CZ20003077A3 - Composition of grafted polypropylene copolymers, employment thereof and products produced from such composition - Google Patents

Abstract

The abrasion and wear resistance polymer composition comprises: 1) a graft copolymer comprising a backbone of a polypropylene polymer to which at least one free radical-capable vinyl monomer is grafted and 2) an additive selected from the group consisting of a) O 5% to 10% of at least one low molecular weight ethylene polymer or functionalized derivative thereof; and b) a mixture of 0.5% to 10% of one of the low molecular weight polyethylenes and 0.5% to 10% of inorganic microspheres based on the total weight of the composition. Optionally, the composition may also contain a compacting agent, such as a propylene polymer, functionalized with an unsaturated carboxylic acid

Description

Composition of graft polypropylene copolymers, method of use, and articles of composition made.

Technical field

The present invention relates to compositions comprising a graft copolymer of propylene polymer material onto which one or more monomers are grafted.

BACKGROUND OF THE INVENTION

Manufactured products prepared from polyolefins have poor abrasion and wear resistance. This means that their surface is easily worn or abraded by slight scratches, such as finger nails. Articles made of modified polyolefins, such as polypropylene materials grafted with one or more monomers, such as styrene and acrylic compounds, also exhibit poor abrasion and wear resistance. When rubber is added to these graft copolymers, the abrasion resistance and wear of such articles will usually deteriorate.

The abrasion and wear resistance of thermoplastic olefins, which are non-crosslinked compositions of crystalline olefin polymers and polyolefine elastomers, have been improved by adding a lubricant such as polysiloxane, either alone or in combination with an aliphatic amide such as erucamide or oleamide, as described in European patent application 832,925 .

There is a need to improve the abrasion and wear resistance of a graft copolymer composed of a polypropylene material forming its backbone on which vinyl monomers ⁷ are grafted while maintaining a good balance between mechanical properties and high surface gloss.

SUMMARY OF THE INVENTION

The composition of the invention consists of 1) a graft copolymer. the backbone of which is a polypropylene material on which at least one vinyl monomer capable of free-radical polymerization is grafted, the polymerized

the monomers are present in an amount of about 10 to 120 parts per hundred parts of the polypropylene material, and 2) an additive selected from the group consisting of a) about 0.5% to 10% of at least one low molecular weight polyethylene or a functional group derivative thereof; and b) a combination of i) about 0.5% to 10% of at least one of the low molecular weight polyethylenes in a) and ii) about 0.5% to 10% of inorganic microspheres based on the total weight of the composition. Optionally, the compositions may also contain a binder, such as polypropylene with carboxyl functional groups.

Optionally, the composition comprises about 2% to 30% of one or more rubber components, about 15% to 50% of a wide molecular weight distribution polypropylene material, or a combination thereof.

The made-up products of these compositions have a glossy surface ⁷ that is far more resistant to abrasion and wear than typical graft copolymers ⁷ of the type described above.

DETAILED DESCRIPTION OF THE INVENTION.

Component 1) of the composition according to the invention is a graft copolymer comprising a polypropylene backbone on which at least one vinyl monomer capable of free radical polymerization is grafted.

The polypropylene material used as the backbone of the graft copolymer may be:

1) a propylene homopolymer having an isotacticity index greater than 80, preferably about 85 to 99;

2) a propylene-olefin copolymer selected from the group consisting of ethylene and 4-10 C alpha-olefins, provided that the olefin is ethylene, the maximum polymerized ethylene content is about 10%, preferably about 4%, and if the olefin is 4 to 10 C alpha-olefin, then the maximum content of its polymer is 20% by weight, preferably about 16%, the copolymer has an isotacticity index greater than 85,

3) a propylene and two olefin terpolymer selected from the group consisting of ethylene and 4 to 8 C alpha-olefins, provided that the maximum content of polymerized 4 to 8 C alpha-olefin is 20 wt%, preferably about 16%, and is if ethylene is one of the olefins, the maximum content of polymerized ethylene is 5% by weight, preferably about 4%, the terpolymer has an isotacticity index greater than 85,

4) an olefin polymer composition comprising:

a) about 10 to 60 wt. preferably about 15% to 55% propylene homopolymer, with an isotacticity index greater than 80, preferably about 85 to 98, or

a copolymer of monomers selected from the group consisting of (i) propylene and ethylene, (ii) propylene, ethylene and 4-8 C alpha-olefin, and iii) propylene and 4-8 C alphaoiefin, the copolymer having a polymerized propylene content of greater than 85% %, preferably about 90% to 99%, and an isotacticity index greater than 85,

b) about 5% to 25% by weight, preferably about 5% to 20%, of an ethylene-propylene copolymer, or 4-8C alpha-olefin which is insoluble in xylene at ambient temperature; and

c) about 30% to 70% by weight, preferably about 40% to 65%, of an elastomeric copolymer formed of copolymers of monomers selected from the group consisting of i) ethylene and propylene, ii) ethylene, propylene and 4-8 C alpha-olefin and iii) ethylene and a 4-8 C alpha-olefin, the copolymer optionally containing about 0.5% to 10% by weight. % of polymerized diene and contains less than 70% by weight, preferably about 10% to 60%, most preferably about 12% to 55% polymerized ethylene and which is soluble in xylene at ambient temperature and has an intrinsic viscosity measured in tetrahydronaphthalene at 135 ° C about 1.5 to 4.0 dkg, wherein the total amount of b) and c) based on the total olefin polymer composition is about 50% to 90%, the weight ratio b) / c) is less than 0.4, preferably 0.1 to 0.3, the composition is prepared by polymerization in at least two steps and the flexural modulus is less than 150 MPa; or

5) thermoplastic olefin, containing:

a) about 10% to 60%, preferably about 20% to 50%, of a propylene homopolymer having an isotacticity index of greater than 80, or a copolymer of monomers selected from the group consisting of i) ethylene and propylene and ii) ethylene, propylene and And (iii) ethylene and a 4-8 C alpha-olefin, the copolymer having a polymerized propylene content greater than 85% by weight, and an isotacticity index greater than 85;

b) about 20% to 60%, preferably about 30% to 50%, of an amorphous copolymer of monomers selected from the group consisting of i) ethylene and propylene, and ii) ethylene, propylene, and 4-8 C alpha-olefin, and iii) of ethylene and 4-8 C alpha-olefin, the copolymer optionally contains about 0.5% to 10% polymerized diene, and has less than 70% polymerized ethylene and is soluble in xylene at ambient temperature; and

c) about 3% to 40%, preferably about 10% to 20% of an ethylene-propylene copolymer or 4 to 8 C alpha-olefin, and is insoluble in xylene at ambient temperature, wherein the thermoplastic olefin has an E-modulus in bend greater than 150 but less than 1200 MPa, preferably about 200 to 1100 MPa, and most preferably about 200 to 1000 MPa.

Room or ambient temperature is ~ 25 ° C.

to 8 C alpha-olefins useful in the preparation of (4) and (5) include, for example, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene, and octene-1.

When a diene is included in the composition, it is typically butadiene; 1,4-hexadiene; 1,5-hexadiene or ethylidennorbomen.

The propylene polymer-based materials of (4) and (5) may be prepared by polymerization in at least two stages wherein propylene is polymerized in the first stage; propylene and ethylene; propylene and alpha-olefin, or propylene, ethylene and alpha-olefin, to form component a) of item 4) or 5), and ethylene and propylene compositions are polymerized in subsequent steps; ethylene and alpha-olefin or ethylene, propylene and alpha-olefin and optionally diene in the presence of components a) to form components b) and c) of 4) or 5).

The polymerization can be carried out in the liquid phase, the gas phase, or the liquid-gas phase, using separate reactors, either in batches or continuously. For example, it is possible to carry out polymerization of component a) using liquid propylene as a diluent, and gas phase polymerization of components b) and c) without intermediate steps, except for partial degassing of propylene. All gas phase polymerizations are preferred.

The preparation of polymeric propylene material 4) is described in more detail in U.S. Pat. 5,212,246 and 5,409,992, which are incorporated herein by reference. The preparation of polymeric propylene material 5) is described in more detail in U.S. Pat. Nos. 5,302,454 and 5,409,992, which are also incorporated herein by reference.

The propylene homopolymer is a more preferred polymeric propylene material forming the backbone of the copolymer.

The monomers that can be grafted onto the backbone of the polypropylene material can be any monomeric vinyl compounds capable of free radical polymerization, wherein the vinyl radical H 3 -C 2 CR-, where R = H or methyl, is added to a straight or branched aliphatic chain or to a substituted or an unsubstituted aromatic, heterocyclic or alicyclic ring in a mono- or polycyclic compound. Typical substituents may be alkyl, hydroxyalkyl, aryl and halogens. Typically, the vinyl monomer will be part of one of the following classes: 1) vinyl substituted aromatic, heterocyclic or alicyclic compounds including styrene, vinyl naphthalene, vinylpyridine, vinylpyrrolidone. vinylcarbazole and their homologues, i.e. alpha- and para-methylstyrene, methylchlorstyrene, p-tert-butylstyrene. methylvinyl pyridine and ethylvinyl pyridine; 2) vinyl esters of aromatic and saturated aliphatic carboxylic acids, including vinyl formate, vinyl acetate, vinyl chloroacetate, vinyl cyanoacetate, vinyl propioate and vinyl benzoate; and 3) unsaturated aliphatic nitriles and carboxylic acids and derivatives thereof, including acrylonitrile, methacrylonitrile, acrylamide, metha blood amide, acrylic acid, esters thereof such as methyl, ethyl, hydroxyethyl, 2-ethylhexyl and butyl acrylates, methacrylic acid, ethacrylic acid, ethacrylic acid methacrylates. such as methyl, ethyl, butyl, benzyl, phenylethyl, phenoxyethyl, epoxypropyl and hydroxypropyl methacrylates, maleic anhydride and N-phenylmaleimide. ⁷ multiple monomers from the same or different classes can be used. Methyl methacrylate and methyl acrylate, or methyl methacrylate and methacrylic acid, wherein the methyl acrylate or methacrylic acid is present in an amount of about 0.5% to 10%. based on the total weight of the monomers, grafting monomers are more preferred.

The polymerized monomers ⁷ contain about 10 to 120 parts per hundred parts of polypropylene material, preferably about 30 to 95 pph.

During the graft polymerization, the monomers also polymerize to form some free or ungrafted polymers. The morphology of the graft copolymers is such that the polypropylene material is a continuous or matrix phase and the polymerized monomer, both grafted and non-grafted, is a dispersed phase.

The graft copolymer can be prepared in various ways. One is to create an active grafting site on the polypropylene chain with peroxide or another chemical compound that initiates radical polymerization, or by irradiation with high energy ionization radiation. Free radicals formed on the polymer, as a result of chemical or radiation action, create active grafting sites on the polymer, and initiate polymerization of monomers at these sites. Graft copolymers prepared by peroxides initiated grafting processes are more preferred.

The preparation of graft copolymers by reacting polypropylene with a vinyl monomer under the action of radical polymerization initiators such as organic peroxides is described in more detail in U.S. Pat. No. 5,140,074, which is incorporated herein by reference. The preparation of graft copolymers by irradiation of an olefin polymer and subsequent reaction with a vinyl monomer is described in more detail in U.S. Pat. No. 5,411,994, which is also incorporated herein by reference.

Component 2) of the composition of the invention may be at least one low molecular weight polyethylene having a number average molecular weight (Mn) of about 300 to 5000. Functionalized derivatives ^{7 of} these ethylene polymers, such as hydroxylated or ethoxylated derivatives, or phosphate esters thereof, or Primary carboxylic acid derivatives

acids or linear polymers of ethylene grafted with maleic acid may also be used. The ethylene polymer, or combination of ethylene polymers, is present in an amount of 0.5% to 10%, preferably about 2% to 5, based on the total weight of the composition.

Component 2) may also be a combination of i) about 0.5% to 10% of at least one of the low molecular weight polyethylenes described above, and ii) about 0.5% to 10%, preferably about 1% to 5%, based on the total weight of the composition, inorganic microspheres. The inorganic microspheres may be, for example, a ceramic silica-alumina alloy, an alkaline aluminosilicate ceramic or glass, and may optionally be coated with a sizing agent such as an aminosilane.

The composition may also comprise a compatibility agent such as polypropylene modified with α, β-unsaturated carboxylic acid or alicyclic carboxylic acid and derivatives thereof such as acrylic acid, methacrylic acid. maleic, fumaric, itaconic, endocyclo (2,2,1) -5-heptene-2,3-carboxylic acid and cis-4-cyclohexane-1,2-carboxylic acid and their anhydrides, esters, amides and imides. Polypropylenes modified with varying amounts of maleic anhydride or maleic acid are more preferred and are commercially available, e.g., from Eastman Chemical Company and Aristech Chemical Corporation. The modified polypropylenes generally contain about 0.2% to 10% maleic acid or maleic anhydride based on the total weight of the modified polymer. When the compatibilizer is included in the composition, it is used in an amount of about 0.2% to 4%, preferably about 0.5% to 2%, based on the total weight of the composition.

Optionally, the composition may also contain about 2% to 30%, preferably about 5% to 30%, based on the total weight of the composition, one or more rubber components, and / or about 15% to 50%. preferably about 40% to 50%, based on the total weight of the composition, of a polypropylene material with a broad molecular weight distribution.

The rubber component is selected from one or more groups comprising i) an olefin copolymer rubber, ii) a monoalkenyl aromatic hydrocarbon-conjugated diene block copolymer, and iii) a core shell rubber. Either of these rubber components may have an acidic or anhydride functional group or may be without them. Preferred rubber components are i) or ii), either alone or in combination.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Suitable olefin copolymer rubbers include, for example, saturated olefin copolymer rubbers such as ethylene / propylene monomer rubbers (EPM), ethylene / octene-1 and ethylene / butene-1 rubbers and unsaturated olefin copolymer rubbers such as ethylene / propylene / diene rubber monomer (EPDM). Preferred olefin copolymer rubbers are ethylene / propylene, ethylene / butene-1 and ethylene / octene-1 copolymers.

The monoalkenyl aromatic hydrocarbon-conjugated diene block copolymer may be a thermoplastic elastomer of AB (or diblock) structure, ABA (or triblock) structure lines, radial (AB) _n type wherein n 3 to 20%, or a combination of these structural types. each A block is a monoalkenyl aromatic hydrocarbon polymer block, each B block is an unsaturated rubber block. Various types of copolymers of this type. are commercially available. The species differ in structure, molecular weight of the middle and terminal blocks, and in the ratio of monoalkenyl aromatic hydrocarbon to rubber. The block copolymer can also be hydrogenated. Typical monomer} ⁷ monoalkenyl aromatic hydrocarbons are styrene, ring-substituted styrenes, linear or branched C 1-4 alkyl group, and vinyl toluene. Styrene is preferable. Suitable conjugated dienes include, for example, butadiene and isoprene. Preferred block copolymers are a tri-block copolymer of hydrogenated styrene / ethylene-butene-1 / styrene.

The weight average molecular weight (M _{w) of} the block copolymers is generally in the range from about 45.000 to 260.000 g / mole, average molecular weights in the range from about 50.000 to 125.000 g / mole are preferred because they provide the composition with the best balance of toughness and stiffness. Although block copolymers with both unsaturated and saturated rubber blocks can be used, copolymers with saturated rubber blocks are preferred because of a better balance of toughness / stiffness of such compositions. The weight ratio of monoalkenyl aromatic hydrocarbon to conjugated diene rubber in the block copolymers is in the range of about 5/95 to 50/50, preferably about 10/90 to 40/60.

The encapsulated rubber components contain small particles of a cross-linked rubber phase, surrounded by a compatible shell, regularly made of glassy polymer or copolymers. The core (eore) is typically a diene rubber, such as butadiene or isoprene rubber, or polyacrylate. The shell is typically a polymer of two or more monomers such as styrene, methyl methacrylate and acrylonitrile. Particularly preferred encapsulated rubbers have a polyacrylate core.

• · · · · · · · · · ·

Suitable rubbers useful as toughness modifiers include, e.g., Engage 8150 or Engage 8200 ethylene octene-1 copolymer, commercially available from DuPont-Dow Eastomers; ΕΡΜ 306P ethylene propylene copolymer, commercially available from Polvsar Rubber Division of Miles, Incorporated; and Kraton RP 6912, a styrene / ethylene / propylene / styrene tri-block copolymer rubber and Kraton FG 190IX, a styrene / ethylene-butene-1 / styrene / copolymer rubber modified with maleic anhydride, commercially available from Shell Chemical Company.

Another optional additive is a wide molecular weight distribution (BMWD PP) polypropylene material with an M _w / M _n ratio of about 5 to 60, preferably about 5 to 40; melt index of about 0.5 to 50, preferably about 1 to 30 g / 10 min, xylene insolubility at 25 ° C greater than or equal to 94%, preferably greater than or equal to 96%, and most preferably greater than or equal to 98% . The polypropylene material with a broader molecular weight distribution can be a propylene homopolymer or ethylene / propylene rubber, a modified toughness propylene homopolymer, wherein the propylene homopolymer has a broad molecular weight distribution.

BMWD PP is prepared by sequential polymerization in two stages, in the presence of a Ziegler-Natta catalyst, supported by magnesium halide in active form. The polymerization takes place in separate and successive stages, and in each stage the polymerization is carried out in the presence of the polymer and catalyst from the previous stage.

The polymerization can be carried out in batches or continuously, by known techniques, in the liquid phase in the presence or absence of an inert solvent, or in the gas phase, or in the liquid-gas phase, preferably in the gas phase. The preparation of BMWD PP is described in more detail in U.S. Pat. No. 5,286,791, which is incorporated herein by reference.

Other additives such as pigments, nucleating agents, pigment dispersants, primary and secondary antioxidants, UV stabilizers, acid scavengers, glidants, and fillers such as talc, calcium carbonate and wollastonite may also be included in the compositions.

Articles can be made from the compositions of the present invention by methods known in the art such as, for example, thermoforming, injection molding, profile extrusion, film extrusion, and blow molding.

The test methods used to evaluate the samples were as follows:

Izod notch tensile strength Tensile strength Yield strength

ASTM-D-256A

ASTM-D-638-89

ASTM-D-638-89

ASTM-D-638-89

ASTM-D-790-86

ASTM-D-790-86

ASTM D-1238

Elongation at break Bending strength E-modulus bending Flow index (230 ° C, 2.16 kg)

Abrasion and wear resistance was measured using the Ford laboratory test method BN 108-13 (abrasion resistance). The apparatus consists of several weighing tips that touch the test specimens. The spikes used for the abrasion test were terminated with highly polished steel spheres of 1.0 mm diameter and the diameter of the spheres of the spikes for the wear test was 7.0 mm. The spikes were loaded with different weights, performing the following standard forces on the surface of the test plates: 7.0 Newtons (N); 6.0 N; 3.0 N; 2.0 N; The tips were then pulled across the panel. All scratches were examined and graded from 1 to 5 with 1 no scratch and 5 = strong scratches. The improvement with respect to the comparative sample was a criterion for acceptable results. A black pigmented test specimen was used because experience has shown that a black surface is easier to observe with the naked eye than surfaces of other colors.

All surface gloss readings were performed on a 20 degree gloss meter on a smooth (unmuted) sample.

The Chrysler crocking gloss test was performed according to the procedure of the Chrysler Laboratory LP-463PB-54-01, using an Atlas AATCC Mar Tester, Model CM-5. A Bon-Ami dry cleaning agent was applied to a half-pressed 10.16 cm x 15.24 cm test plate. The cylindrical acrylic finger of Mar Tester was coated with green felt 14-9956-000 5.08 cm x 5.08 cm, commercially available from Atlas Electric Devices Co. The pad covered with detergent was polished with wool felt ten times (ten double strokes). The 20 ° gloss was measured at several points on worn and unused pad surfaces. The maximum gloss value on an unused surface was designated as the original gloss. The minimum gloss on the worn surface was marked as wear gloss. The gloss retention in%, or wear resistance, is calculated from the value of the worn gloss divided by the value of the original gloss x 100.

The Ford crocking gloss test was performed according to the procedure of Ford Laboratory B1 161-01, Determination of Wear Resistance of Automotive Paints, using an Atlas AATCC Mar Tester, Model CM-5. 28IQ Wetordry Production Polishing Paper, size 50 mm x 50 mm, commercially available from Minnesota Mining and Manufacturing Company (standard quality) 3 gm is better than 2 gm), bvl is laid on green felt 14-9956-000 of similar size, commercially available from Atlas Electric Devices Co., with the abrasive side of the polishing paper facing outwards. The two squares were wrapped and fastened around the finger of the machine so that the felt was between the finger and the polishing paper. The apparatus was fitted with a cylindrical acrylic, brass or wooden finger with a diameter of 16 mm and exerted a force of 9 N on the test surface and had a tension of approximately 100 mm. After the 20 ° gloss of the test surface was measured, it would! on this surface 10 double strokes performed in the wear test. The 20 ° gloss of the abraded pad was measured in a direction parallel to the abrasive strokes of the Mar tester, and the lowest reading was recorded. The gloss retention in%, or wear resistance, is the 20 ° gloss of the abraded facet, divided by the original 20 ° gloss x 100.

The isotacticity index is defined as the% solubility in xylene. The weight percent solubility of the olefin polymer in xylene at room temperature is determined by dissolving 2.5 g of polymer in 250 ml of xylene at room temperature in a stirrer vial, heating to 135 ° C with stirring for 20 minutes. The solution is cooled to 25 ° C, with stirring, then left without stirring for 30 minutes so that the solids settle. The sediment is filtered off with filter paper, the remaining solution is evaporated under a stream of nitrogen and the solid is dried under vacuum at 80 ° C to constant weight. %, Insoluble in xylene, in wt. at room temperature, is the isotacticity index of the polymer. The value obtained in this way essentially corresponds to the isotacticity index determined by extraction in boiling n-heptane, which by definition determines the isotacticity index of the polymer.

The intrinsic viscosity was measured in tetrahydronaphthalene at 135 ° C.

In all of the following examples, the test specimens, according to ASTM, were conditioned at 23 ° C and 50% relative humidity for 48 to 96 hours prior to the test. Before the abrasion and wear test plates were formed, the extruded granules of each sample were dried at 8080 ° C for a minimum of 1 hour but usually overnight. The shaped abrasion and wear plates were given to age at ambient temperature and humidity, at least 48 hours prior to the test.

In the description of this application, all parts and percentages are by weight unless otherwise expressly stated.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

This example describes the effect of low molecular weight polyethylene on the abrasion and wear resistance of a composition comprising 5% rubber and a graft copolymer consisting of a propylene homopolymer forming a backbone to which a methyl methacrylate / methyl acrylate (MMA / MeAc) copolymer is grafted.

In this and the following examples, the propylene homopolymer used as copolymer backbone had the following properties: spherical shape, flow index (A1FR) 9.8 dg / min at 230 ° C and 2.16 kg, and 96.1% insolubility in xylene at room temperature ⁷ .

Monomers (95.6% MMA and 4.4% MeAc, based on the total weight of the monomers) were grafted onto the polypropylene backbone at a grafting temperature of 114 ° C, using the previously described peroxide-initiated graft polymerization process. Ninety-five parts by weight. of monomers was added per 100 parts of polypropylene. Lupersol PMS, 50% t-butylperoxyxy-2-ethylhexanoate in light petroleum, commercially available from Elf Atochem, was used as the peroxide initiator. Monomers were dosed at 1 pph min for 95 minutes. A monomer / initiator molar ratio of 120 was used. After the addition of the monomers, the temperature was raised to 140 ° C for 60 to 120 minutes, the polymerization proceeded under pure nitrogen until the amount of unreacted MMA in the product was <500 ppm.

The graft copolymer was blended with a wide molecular weight distribution polypropylene (BMWD PP) having a flow index of 1.36 g / 10 min, commercially available from Montell USA Inc. The amount of BMWD PP used for each sample is shown in Table 1. Sufficient BMWD PP was added to provide an effective level of 30 pph polymerized monomers per hundred parts of polypropylene (BMWD PP plus backbone polypropylene).

The rubber used was a copolymer of ethylene octene Engage 8150 containing 25% octene and is commercially available from DuPont-Dow Elastomers. The polyethylene wax was polyethylene (PE) Polywax 3000, a fully saturated homopolymer, having a melting point of 129 ° C and a number average molecular weight (M ") of 3000, is commercially available from Baker Petrolite, Polymers Division.

The masterbatch of the UV stabilizer contained 0.05% Pationic 1240, modified with calcium salt, derived from lactic acid, commercially available from the Patco Polymer Additives Division, American Ingredients Company; 0.10% antioxidant

Irganox 1010 which m is tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane; 0.10% of the antioxidant Irgafos 12 which is 2,2,2'-nitrilotriethyltris [3,325,5-tetra-tert-butyl-1,1'-diphenyl-2,2'-diyl] phosphite; 0.30% of Tinuvin 328 antioxidant 2- (2-hydroxyl-3,5-di-tert-amylphenyl) -2H-benzotriazole; 0.25% of the antioxidant Tinuvin 770 which is bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and 0.25% of the antioxidant Chimassorb 119, all commercially available from Ciba Specialty Chemicals Corporation.

The pigment was a 191067 Black concentrate, commercially available from Ampacet Corporation. The amount shown in the table is expressed in parts per hundred parts of the colorless formulation.

The sample material was prepared by mixing on a 40 mm WemerPfleiderer twin screw extruder. with interlocking, co-rotating worms. Each sample was extruded as a granulate.

The test specimens were prepared by injection molding on a 400 g Van Dom injection molding machine at a melt temperature of -227 ° C and an injection temperature of 60 ° C. The results are shown in Table 1. Abrasion and wear plates (10.16 x 15.24 x 0.3 cm) were prepared on a 142 g Battenfeld injection molding machine at a jacket temperature of 238 ° C and an injection temperature of 82 ° C at an injection rate of 0, 51 cm / sec. The results are shown in Table 1.

• • •

j Table 1 Sample Cf. 1 1 Type of graft copolymers MMA / MeAc MMA / MeAc Graft copolymer (wt%) 44.50 42.13 BMWD PP (wt.%) 49.45 46.82 Rubber (% by weight) 5.00 5.00 Polyethylene wax (% by weight) 0 5.00 Stabilizer masterbatch (wt%) 1.05 1.05 Black pigment 3 3 Notch toughness (J / cm) 0.69 0.64 Tensile strength (MPa) 33.8 34.8 Elongation at break (%) 174 57 E-modulus in bending (0.13 cm / min) (MPa) 1559 1629 Bending strength (0.13cm / min) (MPa) 46.8 48.0 and 1 Initial gloss (20 °) (%) 78.3 81.6 Chrysler Crocking Gloss (20 °) (%) 1.3 23 Gloss retention (%) 1.7 28.2 Ford Crocking Gloss (20o) (%) 1 6 Gloss retention (%) 2 7 Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 55433 44332 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 45433 23232 i and

The data show that the addition of a low molecular weight ethylene polymer has improved abrasion and wear resistance while maintaining a good balance of physical properties.

• · ···

Example 2

This example describes the effect of low molecular weight polyethylene, or a combination of low molecular weight polyethylene and ceramic microspheres, on the abrasion and wear resistance of a composition comprising 10% rubber and a graft copolymer consisting of a propylene homopolymer as backbone grafted to an MMA / MeAc copolymer.

The graft copolymer was prepared as described in Example 1.

The graft copolymer was blended with BMWD PP as described in Example 1.

Ceramic microspheres were of the X-155 Zeeospheres type, a ceramic silica-alumina alloy in which 90% by volume of the sample had a particle size of <7.0 to 10 tonnes. The microspheres were treated with Union Carbide A1100 and are commercially available from Zeelan Industries, Inc. All other components of the composition were the same as in Example 1. The samples were prepared and molded as described in Example 1, except the melting point during injection of the test pieces was 238 ° C. The results of the physical properties tests and the abrasion and wear tests are given in Table 2.

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The data show that abrasion and wear resistance is improved by the addition of a low molecular weight polymer of ethylene and ceramic microspheres, while maintaining a good balance of physical properties.

Example 3

This example describes the effect of low molecular weight polyethylene, or a combination of low molecular weight polyethylene and ceramic microspheres, on the abrasion and wear resistance of a composition comprising 10% rubber and a graft copolymer consisting of a propylene homopolymer as backbone onto which methyl methacrylate / methacrylate copolymer MMA / MAA).

The graft copolymer was prepared as described in Example 1. except that the amount of MAA was 10% by weight of the total monomer feed.

The graft copolymer was blended with BMWD PP, as described in Example 1. Ceramic microspheres were described in Example 2. All other components of the compositions were the same as in Example 1.

The samples were prepared and molded as described in Example 1, except for the melting temperature during injection of the test pieces, which was 238 ° C. The results of the physical properties tests and the abrasion and wear tests are given in Table 3.

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The data show that the abrasion and wear resistance is improved by the addition of a low molecular weight ethylene polymer, or a combination of ethylene polymer and ceramic microspheres, while maintaining a good balance of physical properties.

Example 4

This example describes the effect of low molecular weight polyethylene on the abrasion and wear resistance of a composition comprising 20% rubber and a graft copolymer consisting of a homopolymer as backbone onto which an MMA / MeAc copolymer is grafted. This graft copolymer was prepared as described in Example 1.

This copolymer was blended with BMWD PP as described in Example 1.

All components of the compositions were the same as in Example 1.

The samples were prepared and formed as described in Example 1. The results of physical properties and abrasion and wear resistance tests are described in Table 4.

• ·

Table 4 Sample Cf. 1 1 Type of graft copolymer MMAMeAc MMAMeAc Graft copolymer (wt%) 37.40 35,03 BMWD PP (wt.%) 41.55 38,92 Rubber (% by weight) 20,00 20,00 Polyethylene wax (% by weight) 0 5.00 Stabilizer masterbatch (wt%) 1.05 1.05 i What pigment 3 3 Notch toughness (J / cm) 7.4 8.3 Tensile strength (MPa) 26.4 25.1 Elongation at break (%) 511 499 E-modulus in bending (0,13 cra / min) (MPa) 1139 1063 Flexural strength (0.13cm / inin) (MPa) 33.9 31.6 Initial gloss (20 °) (%) 76.6 78.9 Chrysler Crocking Gloss (20 °) (%) 0.4 5 Gloss retention (%) 0.5 6.3 Ford Crocking Gloss (20o) (%) 1 3 Gloss retention (%) 1 4 Ford 5-finger - abrasion (7.6, 3, 2, 0.6 N) 54433 44332 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 55543 44333

The data show that abrasion and wear resistance will be improved by the addition of low molecular weight polyethylene while maintaining a good balance of physical properties.

····· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Example 5

This example describes the effect of various types of low molecular weight polyethylene additives on the abrasion and wear resistance of a composition containing 2.5 wt. ceramic microspheres, 1.0% maleate polypropylene (PP) as a compatibilizer, and graft copolymers containing a propylene homopolymer as backbone to which an MMA / MeAc copolymer is grafted.

The graft copolymer was prepared as described in Example 1. The graft copolymer was blended with BMWD PP as described in Example 1. The amounts of BMWD PP and other components of the composition are shown in Table 5.

The rubber, BMWD PP, black pigment and stabilizer masterbatch were the same as in Example 1. Ceramic microspheres were of the X-92 Zeeospheres type, a silica-alumina ceramic alloy in which 90% by volume of the sample had a particle size <6.0 to 7, 4 pm. Commercially available from Zeelan Industries, Inc. Maleic acid grafted polypropylene (maleate PP) was a type Unit MP 1000, commercially available from Aristech Chemical Corporation.

Polyethylene Polywax 3000 (P-wax 3000) was described in Example 1. Polyethylene Polywax 850 (P-wax 850) is a fully saturated homopolymer with a melting point of 107 ° C and a Mn = 850. Unilin 700, a long chain alcohol has a melting point 105 ° C and M _n = 700 and is commercially available from Baker Petrolite. Polymers Division. Unithox 720, ethoxylated alcohol has a melting point of 106 ° C and M = 875 and is commercially available from Baker Petrolite, Polymers Division. Unicide 700, a carboxylic acid, has an Mn = 700 and a melting point of 110 ° C and is commercially available from Baker Petrolite, Polymers Division, X-5005, X-2025 and X-2026, branched polyethylene waxes, are commercially available from Baker Petrolite, Polymers Division.

The sample material bvl was prepared by mixing on a 34 mm Leistritz twin-screw extruder, with a concurrent clue of interlocking screws, at a melt temperature of 232-237 ° C, with a screw rotation speed of 250 rpm, and a discharge capacity of 9.1 kg'h. Suction was used during extrusion.

Abrasion and wear test plates were prepared on a 142 g Battenfeld injection molding machine with a jacket temperature of 238 ° C and an injection temperature of 82 ° C at an injection rate of 0.51 ciws. The results of the abrasion and wear tests are given in Table 5.

• ·

• · ·

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• • •

• · ·

The data show that the abrasion and wear resistance is improved by the addition of a combination of ceramic microspheres and various low molecular weight polyethylenes, both linear and branched, with or without functional groups.

Example 6

This example describes the effect of different amounts of low molecular weight polyethylenes with three different number average molecular weights on the abrasion and wear resistance of compositions containing 10% rubber and a graft copolymer consisting of a propylene homopolymer as backbone to which an MMA / MeAc copolymer is grafted. .

The graft copolymer was prepared as described in Example 1.

The graft copolymer was blended with BMWD PP as described in Example 1.

The amounts of BMWD PP and other components of the composition are shown in Table 6.

Polyethylene Polywax 3000 was described in Example 1. Polyethylene Polywax 850 was described in Example 5. Polyethylene Polywax 2000 is a fully saturated homopolymer with a melting point of 126 ° C and M 2 = 2000. Rubber, BMWD PP, black pigment and stabilizer premix were described in of Example 1.

The sample material was prepared by mixing on a 34 mm Leistritz twin screw extiuder, with parallel running, interlocking screws, at a melt temperature of 269 to 275 ° C, with a screw speed of 250 rpm, and a discharge rate of 9.1 kg / h. Suction was used during extrusion.

The test specimens were injected on a 142 g Battenfeld injection molding machine, at a melt temperature of 232 ° C and an injection temperature of 66 ° C. The abrasion and wear test plates were prepared as described in Example 1. The results of the abrasion and wear test are given in Table 6.

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The data show that the degree of abrasion and wear resistance improves as the amount of low molecular weight polyethylene increases and that both abrasion and wear are more favorable to the comparative sample at each molecular weight.

Example 7

This example describes the effect of various amounts of low molecular weight polyethylene on the abrasion and wear resistance of a composition comprising 2.5% ceramic microspheres, 1% maleate polypropylene, 10% rubber and a graft copolymer consisting of a polypropylene homopolymer as the backbone on which it is grafted MMA / MeAc copolymer.

Preparation of the graft copolymer and mixing with BMWD PP were described in Example 1. Material preparation and sample forming were described in Example 6.

Ceramic microspheres and maleate polypropylene as compatibilizer were described in ⁷ Example 5. Polyethylene wax was polyethylene, Polywax 3000 and was described in Example 1. The other components of the compositions were the same as in Example 6 and the amount is shown in Table 7. Abrasion and wear test results Table 7.

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The data show that the degree of abrasion and wear increases with increasing amounts of low molecular weight polyethylene.

Example 8

This example describes the effect of different amounts of ceramic microspheres with or without maleate polypropylene as a compatibilizer on the abrasion and wear resistance of a composition comprising 5% low molecular weight polyethylene, 10% rubber and a graft copolymer consisting of a propylene homopolymer as backbone. which is an grafted MMA / MeAc copolymer.

The preparation of the graft copolymer and mixing with BMWD PP were described in Example 1. The sample material was prepared on a 40 mm Wemer-Pfleiderer twin screw extruder, with parallel running, interlocking screws.

Test specimens were prepared on a 142 g Battenfeld injection molding machine with a melt temperature of 232 ° C and a sample injection temperature of 66 ° C. The abrasion and wear test plates were formed as described in Example 1.

Ceramic microspheres and maleate polypropylene were described in Example 5. The other ingredients of the composition were the same as in Example 1 and their amounts are shown in Table 8. The results of physical properties and abrasion and wear tests are shown in Table 8.

• · • ·

Table 8 Sample Cf. 1 1 2 3 Graft copolymer (wt%) 42.13 38.58 37.40 36.45 BMWD PP (wt.%) 46.82 42.87 41.55 40.50 Rubber (% by weight) 10.00 10.00 10.00 10.00 Maleate PP (wt%) 0 0 0 2.00 Ceramic microspheres (% by weight) 0 2.50 5.00 5.00 Polyethylene wax (% by weight) 0 5.00 5.00 5.00 Stabilizer masterbatch (wt%) 1.05 1.05 1.05 1.05 Black pigment (wt%) 3 3 3 3 Notch toughness (J / cm) 2.34 1.5 1.07 1,23 Tensile strength (MPa) 31 31.8 30.2 31.2 Elongation at break (%) 278 152 78 54 Yield strength (%) 6.76 6.4 6.5 6.6 E-modulus in bend (0,13 cm / mm) (MPa) 1455 1504 1477 1449 Flexural strength (0.13cm / min) (MPa) 42.6 43.2 40.9 41.9

Initial gloss (20 °) (%) 79.5 77.9 73 77 Chrysler Crocking Gloss (20 °) (%) 0.3 31.8 62 65 Gloss retention (%) 0.4 40.8 85 84 Ford Crocking Gloss (20 °) (%) 0.9 7.4 32 36 Gloss retention (%) 1.1 9.5 44 47

The data show that both abrasion and wear improve with increasing amount of ceramic beads and that the addition of maleate polypropylene does not reduce the benefit of a combination of polyethylene wax and ceramic microspheres.

• · · ·

Example 9

This example describes the effect of different amounts of ceramic microspheres and compatibilizer on the abrasion and wear resistance of a composition comprising 5% rubber, 5% polyethylene wax and a graft copolymer consisting of propylene homopolymers as the backbone of the copolymer onto which the MMA / MeAc.

The preparation of the graft copolymer and mixing with BMWD PP were described in Example 1. Samples were prepared on a 40 mm Wemer-Pfleiderer twin screw extruder, with simultaneous running of interlocking screws, at a melt temperature of 300 to 310 ° C, screw speeds of 400 to 500 rpm. / min and a discharge rate of 77 to 98 kg / h. The extruder power and speed achieved a flow index of 16-18 g / 10 min at 230 ° C / 3.8 kg. Suction was used during extrusion.

Test specimens were prepared on a 255 g injection molding machine HPM at a melt temperature of 218 ° C and an injection temperature of 60 ° C. Abrasion and wear plates were prepared on a 142 g Battenfeld injection molding machine at a cylinder temperature of 246 ° C, a film temperature of 82 ° C and an injection rate of 1.3 cnvs.

Ceramic microspheres were of the X92 Zeeospheres type and were described in Example 5. The maleate polypropylene was described in Example 5. The other ingredients of the composition were the same as in Example 1 and their amounts are given in Table 9. The results of the physical properties and abrasion and wear tests are shown in Table 9.

• · · · · · · · · · · · · · · · · · · · · · · · ·

Table 9 Sample 1 2 3 ⁴ Graft copolymer (wt%) 42.13 41.42 40.48 38.81 BMWD PP (wt.%) 46.82 46.03 44.97 43.14 Rubber (% by weight) 5 5 5 5 Ceramic microspheres (% by weight) 0 1 5 Maleate PP (wt%) 0 0.5 1 2 Polyethylene wax (% by weight) 5 5 5 5 Stabilizer masterbatch (wt%) 1.05 1.05 1.05 1.05 and Black pigment (wt%) 3 3 3 ³ i Ř and Notch toughness (J / cm) 2,0 0.8 0.8 0.75 E-modulus in bending (0.13 cm / min) (MPa) 1395 1613 1663 1711 Flexural strength (0.13cm / min) (MPa) 40.1 47 47.7 48.6 Initial gloss (20 °) (%) 79.8 79.1 78.5 66.9 í Chtysler Crocking Gloss (20 °) (%) 25.5 43.8 63.4 22.5 Gloss retention (%) 32.0 55.4 80.8 33.6 Ford Crocking Gloss (20 °) (%) 13.6 21.7 32.0 21.9 Gloss retention (%) 17 27 Mar: 41 33 Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 55332 55432 44332 44332 Ford 5-prstv - wear (7.6, 3, 2, 0.6 N) 22222 22221 09999 F 22221

The data show that both abrasion and wear are improved by the addition of ceramic microspheres in the presence of maleate polypropylene as a compatibilizer.

Example 10

This example describes the effect of varying amounts of ceramic microspheres and compatibilizer on the abrasion and wear resistance of a composition comprising 10% rubber, 5% polyethylene wax and a graft copolymer consisting of a propylene homopolymer as the copolymer backbone to which the MMA copolymer is grafted. / MeAc.

The preparation of the graft copolymer and mixing with BMWD PP were described in Example 1. Material preparation and sample forming were described in Example 9.

Ceramic microspheres were of the X92 Zeeospheres type and were described in Example 5.

The maleate polypropylene was described in Example 5. The other components of the compositions were the same as in Example 1 and their amounts are given in Table 10. The results of the physical properties and abrasion and wear tests are shown in Table 10.

Table 10 Sample 1 i ² 3 and ! ⁴ Graft copolymer (wt%) 39.76 39.06 38,11 36.45 BMWD PP (wt.%) 44.19 43.39 42.34 40.5 Rubber (% by weight) 10 10 10 10 Ceramic microspheres (% by weight) 0 1 2.5 5 Maleate PP (wt%) 0 0.5 1 2 Polyethylene wax (% by weight) 5 5 5 5 Stabilizer masterbatch (wt%) 1.05 1.05 1.05 1.05 Black pigment (wt%) 3 3 3 3 Notch toughness (J / cm) 1.5 1.3 0.96 1.1 E-modulus in bending (0.13 cm / min) (MPa) 1461 1454 1468 1474 Flexural strength (0.13cm / min) (MPa) 42.4 42.4 42.4 42.3 Initial gloss (20 °) (%) 80 79.5 76.8 76.2 Chrysler Crocking Gloss (20 °) (%) 24.3 38.9 60.7 55.4 Gloss retention (%) 30.4 48.9 79.0 72.7 Ford Crocking Gloss (20 °) (%) 7.4 9.9 39.4 31.1 Gloss retention (%) 9 12 51 41 and Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 55333 55332 55332 55332 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 22222 22221 22221 22221

The data show that both abrasion and wear improve even at a low content of ceramic microspheres and compatibilizer.

«0 · ··

0 0 «00 · 00 00 00 00 00 00 00 90 00 9

Example 11

This example describes the effect of different amounts of ceramic microspheres and compatibilizer on the abrasion and wear resistance of a composition containing 15% rubber. 5% polyethylene wax and a graft copolymer consisting of a propylene homopolymer as the backbone of the copolymer onto which the MMA / MeAc copolymer is grafted.

Preparation of the graft copolymer and blending with BMWD PP were described in Example 1. Material preparation and sample forming were described in Example 9.

The ceramic microspheres were of the X92 Zeeospheres type and were described in Example 5.

The maleate polypropylene was described in Example 5. The other components of the compositions were the same as in Example 1 and their amounts are given in Table 11. The results of the physical properties and abrasion and wear tests are shown in Table 11.

·· ··

Table 11 Sample 1 2 3 4 Graft copolymer (wt%) 37.4 36.69 35.74 34.08 BMWD PP (wt.%) 41.55 40.76 39.71 37.87 Rubber (% by weight) 15 Dec 15 Dec 15 Dec 15 Dec Ceramic microspheres (% by weight) 0 1 2.5 5 Maleate PP (wt%) 0 0.5 1 Polyethylene wax (% by weight) 5 5 5 5 j Stabilizer premix (wt.%) 1.05 1.05 1.05 1.05 Black pigment (wt%) 3 3 3 3 Notch toughness (J / cm) 6.9 5.6 6.4 3.3 E-modulus in bending (0.13 cm / min) (MPa) 1243 1309 1292 1343 Flexural strength (0.13cm / min) (MPa) 36.2 38.1 37.6 38.5 Elongation at break (%) 438 349 350 300 Initial gloss (20 °) (%) 81.3 81 78.5 77.3 Chrysler Crocking Gloss (20 °) (%) 2.6 8.3 39.3 12.6 Gloss retention (%) 3.2 10.2 50.1 16.3 Ford Crocking Gloss (20 °) (%) 8.2 7.3 9.7 16.0 and Gloss retention (%) 10 9 12 21 Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 55332 55332 55332 55332 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 22221 22221 22221 22222 and

The data show that both abrasion and wear are improved even at a low content of ceramic microspheres and compatibilizer.

• • •

Example 12

This example describes the effect of different amounts of ceramic microspheres and compatibilizer on the abrasion and wear resistance of a composition comprising 20% rubber, 5% polyethylene wax and a graft copolymer consisting of a propylene homopolymer as the copolymer backbone to which the MMA copolymer is grafted. MeAc.

The preparation of the graft copolymers and mixing with BMWD PP were described in Example 1. Material preparation and sample forming were described in Example 9.

Ceramic microspheres were of the X92 Zeeospheres type and were described in Example 5.

The maleate polypropylene was described by λ / Example 5. The other components of the compositions were the same as in Example 1 and their amounts are given in Table 12. The results of the physical properties and abrasion and wear tests are shown in Table 12.

• ·

Table 12 Sample 1 2 3 4 Graft copolymer (wt%) 35,03 34.32 33.37 31.71 BMWD PP (wt.%) 38,92 38.13 37.08 35.24 Rubber (% by weight) 20 May 20 May 20 May 20 May Ceramic microspheres (% by weight) 0 1 2.5 5 Maleate PP (wt%) 0 0.5 1 0 Polyethylene wax (% by weight) 5 5 5 5 Stabilizer masterbatch (wt%) 1.05 1.05 1.05 1.05 What pigment (wt%) 3 3 3 3 Notch toughness (J / cm) 8.5 8.0 8.4 7.7 E-modulus in bending (0.13 cm / min) (MPa) 1132 1150 1065 1139 Flexural strength (0.13cm / min) (MPa) 33.2 33.4 31 32.8 ί Initial gloss (20 °) (%) 78.2 77 78 76 Chrysler Crocking Gloss (20 °) (%) 5.9 6.8 13.8 20.7 Gloss retention (%) 7.5 8.8 17.7 27.2 Ford Crocking Gloss (20 °) (%) 5.1 7.8 10.6 8.1 Gloss retention (%) 7 10 14 11 Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 55443 55332 55332 55332 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 22222 22221 22222 22221

The data show that both abrasion and wear improve even at a low content of ceramic microspheres and compatibilizer.

• · • ·

........

Example 13

This example describes the effect of different amounts of ceramic sizing agent and compatibilizer on the abrasion and wear resistance of a composition comprising 10% rubber, 5% polyethylene wax and a graft copolymer consisting of a propylene homopolymer as the copolymer backbone to which the copolymer is grafted MMA / MeAc.

The preparation of the graft copolymer and mixing with BMWD PP were described in Example 1. The sample material was prepared by mixing on a 34 mm Leistritz twin screw extruder, with concurrent running of interlocking screws, at a melt temperature of 250 ° C, screw speed of 250 rpm and extruder output 10.4 kg / h. Suction was used during extrusion.

The abrasion and wear test plates were prepared on a 142 g Battenfeld injection molding machine with a jacket temperature of 252 ° C, a mold temperature of 82 ° C and an injection rate of 1.27 cm / s.

The X-292 Zeeosphere ceramic microspheres were a silica-alumina ceramic alloy in which 90% by volume of the sample had a particle size <5.0-6.2 µm, treated with Union Carbide A 1100 sizing agent. The X-293 Zeeosphere ceramic microspheres. were a ceramic alloy of silica and alumina in which 90% by volume of the sample had a particle size of 0 to 7.4 µm, treated with Llnion Carbide A 1100. Both types are commercially available from Zeelan Industries, Inc.

The maleate polypropylene was described in Example 5. The other components of the compositions were the same as in Example 1 and their amounts are shown in Table 13. The results of the abrasion and wear tests are also shown in Table 13.

• · • ·

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• ·

The data show that the diameter of the ceramic microspheres does not significantly affect the abrasion and wear resistance.

Example 14

This example describes the effect of different amounts of X-61 Zeeosphere ceramic microspheres and compatibilizer on the abrasion and wear resistance of a composition comprising 10% rubber, 5% polyethylene wax, and a graft copolymer consisting of propylene homopolymers as copolymer backbone on is an grafted MMA / MeAc copolymer.

The preparation of graft copolymers and mixing with BMWD PP were described in Example 1. The preparation and forming of samples was described in Example 13.

Ceramic microspheres X-61 Zeeosphere ceramic composite are silica and alumina having a particle size of <4.2 to 5.2 _(microns and are commercially available from Zeelan Industries, Inc, maleated polypropylene was described in Example 5. The other components of the composition were the same as in Example 1 and their amounts are shown in Table 14. The results of the abrasion and wear tests are given in Table 14.

• · · · · · · · · · · · · ·

Table 14 Sample 1 2 3 4 Graft copolymer (wt%) 39.76 39.05 38,11 36.45 BMWD PP (wt.%) 44.19 43.4 42.34 40.5 Rubber (% by weight) 10 10 10 10 Ceramic microspheres (X61) (w / w) 0 1 2.5 5 Maleate PP (wt%) 0 0.5 1 0 4-, Polyethylene ⁷ wax (wt%) 5 5 5 5 Stabilizer masterbatch (wt%) 1.05 1.05 1.05 1.05 Black pigment (wt%) 3 3 3 3 Initial gloss (20 °) (%) 82.7 80.2 80 77 Slice crocking gloss (20 °) (%) 23.4 28.5 59.6 63.9 Gloss retention (%) 28.3 35.5 74.5 83 Ford Crocking Gloss (20 °) (%) 4,5 6.6 9.6 12.7 Gloss retention%%) 5.4 8.2 12 16.5 Ford 5-finger - abrasion (7, 6, 3, 2, 0.6 N) 53332 53323 53323 53323 Ford 5-finger - wear (7, 6, 3, 2, 0.6 N) 22221 51431 51431 52432

The data show that a small amount of ceramic microspheres is effective and that it improves both abrasion and wear with increasing microsphere content.

Example 15

This example describes the effect of using different types of inorganic microspheres, with or without maleate polypropylene as a binder, on the abrasion and wear resistance of a composition comprising 10% rubber, 5% polyethylene wax and a graft copolymer consisting of propylene homopolymer as the copolymer backbone onto which the MMA / MeAc copolymer was grafted.

• · · · · · · · · · · ·

Execution of the graft copolymer and mixing with BMWD PP were described in Deposit 1. Execution of samples was the same as in Deposit 5 except that the melt temperature was -240 ° C. Abrasion and wear plates were prepared as described in Example 1. BMWD PP, rubber, polyethylene wax, stabilizer premix, and black pigment were described in Example 1. Maleate polypropylene was described in deposit 5. White pigment was RCL6 type, commercially available at Millenium.

W210 Zeosheres were alkaline aluminosilicate ceramic microspheres in which 90% by volume of the sample had a particle size <11 mg and are commercially available from Zeelan Industries, Inc. X273 Zeeospheres was an alkaline aluminosilicate ceramic in which 90% by volume of the sample had a particle size <6.0 to 7.4 mg, also commercially available from Zeelan Industries, Inc. Spheriglass 6000, glass beads, had a particle size distribution such that 90 wt. The particles were finer than 15 gm, and are commercially available from Potters Industries Inc.

The amount of each component and the results of the abrasion and wear tests are shown in Table 15.

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The data show that both abrasion and wear are improved by adding two types of alkaline aluminosilicate microspheres as well as by adding glass microspheres.

Other features, advantages and wording of the invention set forth herein will be apparent to those skilled in the art from reading the foregoing data. In this regard, specific aspects of the invention have been described in great detail, however variations and modifications of these texts may be varied without departing from the spirit and scope of the invention as described and claimed.

Claims (10)

PATENT CLAIMS 1) ethylene and propylene, 2) ethylene, propylene, and 4 to 8 C alpha-olefin, and 3) ethylene and 4 to 8 C alpha olefin, the copolymer has a polymerized propylene content of greater than 85% by weight, and an isotactic index greater than 85, ii) about 20% to 60% amorphous copolymer of monomers selected from the group consisting of 1) ethylene and propylene, 2) ethylene, propylene, and 4-8 C alpha-olefin, and 3) % of ethylene and 4-8 C alpha-olefin, the copolymer optionally containing about 0.5% to 10% polymerized diene, and contains less than 70% polymerized ethylene and is soluble in xylene at ambient temperature, and iii. ) about 3% to 40% of an ethylene-propylene copolymer or 4 to 8C of an alphaolefin that is insoluble in xylene at ambient temperature. wherein the thermoplastic olefin has an E-modulus in bend greater than 150 but less than 1200 MPa. 1) from propylene and ethylene, 2) from propylene, ethylene and 4-8 C alpha-olefin, and 3) from propylene and 4-8 C alpha-olefin, the copolymer having a polymerized propylene content of greater than 85% by weight, and an index ii) about 5% to 25% by weight of isotacticity; a copolymer of ethylene and propylene, or a 4-8 C alpha-olefin which is insoluble in xylene at ambient temperature; and iii) about 30% to 70% by weight of an elastomeric copolymer of monomer selected from the group consisting of 1) ethylene and propylene 2) ethylene, propylene and 4 to 8 C alpha-olefin, and 3) ethylene and 4 to 8 C alpha-olefin, the copolymer optionally containing about 0.5% to 10% by weight. % polymerized diene and contains less than 70 wt. polymerized ethylene, is soluble in xylene at ambient temperature and has an intrinsic viscosity, measured in tetrahydronaphthalene at 135 ° C, of about 1.5 to 4.0 dkg, wherein the total amount of ii) and iii), based on the total olefin polymer composition, is about 50% to 90%. the weight ratio ii) / iii) is less than 0.4. and the composition is prepared by polymerization in at least two stages and the flexural modulus is less than 150 MPa, and (e) a thermoplastic olefin containing: i) about 10% to 60%, a propylene homopolymer having an isotactic index greater than 80, or a copolymer of monomers selected from the group consisting of: (1) ethylene and propylene, (2) ethylene, propylene, and 4-8 C alpha-olefin, and (3) ethylene and 4-8 C alpha-olefin, the copolymer having a polymerized propylene content of greater than 85% by weight, and an index of isotacticity greater than 85, ii) about 20% to 60% amorphous copolymer of monomers selected from the group consisting of 1) ethylene and propylene, 2) ethylene, propylene, and 4-8 C alpha-olefin, and 3) ethylene and 4; an alpha-olefin, the copolymer optionally containing about 0.5% to 10% polymerized diene, and contains less than 70% polymerized ethylene and is soluble in xylene at ambient temperature, and iii) about 3% to 40% ethylene copolymer; and propylene, or 4-8 C alphaolefin, which is insoluble in xylene at ambient temperature, wherein the thermoplastic olefin has a flexural E-modulus of greater than 150 but less than 1200 MPa. 1) from propylene and ethylene, 2) from propylene, ethylene and from 4 to 8 C alpha-olefin, and 3) from propylene and from 4 to 8 C alpha-olefin, the copolymer has a polymerized propylene content of greater than 85% by weight. and an isotacticity index greater than 85; ii) about 5% to 25% by weight; % of an ethylene-propylene copolymer, or a 4-8 C alpha-olefin which is insoluble in xylene at ambient temperature; an elastomeric copolymer of monomers selected from the group consisting of 1) ethylene and propylene, 2) ethylene, propylene and 4-8 C alpha-olefin, and 3) ethylene and 4-8 C alpha-olefin, the copolymer optionally containing about 0.5 % to 10 wt. % of polymerized diene and contains less than 70 wt. % of polymerized ethylene, is soluble in xylene at ambient temperature and has an intrinsic viscosity, measured in tetrahydronaphthalene at 135 ° C, of about 1.5 to 4.0 dl / g, the total amount of ii) and iii) based on the total olefin polymer composition is about 50% to 90%, the weight ratio ii) / iii) is less than 0.4, and the composition is prepared by polymerization in at least two stages, and the flexural modulus is less than 150 MPa. or (e) thermoplastic olefins, containing: i) about 10% to 60 ^{O /} o, propylene homopolymers having an isotacticity index greater than 80, or a copolymer of monomers selected from the group consisting of: 1. A composition comprising: (a) a graft copolymer consisting of a polymeric backbone material forming a backbone onto which the polymerization is grafted with at least one free-radical polymerizable vinyl monomer, wherein the polymerized monomers are present in an amount of about 10 to 120 parts per hundred parts of polypropylene material , and b) an additive selected from the group consisting of i) about 0.5% to 10% of at least one low molecular weight polymer of ethylene or a functionalized derivative thereof having a number average molecular weight of about 300 to 5000, and ii) a combination of about 0.5% to 10% 1) of at least one of the low molecular weight polymers of ethylene vi) and 2) about 0.5% to 10% of inorganic microspheres based on the total weight of the composition. 2. The composition of claim 1, wherein the semi-polypropylene material is selected from the group consisting of: (a) from a propylene homopolymer with an isotactic index greater than 80; b) a propylene-olefin copolymer selected from the group consisting of ethylene and 4-10 C alpha-olefins, provided that the olefin is ethylene, the maximum polymerized ethylene content is about 10% by weight. and when the olefin is from 4 to 10 C alphaolefin, the maximum of its polymer is about 20 wt. the copolymer has an isotactic index greater than 85; (c) a terpolymer of propylene and two olefins selected from the group consisting of ethylene and 4 to 8 C alpha-olefins, provided that the maximum content of polymerised 4 to 8 C alpha-olefin is 20% by weight, and if ethylene is one of the olefins, the maximum polymerized ethylene content is 5% by weight, the terpolymer has an isotactic index greater than 85, (d) an olefin polymer composition comprising: i) about 10 to 60 wt. a propylene homopolymer having an isotactic index greater than 80 or a copolymer of monomers selected from the group consisting of: Composition according to claim 2, characterized in that the propylene polymer material is a propylene homopolvmer. ··· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Composition according to claims 1 to 3, characterized in that the vinyl monomers are selected from the group consisting of a) methyl methacrylate and methacrylate and b) methyl methacrylate and methacrylic acid. The composition according to claims 1 to 4, further comprising about 0.2% to 4 °, based on the total weight of the composition, of a compatibilizer comprising an acid-functional propylene polymer and about 2% to 30%. based on the total weight of the composition, at least one rubber component selected from the group consisting of a) olefin copolymer rubber, b) monoalkenyl aromatic hydrocarbon-conjugated diene block copolymer, and c) encapsulated rubber. The composition according to claims 1 to 5, further comprising about 15 ° to 50%, based on the total weight of the composition, of a propylene polymer material having a broad molecular weight distribution. 7. A method of improving the abrasion and wear resistance of a graft copolymer mixed with a) a graft copolymer comprising a propylene polymer backbone polymer material to which at least one vinyl monomer capable of free radical polymerization is grafted, wherein the polymerized monomers are present in an amount of about 10 to 120 parts per hundred parts of the propylene polymer material; and b) additives selected from the group consisting of: i) about 0.5% to 10% of at least one low molecular weight polymer of ethylene, or a functionalized derivative thereof, having a number average molecular weight of about 300 to 5000, and ii) a combination of 1) about 0.5% to 10% of at least one of the low molecular weight polymers and 2) about 0.5% to 10% of inorganic microspheres based on the total weight of the composition. Composition according to claim 7, characterized in that the propylene polymer material is selected from the group consisting of: (a) from a propylene homopolymer with an isotacticity index greater than 80; b) a propylene-olefin copolymer selected from the group consisting of ethylene and 4-10 C alpha-olefins, provided that the olefin is ethylene, the maximum content of polymerized ethylene is about 10% by weight. and when the olefin is from 4 to 10 C alphaolefin, the maximum of its polymer is about 20 wt. , the copolymer has an isotacticity index greater than 85, (c) a terpolymer of propylene and two olefins selected from the group consisting of ethylene and 4 to 8 C alpha-olefins, provided that the maximum content of polymerised is 4 to 8 The alpha-olefin is 20% by weight, and if ethylene is one of the olefins, the maximum content of polymerized ethylene is 5% by weight, the terpolymer has an isotacticity index greater than 85 (d) an olefin polymer composition comprising: i) about 10 to 60 wt. a propylene homopolymer having an isotacticity index greater than 80 or a copolymer of monomers selected from the group consisting of: A method according to claims 7 and 8, characterized in that about 0.2% to 4%, based on the total weight of the composition, of a compatibilizer comprising an acid-functional propylene polymer is added to the composition. An article made from the composition of claims 1 to 6.