/propylene olefin polymer material gave both good adhesion and durability. Examples 2 and 5 show that combining MA-grafted polyethylene with the MA-grafted polypropylene and MA-grafted olefn polymer material gave a slight improvement in paint adhesion and an improvement in durability.
*.
Trade=mark Cvm~arative Examples I-4 In Table 2, the ungrafted rubber used in Comparative Example 1 was Dutral*4038 ethylene/propylene/ethylidenenorbotnene terpolymer rubber containing 4%
ethylidenenorbornene, commercially available from Enichem America. Inc.. All of the other components of the formulations were the same as in Examples I-7.
Table 2 Coin . Ex. Com . Ex. Com . Ex. Com . Ex.
TPO ~ .-I00 I00 100 100 Rubber 10 - - -1) Antioxidant0.2 0.2 0.2 0.2 Paint Adhesion,45 0 54 28 Failure ,Durability, .
%
Failure 25 C cles 28 45 28 0 SU C cles 44 55 50 1 Comparative Example 1 showed that adding rubber that is not grafted with malefic anhydride gave both poor adhesion and poor durability. Comparative Example 2 showed that adding higher levels of MA-grafted polypropylene but no 1~ZA
grafted to OPM gave good adhesion, but durability was still poor. Comparative Example showed that low levels of MA-grafted polypropylene (5 parts) in combination with a MA-grafted OPM gave both poor adhesion and poor durability. Comparative Example 4 showed that combining MA-grafted polypropylene and MA-grafted polyethylene without MA-grafted olefin polymer material gave good durability, but poor paint adhesion.
Trade-mark Examples 8-i i Examples 8-1 I slow tb~e:paint adhesion and durability of compositions containing a therriioplastic olefin (TPO); -malefic anhydride-grafted olefin polymer materials (MA g-OPM), malefic anhydride-grafted polypropylene (MA-g-PP), and three types of functionalized polymers, i.e., amine-terminated polyethylene oxide (ATPEO), hydroxylated polyethylene (HPE), and hydroxylated polybutene (HPB). The results are given in Table 3.
In Table 3; the thermoplastic elastomer, the malefic anhydride-grafted olefin polymer materials (1) and~(2), the malefic anhydride-grafted polypropylene, the amine-terminated polyethylene oxide, and the antioxidant are the same as in Examples 1-7.
The malefic anhydride-grafted OPM (3) was a propylene polymer material comprising (a) 30% of a propylene/ethylene random copolymer having an ethylene.-content of 3.3%, (b) 6.8% of a semi-crystalline ethylene/propyIene copolymer fraction that is insoluble in xylene at room temperature, and (c) 63.2% of an amorphous ethylene/propylene copolymer fraction that is soluble in xylene at room temperature, and contained I% grafted malefic anhydride.
The MA-g-PE was Ceramer 67 malefic anhydride-grafted polyethylene wax, commercially available from Petrolite Corporation.
The HPE was Unilin~350 hydroxylated polyethylene wax, commercially available form Petrolite Corporation.
The HPB was HPVM 2202 hydroxylated polybutene, commercially available from Shell Chemical Company.
Trade-mark Table Ex.8 Ex.9 Ex.lO Ex.ll Z'pp 100 100 100 100 MA-g-OPM - _ _ 5 1) MA-g-OPM - 10 10 2) MA-g-OPM 10 - - -(3 ~- -pP 10 10 10 10 MA- -PE - _ - 10 HPE - 6 - _ HPB _ - 3 3 Antioxidant0.2 0.2 0.2 0.2 Paint 0 0 0 0 Adhesion, Failure Durability, Failure 25 cles 0 18 13 0 50 cles 0 26 18 0 Comparative Examples 5-9 In Table 4, the thermoplastic olefin, malefic anhydride-grafted olefin polymer materials (1) and (3), the malefic anhydride-grafted polypropylene, the amine-terminated polyethylene oxide, and the antioxidant were the same as in Examples 8-13.
The malefic anhydride-grafted OPM (4) was the same as malefic anhydride-grafted OPM
(3), except that it contained 3% grafted malefic anhydride instead of 1%.
Table 4 Comp. Comp.
Comp.
Comp.
Comp.
Ex.S Ex.6 Ex.7 Ex.8 Ex.9 Tp0 100 100 100 100 100 MA-g-0PM - 10 10 - -(1 MA-g-OPM _ - _ 10 -(3) MA-g-OPM 10 - _ 4) -PP 10 10 10 - _ MA
ATPEO 3 2.5 7 3 3 Antioxidant0.2 0.2 0.2 0.2 0.2 Paint 30 18 30 100 100 Adhesion, Failure Durability, Failure 25 cles 45 35 50 100 100 50 cles 55 38 75 100 100 These comparative examples show that both adhesion and durability are unacceptable when the MA-g-OPM contains 3% or more grafted malefic anhydride (Comp. Ex. 5 and 9), too much or too little ATPEO is used (Comp. Ex. 6 and 7), and when MA-g-PP is not included in the composition (Comp. Ex. 8 and 9).
Examples 12 and 13 These examples illustrate the use of a mixture of an amine-terminated polyalkylene glycol and a hydroxylated polymer as the functionalized polymer, component (4) of the composition of this invention. The results are shown in Table 5.
In Table 5, the thermoplastic olefin, the malefic anhydride-grafted polypropylene, the malefic anhydride-grafted olefin polymer materials (1) and (2), the ATPEO, and the antioxidant are the same as those used in Examples 1-7. The HPE and HPB are the same as those used in Examples 8-11.
Table 5 Ex. 12 Ex. 13 MA-g-OPM (1) 5 5 MA-g-OPM (2) S 5 MA-g-PP 10 10 HI,E
Antioxidant 0.2 0.2 Paint Adhesion, 0 0 Failure Durability, % Failure 25 cycles 8 16 50 cycles 20 28 Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosure. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be erected without departing from the spirit and scope of the invention as described and claimed.
(b) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and (c) about 2 to about 6 parts of a mixture of (a) + (b) per hundred parts of the thermoplastic olefin, wherein the ratio of (a) to (b) is about 0.1 to about 0.9; and, optionally, (5) about 4 parts to about 15 parts per hundred parts of the thermoplastic olefin of a malefic anhydride-grafted ethylene polymer having a malefic anhydride content of about 2% to about 13% and a molecular weight Mn of about 500 to about 3000, CA 02228684 1998-02-04~
wherein (2) + (3), or (2) + (3) + (5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin, and when the malefic anhydride-grafted polyethylene is present, (3) + (5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
Injection molded parts such as automobile bumpers made from this composition are directly paintable with polar paints or coatings without the need for a layer of adhesion promoter between the thermoplastic olefin surface and the paint.
Component (1) of the composition of this invention is a thermoplastic olefin comprising, by weight, (a) about 10% to about 60%, preferably about 20% to about 50%, of a propylene homopolymer having an isotactic index greater than 90, preferably between 95 and 98, or a crystalline propylene copolymer with ethylene and/or a C4_g oc-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60%, preferably about 30% to about SO%, of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing about 1% to about 10% of a diene, which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20%, preferably about 7% to about 1 S%, of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92%
ethylene; and (d) about 5% to about 20%, preferably about 7% to about 15%, of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 min, preferably about 15 to about SO g/10 min. Ethylene homopolymer is preferred. However, copolymers containing 8% or less ofan a-olefn comonomer can also be used.
The thermoplastic olefin is typically prepared by sequential polymerization in at least three stages. Fraction (a) can be made in the first reactor, fractions (b) and (c~ in the second reactor, and fraction (d) in the third. reactor. Alternatively, fraction (d) can be made in the second reactor and fractions (b) and ,(c) in the third reactor.
The polymerization conditions and the polymerization catalyst are described in more detail in U.S. Patent 5,302,454. Alternative7.y, the four fractions can be prepared separately and then blended together.
Sequential ZO polymerization is preferred.
The Ca.s a-olefins useful in the preparation of the thermoplastic olefin include, for example, butene-1; pentene-1; hexene-I; 4-methylpentene-1, and octene-1.
The diene, when present, is typically a butadiene; I,4-hexadiene; I,5-hexadiene, or ethylidenenorbornene.
The thermoplastic olefn is present in an amount of 100 parts by weight.
Component (2) is a malefic anhydride=grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of about 0.5%
to about 4%, preferably about l% to about 3%. Propylene homopolymer is preferred.
The polymer has a malefic anhydride content of about 2% to about 5%, preferably about 20 3% to about 4%, and preferably has a molecular weight M" of about 2500 to about 25,000, most preferably about 3000 to about 10,000. Component (2) is present in an amount of about 8 to about 14 parts, preferably about 10 to about 12 parts, per hundred parts of the thermoplastic olefin.
Component (3) is a malefic anhydride-grafted olefin polymer material selected from the group consisting of (a) a malefic anhydride-grafted poiyolefin rubber comprising an ethylenelpropylene or ethylene<butene copolymer rubber, optionally containing about 0.5 % to b CA 02228684Y 1998-02-04 .._,. ..... ...._,....
about 10% of a dime, preferably about 2% to about 6%, which contains about 30% to about 70%; preferably about 40% to about 60%, ethylene, and (b~ a malefic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of (i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CHZ=CHR a-olefin, where R is a C2.8 straight or branched alkyl group, and (c) propylene and an a-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an a-olefin as defined above in (i)(b), containing about 1% to about 10% ofthe a-olefin and over 50% up to 98% of both ethylene and the a-olefin; and (c) ethylene and an a-olefin as defined in (i)(b), containing over 50% up to 98% of the a-olefin, which copolymer is insoluble in xylene at room or ambient temperature; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene; (b) ethylene, propylene, and an a-olefin as defined in (i)(b), wherein the a-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and a-olefin present is from 20% to less than 45%; and (c) CA 02.2286.84. ,1.998-02-p4~" ...... __ __. .__.___ ethylene and an oc-olefin as defined in (i)(b), containing from 20% to less than 45% of the a-olefin, and optionally containing about 0.5% to about 10% of a dime, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or Ca-a a-olefin or combination thereof in fractions (ii) + (iii) is less than 50%.
Fraction (i) is preferably present in an amount of about 10% to about 40%, most preferably about 20% to about 35%. When (i) is a propylene homopolymer, the isotactic index is preferably about 85 to about 98. When (i) is a copolymer, the amount of propylene in the copolymer is preferably about 90% to about 99%.
Fraction (ii) is preferably present in an amount of about 7% to about 15%.
Typically the crystallinity is about 20% to about 60% by DSC. Generally, the ethylene or oc-olefin content or the combination of ethylene and the oc-olefin when both are used is over 55% up to 98%, preferably about 80% to about 95%.
Fraction (iii) is preferably present in an amount of about SO% to about 70%.
The ethylene or the a-olefin content or ethylene and the a-olefin content of component (iii) is preferably about 20% to about 38%, most preferably about 25% to about 38%.
Component (3)(a) can be made with a Ziegler-Natta catalyst, a metallocene catalyst, or a mixed catalyst, and can be amorphous or contain from about 1%
to about 10% crystallinity as measured by DSC.
Component (3)(b) has at least one melt peak, determined by DSC, present at temperatures higher than 120°C, and at least one peak, relative to the vitreous transition, present at temperatures from -10°C and -35°C. In addition, these materials have a flexural modulus of less than 150 MPa, generally 20 to 100 MPa; a tensile strength at yield of 10 to 20 MPa; elongation at break over 400%; a tension set, at 75% strain, of 20%
to 50%; a Shore D hardness of 20 to 35; a haze value of less than 40%, preferably less than 35%, and does not break (no brittle 'smpaet failure) when an Izod impact test is conducted at -50°C.
Suitable a-olefins of the formula CH2=CHR include, for example, butene-I;
pentene-1; 4-methylpentene-1; hexene-1, and octene-I.
When a diene is present in Component (3)(a), it is typically 1,4-hexadiene, ethylidenenorbornene, or dicyclopentadiene. When a dime is present in Component (3)(b), it is typically a butadiene; I,4-hexadiene; 1,5-hexadiene; or ethylidenenorbornene.
Component 3(b) can be prepared by a polymerization process comprising at least two stages, where in the first stage the propylene, or propylene and ethylene or the a-olefin, or propylene, ethylene and the a-olefin are polymerized to form component (i), and in the following stages the mixtures of ethylene and propylene or a-olefin, or propylene, ethylene and a-olefin, and optionally a dime, are polymerized to form components (ii) and (iii).
The polymerization can be conducted in the liquid phase, gas phase, or liquid-gas phase using separate reactors, all of which can be done either by batch or continuously. For example, it is possible to carry out the polymerization of component (i) using liquid propylene as a diIuent, and the polymerization of components (ii) and (iii) in the gas phase, without intermediate stages except for the partial degassing of the propylene. The preparation of the propylene polymer material is described in more .
detail in U.S. 5,212,246.
The olefin polymer material (3) is present in an amount of about 5 to about I4 parts, preferably about 8 to about 12 parts, per hundred parts of the thermoplastic olefin. The olefin polymer material has a malefic anhydride content of at least 0.3%, but less than 3%, preferably less than 1%, and most preferably less than 0.8%.
Levels of malefic anhydride equal to or greater than 3% give gels, poor adhesion;, and poor durability.
_.CA 02228684 1998-02-04 Component (4) is a fimctionalized polymer that can react with the malefic anhydride groups in components (2), (3), and, if present, (S) selected from the group consisting of (a) an amine-terminated polyalkylene glycol such as polyethylene glycol, polypropylene glycol, copolymers of polyethylene glycol and polypropylene glycol, poly(1,2-butylene glycol), and poly(tetramethylene glycol), and (b) a hydroxylated polymer selected from the group consisting of (i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene. Amine-terminated polyethylene oxide is preferred.
Component (4)(a), when present, is used in an amount of about 2.7 to about 6 parts, preferably about 2.8 to about 4 parts, per hundred parts of the thermoplastic olefin, and Component (4)(b), when present, is used in an amount of about 2 to about 6 parts, preferably about 3 to about 5 parts, per hundred parts of the thermoplastic olefin.
A mixture of (a) + (b) can also be used in an amount of about 2 to about 6 parts peT
hundred parts of the thermoplastic olefin, where the ratio of (a) to (b) is about 0.1 to about 0.9.
Optional component (5) is a malefic anhydride-grafted ethylene polymer having a malefic anhydride content of about 2% to about 13%, preferably about 3% to about 6%.
Ethylene homopolymer is preferred. However, copolymers containing 10% or less of an a,-olefin comonomer can also be used. The ethylene polymer preferably has a molecular weight M" of about 500 to about 3000, most preferably about 650 to about 2500; a melting point of about 90°C to about 129°C, most preferably about 92° to about 126°C, and a viscosity of about 20 to about 1000, most preferably about 100 to about 500, SUS at 1~9°C (ASTM D-88). When component (5) is used, it is present in an amount of about 4 to about 15 parts, preferably about 5 to about 10 parts, per hundred parts of the thermoplastic olefin, and the amount of (3) + (5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
The total amount of (2) + (3), or (2) + (3) + (5) is at least 16 parts but less than 27 parts, preferably about 18 to'about 22 parts, per hundred parts of the thermoplastic olefin.
If non-polymeric additives such as conductive carbon black are used, they should be added after the functionalized polymer has reacted with the malefic anhydride-grafted polymers. Alternatively, an adduct of the functionalized polymer and malefic anhydride-grafted poIyolefin can be prepared separately, then blended with the thermoplastic olefin.
The composition of the present invention can also contain other conventional I O additives, for example, antioxidants; stabilizers; extender oils such as paraffinic and naphthenic oils; fillers such as CaC03, talc, and zinc oxide, or flame retardants.
The compounding or melt blending of the components of the composition cart be carried out on an open roll, in an internal mixer (Banbury ar Haake mixers), and single-screw or twin-screw extruders.
Optionally the malefic anhydride-grafted polymers can be preblended, or they can be prereacted with component (4) prior to blending with the thermoplastic olefin. The former method is preferred, however.
In the following examples and comparative examples, the samples for testing were prepared by dry blending the ingredients and reactive mixing in a twin screw extruder at 20 a temperature of 450°F and pelletizing the resultant material. The pellets were injection molded into disks that were painted with about a 1.2 to 2 mil thick coating using Du 'Pont 872 white paint and cured at 250°F for thirty minutes. A lattice pattern of squares with each square about'/4 inch in size was scribed on the painted disk at the end opposite the gate area of the disk. Adhesive tape (3 M~'898) was pressed onto the paint and pulled off to test the amount of paint removed or the paint adhesion. The % failure was recorded as the % of the squares removed by the tape after one pull. The durability was determined by using a Taber abrader with a type C scuffing head assembly and a one pound load. The painted disk was placed in an oven at 70°C for one hour, removed .Trade-mark and placed on the platform of the abrader. The scu~ng head was placed in contact with the painted surface and the disk was rotated fox a specified number of c;ycIes. The amount of paint removed from the complete circumference subtended by the scuffing head was recorded as the % failure.
The criteria set for acceptable paint adhesion was less than 10% failure (paint removed) by the adhesive tape and less than 20% of the paint removed by the Taber abrader after 25 cycles and 30% or less removed after SO cycles.
In this specification all parts and percentages are by weight unless otherwise noted.
Examples l -7 Examples 1-7 show the paint adhesion and durability of compositions containing a thermoplastic olefin (TPO), various amounts of malefic anhydride-grafted olefin polymer material (MA-g-OPM), malefic anhydride-grafted polypropylene (MA-g-PP), and amine-terminated polyethylene oxide (ATPEO), with and without malefic anhydride-grafted polyethylene (MA-g-PE). The results are shown in Table I.
In the table, the thermoplastic olefin contains 55% propylene homopolymer,'3%
semi-crystalline ethylene/propylene copolymer that has a propylene coni:ent of~l0%
and is insoluble in xylene at room temperature, 30% amorphous ethylene/propylene copolymer rubber that has an ethylene content of 50% and is soluble in xylene at room temperature, and 12% ethylene homopolymer having a melt index of about 50 g/10 min.
The MA-grafted OPM (I) was Exxeloi VA-1803 ethylenelpropylene rubber containing 0.7% grafted malefic anhydride, commercially available from Exxon Chemical Company.
The MA-grafted OPM (2) was Royaltuf*465A ethylene/propyienehnon-conjugated diene terpolymer rubber containing 0.4% grafted malefic anhydride, having a Mooney viscosity (ML 1 + 4 @ 125°C) of 60 and an ethylene/propylene ratio of 75/25, commercially available from Uniroyal Chemical Co. Inc..
The MA-grafted polypropylene was Epolene*E-43 malefic anhydride-modified polypropylene wax, commercially available from Eastman Chemical Company.
Trade=mark IZ
The MA-graded polyethylene was Ceramer 67 maIeic anhydride-grafted polyethylene wax, commerdally available from Petrolite Corporation.
The ATPEO was XTJ-418 monaamine-terminated polyethylene oxide, commercially available from Huntsman Corporation.
The antioxidant was IrganoX B 225, a blend of I part Irgano~C ~I010 2,2-bas[[3-(3,5-bas(1,1-dimethylethyl)-4-hydroxypheayl]-1-oxopropoxy)methyl]-i,.3-propanediyl-3,5-bas(1,1-dimethylethyl)-4-hydroxybenzene propanoate stabilizer and 1 part Irgafos*
168 tris(2,4-di-t-butylphenyl) phosphate, commercially available from Ciba-Geigy.
Table 1 Ex. Ex. Ex. Ex. Ex. Ex. Ex.
1 2 3 4 5 6 ?
MA-g- 5 5. 10 10 5 10 ~ 10 OPM (1) MA-g- 5 5 - - - -OPM (2 MA- -PP 10 IO 10 10 10 10 ' 10 Antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Paint 3 0 G 0 0 9 0 Adhesion, .
%
Failure Durability, Failure 25 cies 10 0 8 15 0 15 15 50 C cles 20 0 8 20 12 15 25 lo Examples 1, 3, 4, 6 and 7 show that the combination of MA-grafted polypropylene and MA-grafted ethylene/propylene olefin polymer material gave both good adhesion and durability. Examples 2 and 5 show that combining MA-grafted polyethylene with the MA-grafted polypropylene and MA-grafted olefn polymer material gave a slight improvement in paint adhesion and an improvement in durability.
*.
Trade=mark Cvm~arative Examples I-4 In Table 2, the ungrafted rubber used in Comparative Example 1 was Dutral*4038 ethylene/propylene/ethylidenenorbotnene terpolymer rubber containing 4%
ethylidenenorbornene, commercially available from Enichem America. Inc.. All of the other components of the formulations were the same as in Examples I-7.
Table 2 Coin . Ex. Com . Ex. Com . Ex. Com . Ex.
TPO ~ .-I00 I00 100 100 Rubber 10 - - -1) Antioxidant0.2 0.2 0.2 0.2 Paint Adhesion,45 0 54 28 Failure ,Durability, .
%
Failure 25 C cles 28 45 28 0 SU C cles 44 55 50 1 Comparative Example 1 showed that adding rubber that is not grafted with malefic anhydride gave both poor adhesion and poor durability. Comparative Example 2 showed that adding higher levels of MA-grafted polypropylene but no 1~ZA
grafted to OPM gave good adhesion, but durability was still poor. Comparative Example showed that low levels of MA-grafted polypropylene (5 parts) in combination with a MA-grafted OPM gave both poor adhesion and poor durability. Comparative Example 4 showed that combining MA-grafted polypropylene and MA-grafted polyethylene without MA-grafted olefin polymer material gave good durability, but poor paint adhesion.
Trade-mark Examples 8-i i Examples 8-1 I slow tb~e:paint adhesion and durability of compositions containing a therriioplastic olefin (TPO); -malefic anhydride-grafted olefin polymer materials (MA g-OPM), malefic anhydride-grafted polypropylene (MA-g-PP), and three types of functionalized polymers, i.e., amine-terminated polyethylene oxide (ATPEO), hydroxylated polyethylene (HPE), and hydroxylated polybutene (HPB). The results are given in Table 3.
In Table 3; the thermoplastic elastomer, the malefic anhydride-grafted olefin polymer materials (1) and~(2), the malefic anhydride-grafted polypropylene, the amine-terminated polyethylene oxide, and the antioxidant are the same as in Examples 1-7.
The malefic anhydride-grafted OPM (3) was a propylene polymer material comprising (a) 30% of a propylene/ethylene random copolymer having an ethylene.-content of 3.3%, (b) 6.8% of a semi-crystalline ethylene/propyIene copolymer fraction that is insoluble in xylene at room temperature, and (c) 63.2% of an amorphous ethylene/propylene copolymer fraction that is soluble in xylene at room temperature, and contained I% grafted malefic anhydride.
The MA-g-PE was Ceramer 67 malefic anhydride-grafted polyethylene wax, commercially available from Petrolite Corporation.
The HPE was Unilin~350 hydroxylated polyethylene wax, commercially available form Petrolite Corporation.
The HPB was HPVM 2202 hydroxylated polybutene, commercially available from Shell Chemical Company.
Trade-mark Table Ex.8 Ex.9 Ex.lO Ex.ll Z'pp 100 100 100 100 MA-g-OPM - _ _ 5 1) MA-g-OPM - 10 10 2) MA-g-OPM 10 - - -(3 ~- -pP 10 10 10 10 MA- -PE - _ - 10 HPE - 6 - _ HPB _ - 3 3 Antioxidant0.2 0.2 0.2 0.2 Paint 0 0 0 0 Adhesion, Failure Durability, Failure 25 cles 0 18 13 0 50 cles 0 26 18 0 Comparative Examples 5-9 In Table 4, the thermoplastic olefin, malefic anhydride-grafted olefin polymer materials (1) and (3), the malefic anhydride-grafted polypropylene, the amine-terminated polyethylene oxide, and the antioxidant were the same as in Examples 8-13.
The malefic anhydride-grafted OPM (4) was the same as malefic anhydride-grafted OPM
(3), except that it contained 3% grafted malefic anhydride instead of 1%.
Table 4 Comp. Comp.
Comp.
Comp.
Comp.
Ex.S Ex.6 Ex.7 Ex.8 Ex.9 Tp0 100 100 100 100 100 MA-g-0PM - 10 10 - -(1 MA-g-OPM _ - _ 10 -(3) MA-g-OPM 10 - _ 4) -PP 10 10 10 - _ MA
ATPEO 3 2.5 7 3 3 Antioxidant0.2 0.2 0.2 0.2 0.2 Paint 30 18 30 100 100 Adhesion, Failure Durability, Failure 25 cles 45 35 50 100 100 50 cles 55 38 75 100 100 These comparative examples show that both adhesion and durability are unacceptable when the MA-g-OPM contains 3% or more grafted malefic anhydride (Comp. Ex. 5 and 9), too much or too little ATPEO is used (Comp. Ex. 6 and 7), and when MA-g-PP is not included in the composition (Comp. Ex. 8 and 9).
Examples 12 and 13 These examples illustrate the use of a mixture of an amine-terminated polyalkylene glycol and a hydroxylated polymer as the functionalized polymer, component (4) of the composition of this invention. The results are shown in Table 5.
In Table 5, the thermoplastic olefin, the malefic anhydride-grafted polypropylene, the malefic anhydride-grafted olefin polymer materials (1) and (2), the ATPEO, and the antioxidant are the same as those used in Examples 1-7. The HPE and HPB are the same as those used in Examples 8-11.
Table 5 Ex. 12 Ex. 13 MA-g-OPM (1) 5 5 MA-g-OPM (2) S 5 MA-g-PP 10 10 HI,E
Antioxidant 0.2 0.2 Paint Adhesion, 0 0 Failure Durability, % Failure 25 cycles 8 16 50 cycles 20 28 Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosure. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be erected without departing from the spirit and scope of the invention as described and claimed.
Claims (12)
1. A composition comprising, by weight:
(1) 100 parts of a thermoplastic olefin comprising:
(a) about 10% to about 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4-8 .alpha.-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60% of an amorphous ethylene-propylene or ethylene-butane copolymer fraction, optionally containing about 1% to about 10% of a diene, Which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20% of a semi-crystalline ethylene-propylene or ethylene-butane copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92% ethylene; and (d) about 5% to about 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to about 100 g/10 min;
(2) about 8 parts to about 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of about 0.5% to about 4%, each having a maleic anhydride content of about 2 to. about 5% and a molecular weight M n of about 2500 to about 25,000;
(3) about 5 parts to about 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted olefin polymer material having a maleic anhydride content of at least 0.3% but less than 3%, selected from the group consisting of:
(a) a maleic anhydride-grafted polyolefin rubber comprising an ethylene/propylene or ethylene/butene copolymer rubber, optionally containing about 0.5% to about 10% of a diene, which contains about 30% to about 70% ethylene, and (b) a maleic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of:
(i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CH2=CHR .alpha.-olefin, where R
is a C2-8 straight or branched alkyl group, and (c) propylene and an .alpha.-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50%
ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined above in (i)(b), containing about 1% to about 10% of the .alpha.-olefin and over 50% up to 98% of both ethylene and the .alpha.-olefin: and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing over 50% up to 98% of the .alpha.-olefin, which copolymer is insoluble in xylene at room or ambient temperatures; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined in (i)(b), wherein the .alpha.-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and .alpha.-olefin present is from 20% to less than 45%; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing from 20% to less than 45% of the .alpha.-olefin, and optionally containing about 0.5% to about 10% of a diene, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or C4-8 .alpha.-olefin or combination thereof in fractions (ii) + (iii) is less than 50%; and (4) a functionalized polymer that is reactive with the anhydride groups of the grafted polymers, selected from the group consisting of:
(a) about 2.7 to about 6 parts of an amine-terminated polyalkylene glycol per hundred parts of thermoplastic olefin;
(b) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and (c) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a mixture of (a)+(b), where the ratio of (a) to (b) is about 0.1 to about 0.9, wherein (2)+(3) is at least 16 parts but less thaw 27 parts per hundred parts of the thermoplastic olefin.
(1) 100 parts of a thermoplastic olefin comprising:
(a) about 10% to about 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4-8 .alpha.-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) about 30% to about 60% of an amorphous ethylene-propylene or ethylene-butane copolymer fraction, optionally containing about 1% to about 10% of a diene, Which is xylene soluble at room temperature and contains about 30% to about 70% ethylene;
(c) about 2% to about 20% of a semi-crystalline ethylene-propylene or ethylene-butane copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92% ethylene; and (d) about 5% to about 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to about 100 g/10 min;
(2) about 8 parts to about 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of about 0.5% to about 4%, each having a maleic anhydride content of about 2 to. about 5% and a molecular weight M n of about 2500 to about 25,000;
(3) about 5 parts to about 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted olefin polymer material having a maleic anhydride content of at least 0.3% but less than 3%, selected from the group consisting of:
(a) a maleic anhydride-grafted polyolefin rubber comprising an ethylene/propylene or ethylene/butene copolymer rubber, optionally containing about 0.5% to about 10% of a diene, which contains about 30% to about 70% ethylene, and (b) a maleic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of:
(i) about 10% to about 50% of a propylene homopolymer having an isotactic index of about 80% to about 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CH2=CHR .alpha.-olefin, where R
is a C2-8 straight or branched alkyl group, and (c) propylene and an .alpha.-olefin as defined above in (i)(b), the copolymer containing about 85% to about 99% propylene and having an isotactic index of about 80% to about 98%;
(ii) about 3% to about 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of about 20% to about 60% by differential scanning calorimetry (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50%
ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined above in (i)(b), containing about 1% to about 10% of the .alpha.-olefin and over 50% up to 98% of both ethylene and the .alpha.-olefin: and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing over 50% up to 98% of the .alpha.-olefin, which copolymer is insoluble in xylene at room or ambient temperatures; and (iii) about 40% to about 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined in (i)(b), wherein the .alpha.-olefin is present in an amount of about 1% to about 10%, and the amount of ethylene and .alpha.-olefin present is from 20% to less than 45%; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing from 20% to less than 45% of the .alpha.-olefin, and optionally containing about 0.5% to about 10% of a diene, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of about 1.7 to about 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is about 65% to about 80%, the weight ratio of fractions (ii)/(iii) is about 0.1 to about 0.3, and the total content of ethylene or C4-8 .alpha.-olefin or combination thereof in fractions (ii) + (iii) is less than 50%; and (4) a functionalized polymer that is reactive with the anhydride groups of the grafted polymers, selected from the group consisting of:
(a) about 2.7 to about 6 parts of an amine-terminated polyalkylene glycol per hundred parts of thermoplastic olefin;
(b) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and (c) about 2 to about 6 parts per hundred parts of the thermoplastic olefin of a mixture of (a)+(b), where the ratio of (a) to (b) is about 0.1 to about 0.9, wherein (2)+(3) is at least 16 parts but less thaw 27 parts per hundred parts of the thermoplastic olefin.
2. The composition of claim 1, wherein (4) is an amine-terminated polyalkylene glycol.
3. The composition of claim 1, wherein (4) is a mixture of (a) and (b), the total amount of (a) + (b) is about 2 to about 6 parts per hundred parts of the thermoplastic olefin, and the ratio of (a) to (b) is about 0.1 to about 0.9.
4. The composition of claim 1 which additionally comprises (5), about 4 parts to about 15 parts per hundred parts of the thermoplastic olefin, of a maleic anhydride grafted ethylene polymer having a maleic anhydride content of about 2% to about 13% and a molecular weight Mn of about 500 to about 3000, wherein (2)+(3)+(5) is at least 16 parts but less than 27 parts par hundred parts of the thermoplastic olefin, and (3)+(5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
5. The composition of claim 4, wherein (4) is an amine-terminated polyalkylene glycol.
6. The composition of claim 4, wherein (4) is a mixture of (a)+(b), the total amount of (a)+(b) is about 2 to about 6 parts per hundred parts of the thermoplastic olefin, and the ratio of (a) to (b) is about 0.1 to about 0.9.
7, An injection molded article comprising the composition of claim 1.
8. An injection molded article comprising the composition of claim 4.
9, A composition comprising, by weight:
(1) 100 parts of a thermoplastic olefin comprising:
(a) 10% to 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4-8 .alpha.-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) 30% to 60% of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing 1% to
(1) 100 parts of a thermoplastic olefin comprising:
(a) 10% to 60% of a propylene homopolymer having an isotactic index greater than 90, or a crystalline propylene copolymer with ethylene and/or a C4-8 .alpha.-olefin having a propylene content greater than 85% and an isotactic index of greater than 85%;
(b) 30% to 60% of an amorphous ethylene-propylene or ethylene-butene copolymer fraction, optionally containing 1% to
10% of a diene, which is xylene soluble at room temperature and contains 30% to 70% ethylene;
(c) 2% to 20% of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92%
ethylene: and (d) 5% to 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 mint (2) 8 parts to 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of 0.5% to 4%, each having a maleic anhydride content of 2 to 5% and a molecular weight M n of 2500 to 25,000;
(3) 5 parts to 14 parts par hundred parts of the thermoplastic olefin of a maleic anhydride-grafted olefin polymer material having a maleic anhydride content of at least 0.3% but less than 3%, selected from the group consisting of:
(a) a maleic anhydride-grafted polyolefin rubber comprising an ethylene/propylene or ethylene/butene copolymer rubber, optionally containing 0.5% to 10% of a dime, which contains 30% to 70% ethylene, and (b) a maleic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of:
(i) 10% to 50% of a propylene homopolymer having an isotactic index of 80% to 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CH2=CHR .alpha.-olefin, where R is a C2-8 straight or branched alkyl group, and (c) propylene and an .alpha.-olefin as defined above in (i)(b), the copolymer containing 85% to 99%
propylene and having an isotactic index of 80% to 98%;
(ii) 3% to 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of 20% to 60% by differential scanning calorimeter (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined above in (i)(b), containing 1% to 10% of the .alpha.-olefin and over 50% up to 98% of both ethylene and the .alpha.-olefin; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing over 50% up to 98% of the .alpha.-olefin, which copolymer is insoluble in xylene at room or ambient temperatures and (iii) 40% to 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene (b) ethylene, propylene, and an .alpha.-olefin as defined in (i)(b), wherein the .alpha.-olefin is present in an amount of 1% to 10%. and the amount of ethylene and .alpha.-olefin present is from 20%
to less than 45%; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing from 20% to less than 45% of the .alpha.-olefin, and optionally containing 0.5% to 10% of a diene, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of 1.7 to 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is 65% to 80%, the weight ratio of fractions (ii) / (iii) is 0.1 to 0.3, and the total content of ethylene or C4-8 .alpha.-olefin or combination thereof in fractions (ii) + (iii) is less than 50%; and (4) a functionalized polymer that is reactive with the anhydride groups of the grafted polymers, selected from the group consisting of:
(a) 2.7 to 6 parts of an amine-terminated polyalkylene glycol per hundred parts of thermoplastic olefin;
(b) 2 to 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and c) 2 to 6 parts per hundred parts of the thermoplastic olefin of a mixture of (a) + (b) , where the ratio of (a) to (b) is 0.1 to 0.9, wherein (2)+(3) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin.
10. The composition of claim 9 which additionally comprises (5), 4 parts to 15 parts per hundred parts of the thermoplastic olefin, of a maleic anhydride grafted ethylene polymer having a maleic anhydride content of 2% to 13% and a molecular weight M n of 500 to 3000, wherein (2)+(3)+(5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin, and (3)+(5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
(c) 2% to 20% of a semi-crystalline ethylene-propylene or ethylene-butene copolymer that is xylene insoluble at room temperature and contains greater than 75% but less than 92%
ethylene: and (d) 5% to 20% of an ethylene polymer having a density of 0.91 to 0.96 g/cm3 and a melt index of 0.1 to 100 g/10 mint (2) 8 parts to 14 parts per hundred parts of the thermoplastic olefin of a maleic anhydride-grafted propylene homopolymer or ethylene/propylene random copolymer having an ethylene content of 0.5% to 4%, each having a maleic anhydride content of 2 to 5% and a molecular weight M n of 2500 to 25,000;
(3) 5 parts to 14 parts par hundred parts of the thermoplastic olefin of a maleic anhydride-grafted olefin polymer material having a maleic anhydride content of at least 0.3% but less than 3%, selected from the group consisting of:
(a) a maleic anhydride-grafted polyolefin rubber comprising an ethylene/propylene or ethylene/butene copolymer rubber, optionally containing 0.5% to 10% of a dime, which contains 30% to 70% ethylene, and (b) a maleic anhydride-grafted propylene polymer material, wherein the propylene polymer material consists essentially of:
(i) 10% to 50% of a propylene homopolymer having an isotactic index of 80% to 99%, or a copolymer selected from the group consisting of (a) propylene and ethylene, (b) propylene, ethylene and a CH2=CHR .alpha.-olefin, where R is a C2-8 straight or branched alkyl group, and (c) propylene and an .alpha.-olefin as defined above in (i)(b), the copolymer containing 85% to 99%
propylene and having an isotactic index of 80% to 98%;
(ii) 3% to 20% of a semi-crystalline, essentially linear copolymer fraction having a crystallinity of 20% to 60% by differential scanning calorimeter (DSC), wherein the copolymer is selected from the group consisting of (a) ethylene and propylene containing over 50% ethylene; (b) ethylene, propylene, and an .alpha.-olefin as defined above in (i)(b), containing 1% to 10% of the .alpha.-olefin and over 50% up to 98% of both ethylene and the .alpha.-olefin; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing over 50% up to 98% of the .alpha.-olefin, which copolymer is insoluble in xylene at room or ambient temperatures and (iii) 40% to 80% of a copolymer fraction selected from the group consisting of a copolymer of (a) ethylene and propylene, wherein the copolymer contains from 20% to less than 40% ethylene (b) ethylene, propylene, and an .alpha.-olefin as defined in (i)(b), wherein the .alpha.-olefin is present in an amount of 1% to 10%. and the amount of ethylene and .alpha.-olefin present is from 20%
to less than 45%; and (c) ethylene and an .alpha.-olefin as defined in (i)(b), containing from 20% to less than 45% of the .alpha.-olefin, and optionally containing 0.5% to 10% of a diene, the copolymer fraction (iii) being soluble in xylene at ambient temperature, and having an intrinsic viscosity of 1.7 to 3.0 dl/g, wherein the total amount of fractions (ii) and (iii), based on the total olefin polymer composition is 65% to 80%, the weight ratio of fractions (ii) / (iii) is 0.1 to 0.3, and the total content of ethylene or C4-8 .alpha.-olefin or combination thereof in fractions (ii) + (iii) is less than 50%; and (4) a functionalized polymer that is reactive with the anhydride groups of the grafted polymers, selected from the group consisting of:
(a) 2.7 to 6 parts of an amine-terminated polyalkylene glycol per hundred parts of thermoplastic olefin;
(b) 2 to 6 parts per hundred parts of the thermoplastic olefin of a hydroxylated polymer selected from the group consisting of:
(i) hydroxylated polyethylene, (ii) hydroxylated polybutene, and (iii) hydroxylated polybutadiene; and c) 2 to 6 parts per hundred parts of the thermoplastic olefin of a mixture of (a) + (b) , where the ratio of (a) to (b) is 0.1 to 0.9, wherein (2)+(3) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin.
10. The composition of claim 9 which additionally comprises (5), 4 parts to 15 parts per hundred parts of the thermoplastic olefin, of a maleic anhydride grafted ethylene polymer having a maleic anhydride content of 2% to 13% and a molecular weight M n of 500 to 3000, wherein (2)+(3)+(5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin, and (3)+(5) is equal to or greater than 10 parts per hundred parts of the thermoplastic olefin.
11. The composition of any one of claims 1 to 6 or claim 9 or 10, wherein the ingredient (2) is the maleic anhydride-grafted propylene homopolymer.
12. The composition of any one of claims 1 to 6 or claim 9, or 11, wherein the ingredient (3) is the maleic anhydride-grafted polyolefin rubber (a).
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/792,915 US5959030A (en) | 1997-01-22 | 1997-01-22 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
| CA002228684A CA2228684C (en) | 1997-01-22 | 1998-02-04 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
| AU53020/98A AU753061B2 (en) | 1997-01-22 | 1998-02-09 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
| TW087102625A TW464673B (en) | 1997-01-22 | 1998-02-24 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
| RU98103650/04A RU2202571C2 (en) | 1997-01-22 | 1998-02-25 | Colorable thermoplastic olefin composition containing maleic anhydride-modified polymers, and product |
| US09/347,811 US6166132A (en) | 1997-01-22 | 1999-07-02 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/792,915 US5959030A (en) | 1997-01-22 | 1997-01-22 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
| CA002228684A CA2228684C (en) | 1997-01-22 | 1998-02-04 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2228684A1 CA2228684A1 (en) | 1999-08-04 |
| CA2228684C true CA2228684C (en) | 2003-01-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002228684A Expired - Fee Related CA2228684C (en) | 1997-01-22 | 1998-02-04 | Directly paintable thermoplastic olefin composition containing maleic anhydride-modified polymers |
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| Country | Link |
|---|---|
| US (2) | US5959030A (en) |
| AU (1) | AU753061B2 (en) |
| CA (1) | CA2228684C (en) |
| RU (1) | RU2202571C2 (en) |
| TW (1) | TW464673B (en) |
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| US6391461B1 (en) * | 1998-08-24 | 2002-05-21 | Visteon Global Technologies, Inc. | Adhesion of paint to thermoplastic olefins |
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| WO2004026956A1 (en) * | 2002-09-17 | 2004-04-01 | Basell Poliolefine Italia S.P.A. | Polyolefin composition with improved abrasion resistance |
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| CN102876052A (en) * | 2012-09-28 | 2013-01-16 | 新昌县绿泰塑胶有限公司 | Printable thermoplastic elastomer composition |
| DE102014218260A1 (en) * | 2014-09-11 | 2016-03-17 | Albis Plastic Gmbh | Adhesion-modified olefinic thermoplastic elastomers, in particular TPE-V, TPE-O |
| WO2016057124A1 (en) | 2014-10-06 | 2016-04-14 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin containing amorphous ethylene elastomer |
| WO2016130556A1 (en) * | 2015-02-13 | 2016-08-18 | Equistar Chemicals, Lp | Polyolefin-based compositions, adhesives, and related multi-layered structures prepared therefrom |
| US10364308B2 (en) | 2016-12-08 | 2019-07-30 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin compositions |
| US10513601B2 (en) | 2017-01-05 | 2019-12-24 | Exxonmobil Chemical Patents Inc. | Ethylene-propylene copolymers with amorphous and semi-crystalline components |
| US10822481B2 (en) | 2017-01-05 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin compositions with ethylene-propylene copolymers |
| ES2958562T3 (en) | 2017-02-03 | 2024-02-09 | Borealis Ag | Use of a polymer composition for the production of articles with improved paintability and surface appearance |
| CN112759768B (en) * | 2019-10-21 | 2022-01-28 | 国家能源投资集团有限责任公司 | Polypropylene modifier and preparation method thereof, polypropylene composition, polypropylene material and preparation method thereof |
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| ES2100166T3 (en) * | 1989-11-14 | 1997-06-16 | Mitsubishi Chem Corp | RESIN MOLDED PIECES WITH LINING. |
| US6031048A (en) * | 1993-07-13 | 2000-02-29 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| DE69403398T2 (en) * | 1993-07-13 | 1997-09-25 | Huntsman Spec Chem Corp | Modification of polypropylene by polyether amines |
| US5783630A (en) * | 1993-07-13 | 1998-07-21 | Huntsman Petrochemical Corporation | Polyether amine modification of polypropylene |
| EP0662496A3 (en) * | 1994-01-06 | 1995-09-27 | Goldschmidt Ag Th | Additives for paintable and printable polyolefin compositions. |
| US5815946A (en) * | 1996-09-10 | 1998-10-06 | Dean; Miles W. | Method for dehydrating wet coal |
-
1997
- 1997-01-22 US US08/792,915 patent/US5959030A/en not_active Expired - Fee Related
-
1998
- 1998-02-04 CA CA002228684A patent/CA2228684C/en not_active Expired - Fee Related
- 1998-02-09 AU AU53020/98A patent/AU753061B2/en not_active Ceased
- 1998-02-24 TW TW087102625A patent/TW464673B/en active
- 1998-02-25 RU RU98103650/04A patent/RU2202571C2/en not_active IP Right Cessation
-
1999
- 1999-07-02 US US09/347,811 patent/US6166132A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| RU2202571C2 (en) | 2003-04-20 |
| TW464673B (en) | 2001-11-21 |
| AU5302098A (en) | 1999-08-26 |
| US5959030A (en) | 1999-09-28 |
| AU753061B2 (en) | 2002-10-10 |
| CA2228684A1 (en) | 1999-08-04 |
| US6166132A (en) | 2000-12-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |