MXPA95000683A - Thermoplastic compositions containing ground vulcanized rubber and polyolefin re - Google Patents

Abstract

A thermoplastic composition blend having a ground vulcanized rubber component, characterized in that the blend includes from 1-90 parts by weight of the ground vulcanized rubber in the form of small dispersed particles essentially of 1.5 mm number average or below, wherein said rubber is selected from the group consisting of natural rubber, synthetic polymer or copolymer rubber derived from alkadienes, or mixtures thereof, and correspondingly, 90-1 parts by weight of polyolefin resin and at least 0.5 parts by weight of one or more functionalized olefin polymers per 100 parts by weight of polyolefin resin wherein said functionalized olefin polymer is a copolymer of at least one olefin and at least one ethylenically unsaturated organic monomer;wherein said organic monomer is selected from the group consisting of unsaturated mono or dicarboxylic acids having from 3 to 20 carbon atoms;acid anhydride, maleamic acid, acid halide, ester and metal salt derivatives of said unsaturated mono o r dicarboxylic acids;vinyl esters of saturated carboxylic acids wherein the acid constituent of said saturated carboxylic acid has from 2 to 18 carbon atoms;vinyl alkyl ethers wherein said alkyl constituent has from 1 to 18 carbon atoms;vinyl halides;vinylidene halides;acrylonitrile;methacrylonitrile;and styrene.

Description

OLE THERMOPLASTIC COMPOSITIONS CONTAIN VULCANIZED HULE AND MOLDED POLYOLEFINE RESIN Inventor: Lane D. Johnson, of North American nationality, with address in 2011 West Second Street # 101, Duluth, Minnesota 55803, United States of America.

• Owner: SYNESIS COMPANY, of North American nationality, with address at P.O. 54, Seville, Ohio 44273, United States of America.

Extract of the Invention Thermoplastic compositions are described # include mixtures of vulcanized rubber and ground polyolefin resin; these are improved by the incorporation of a functionalized olefin polymer.

Technical Field This invention relates to improved polymer blends of vulcanized rubber and ground polyolefin resin, and in particular to mixtures of increased compatibility due to the presence of a functionalized olefin polymer.

Related Patent Applications The application is a continuation in part of the previous application filed, series No. 08 / 139,214 filed * «. on October 20, 1993. F Background of the Invention Mixtures of vulcanized rubber and ground thermoplastic polymer are known, for example, in US Pat. No. 4,028,288, a method for preparing mixtures of vulcanized rubber particles and a thermoplastic polymer is described. However, due to insufficient bonding between the rubber particles and the polymer phase, the resulting compositions exhibit poor mechanical properties, especially low elongation, therefore, if the compatibility of the mixing components can be increased, improved compositions can be obtained. .

In U.S. Patent No. 4,386,182, a thermoplastic elastomeric composition is disclosed, which consists of a vulcanized cured rubber, a thermoplastic olefin or an olefin polymer, and a compatibilizer additive. This patent, however, is not pertinent to the present invention, since the compatibilizer additive is the reaction product of the hydroxyl compound with an alkene oxide. As will be shown in a comparative example given below, the mechanical properties of such a composition, (for example, percent elongation at break) are lower in relation to the mechanical properties of the compositions of the present invention.

Each year, in the United States of America, more than 240 million used tires are discarded. This in addition to an estimate of 2 billion tires that already exist. Above ground the storage of the tires presents a danger to health and fire. Once lit, the tire batteries can burn for months, polluting the air with black smoke and a strong smell. The tires are an ideal growth ground for mosquitoes carrying diseases and rodents. When they are buried, the complete tires settle unevenly and rise to the surface creating land management problems. These dangers are very »Documented in various tire studies sponsored by the EPA, other federal agencies and state agencies. Both the US Congress and the EPA have previously determined that waste strips are a significant waste management problem. For example, in the 1984 amendment to the Resource Conservation and Recovery Act of 1976, Congress advised the EPA to issue procurement guidelines for tires. Many state laws have dictated or are considering legislating the storage and / or disposal of tire waste. Due to economic and environmental reasons, the reclamation of waste tires by thermal and / or chemical "devulcanization" has been dramatically reduced in recent years. Over the period of 1941 and 1985, the consumption of reclaimed rubber has decreased from 32% of new rubber to less than 5%. The burning of tires as a fuel has raised concerns about air pollution.

Summary of the Invention It has now been discovered that an improved composition comprising a mixture of ground vulcanized rubber and a polyolefin resin is obtained by incorporating therein, a functionalized olefin polymer. Mixtures containing high proportions of ground vulcanized rubber are elastoplastic, which means that they are elastomeric, but can be processed as a thermoplastic. The processability of the melted of these * Compositions allow shaped articles of these compositions to be molded thereof without the time-consuming setting step required with conventional rubbers, thereby reducing the finished part cost.

More specifically, the improved compatibilized polymer blends comprise (a) ground vulcanized rubber jr in the form of small, dispersed particles of specifically 1.5 mm. number average or below, (b) polyolefin resin, (c) functionalized olefin polymer, and if desired, additives such as fillers, pigments, reinforcers, stabilizers, processing aids, colorants, plasticizers and other compounds or Modifying ingredients which can be included in order to meet the specific operating needs of each client.

F Preferred Modality for Carrying Out the Invention The component (a) is vulcanized rubber ground mechanically or cryogenically in the form of small particles essentially of an average number of 1.5 mm. or lower, and more preferably of a particle size between 0.1 mm and 1.0 mm. of average number. Examples of the vulcanized rubber include natural rubber, synthetic copolymer rubber polymer derived from alkadienes, or mixtures thereof. For economic reasons, the vulcanized rubber of scrap tires, coated tire scrapers, rim tubes and miscellaneous waste thermosetting rubber articles is especially preferred for the purposes of the present invention.

The polyolefin resin listed as the component (b) is a solid high molecular weight polymeric material made by the polymerization of one or more olefinic monomers in a conventional manner. Examples of such olefins are ethylene, propylene, 1-butene, 1-pentene, 2-methyl-1-propene, or mixtures thereof. Preferred polyolefin resins are polyethylene or polypropylene. Also suitable for the practice of the invention are copolymers of two or more olefins with the ethylene and propylene copolymers being preferred.

The functionalized olefin polymer listed as component (c) is a copolymer of at least one olefin and one or more ethylenically unsaturated organic monomers. Preferred olefins include ethylene, propylene, butylene, butadiene, isoprene, including hydrogenated butadiene or isoprene. Examples of the organic monomers are those selected from the group consisting of unsaturated mono or dicarboxylic acids of 3-20 carbon atoms and their derivatives such as acid anhydrides, maleamic acids, acid halides, esters, metal salts and the like; the vinyl esters of the saturated carboxylic acids wherein the acid group has 2-18 carbon atoms, alkyl vinyl ethers wherein the alkyl group has 1-18 carbon atoms, vinyl or vinylidene halides, acrylonitrile, methacrylonitrile , and vinyl aromatics. Of course, more than one of these organic monomers can be copolymerized with an olefin to form the functionalized olefin polymer useful in the practice of the present invention. Preferred functionalized olefin polymers contain at least one olefin, including hydrogenated butadiene or isoprene, modified by a reactive functional group such as a carboxylic acid or its derivatives. The functional groups can be either (i) on the polymer column such as in copolymers or acrylic acid and ethylene available from Dow Chemical Company under the trademark Primacor or (ii) grafted onto the main polymer column, examples of which they are polypropylene grafted with maleic acid anhydride available from Hercules-Himont as Hercoprime and polypropylene grafted with acrylic acid available from BP Performance Polymers, Inc. under the Polybond brand. The industrial technology that is used for # making such functionalized olefin polymers is known and covered in several patents of the United States of America. Examples of such technology include U.S. Patent No. 3,862,265 issued to Stein amp. Et al., U.S. Patent No. 4,001,172 issued to Steinkamp et al .; U.S. Patent No. 3,658,948, issued to McConnel; U.S. Patent No. 3,746,676 issued to Joymer et al .; U.S. Patent No. 3,882,194 issued to Krebaum et al .; the Japanese patent Kokai 58/11508 (1983) granted to Okono and others; U.S. Patent No. 4,146,590 issued to Yamamoto et al .; U.S. Patent No. 3,177,269 issued to Nowak et al .; U.S. Patent No. 3,131,990 issued to Alberto et al. and the like. Generally, the amount of organic monomer was used at a rate of about 0.5 to 30 parts by weight per 100 parts by weight of functionalized olefin polymer. This may, however, be considerably lower, with amounts in the vicinity of 0.1% being sufficient to improve the compatibility of the ground vulcanized rubber particles and the polyolefin resin.

Although they are not essential components of the compositions of this invention, various amounts of any number of conventional fillers or compounding ingredients may be combined. Examples of such * ingredients include various carbon blacks, clay, silica, alumina, calcium carbonate, titanium dioxide, pigments, flame retardants, reinforcers, stabilizers, setting agents, antioxidants, anti-degradants, adhesives, processing aids such as lubricants and waxes , plasticizers, etc. The amount used depends at least in part on the amounts of the ingredients in the composition.

A blend composition of the present invention can be manufactured in a single operation or in a number of operational steps. In the one-step operation, the particles * of vulcanized rubber, the functionalized olefin polymer and the polyolefin resin, with the necessary fillers and additives are charged at the desired rates to a suitable mixer, for example, an internal Banbury mixer, a two-roll extruder or mill, or any device that allows efficient mixing of the mixture at the appropriate temperature to obtain a composition of the invention. Alternatively, as an example of a multiple pass operation, a composition of the invention can be prepared by first mixing separately a combination of ground vulcanized rubber and polyolefin resin. The independently prepared mixture is then mixed with melt together with the functionalized olefin polymer in a suitable mixer to obtain a composition of the invention. The mixing is done at a temperature high enough to soften the polymers for proper mixing, but not so high as to degrade the # polymers. Generally speaking, this mixing temperature varies from 140 ° C to 200 ° C, and the mixing is carried out for a sufficient time to homogeneously mix the components.

According to this invention, the relative proportions of the vulcanized rubber particles of the polyolefin resin and the functionalized olefin polymer depend, at least in part, on the type and molecular weight of the rubber, polyolefin resin and functionalized olefin polymer. , and the presence of other ingredients in the composition such as * fillers, reinforcements, plasticizers, etc. In general, the compositions of the invention comprise about 1-90 parts by weight of ground vulcanized rubber, and correspondingly, about 90-1 parts by weight of polyolefin resin. Compositions comprising about 20 to about 80 parts by weight of ground vulcanized rubber are preferred., and correspondingly about 80 to about 20 parts by weight of polyolefin resin. An amount of the functionalized olefin polymer that is sufficient to improve the compatibility between the ground vulcanized rubber and the polyolefin resin is satisfactory for the compositions of the invention. Improved compatibility is generally indicated by an increase in tensile strength or elongation or both. An increase in elongation of 25%, preferably 50% more, indicates improved compatibility. The amount of functionalized olefin polymer required is easily determined by increasing the amount of functionalized olefin polymer in the mixture incrementally until the improved properties are observed. Generally, at least 0.5 parts by weight of the functionalized olefin polymer per 100 parts by weight of polyolefin resin is sufficient to observe an improvement in compatibility. Typically, the amount of functionalized olefin polymer is from about 0.5 to 50 parts by weight per 100 parts by weight of polyolefin resin. Increasing the amount of functionalized olefin polymer within this range usually increases compatibility. Of course, it is understood that the polymer of * Functionalized olefin can replace all polyolefin resin, if desired, but the improvement in properties may not be substantially greater than what is obtained by using smaller amounts of functionalized olefin polymer.

The blend composition of the present invention is processable with melt using conventional plastic processing equipment. The properties of the mixture depend on the properties of the components with a wide range of properties being available simply by varying the proportions of the mixing components. Mixtures containing a high proportion of ground vulcanized rubber are elastoplastic, which means they are elastomeric, but can be processed using conventional plastic processing equipment. For example, these components have elongation at break-up values of 100 to 300% without a substantial permanent stress settlement (eg, less than 50%). In addition, the melt processability of these compositions allows shaped articles of these compositions to be molded thereof without a time-consuming setting step required with conventional rubbers, thereby significantly reducing the finished part cost. Mixtures containing high proportions of polyolefin resin are rigid moldable thermoplastic compositions that exhibit improved impact resistance. Since in the process the waste can be melted again and recycled there is no waste, resulting in additional cost savings. The thermoplastic nature of the compositions of the present invention allows shaped articles made from the compositions to be recycled in the same manner as conventional thermoplastics, thereby helping to alleviate the growing environmental problem of solid waste waste. In addition, the composition of the present invention is adaptable to reprocessing vulcanized rubber from scrap tires, and thus can serve environmental protection by reducing solid waste and health / fire hazards associated with the storage of waste. tires above the grounds. The improved compositions of the invention can be used to form a variety of molded, extruded or calendered articles. Various uses for the compositions of the invention include seals and gaskets, automotive parts, anti-skid surfaces, and reinforced hoses.

* These can be used to coat fabrics, industrial belts and various hard surfaces by extrusion coating. They can also find utility as impact modifiers for other polymer systems. The compositions within the scope of the invention can be used as the protective coating of reinforced or unreinforced tubes or of similar or different compositions.

The invention object of the invention will be more fully appreciated with reference to the following examples. In the non-restrictive examples declared all percentages are for * weight of the total compositions unless otherwise indicated.

Example 1 The vulcanized rubber particles were obtained by grinding the rims of passenger cars, 3 consisting mainly of SBR rubber. The average particle size was 0.5 mm. The rubber particles, the functionalized olefin polymer and the polyolefin resin were mixed in a Brabender mixer at 100 revolutions per minute with the oil bath controlled at 180 ° C to 190 ° C for five minutes. After mixing, to demonstrate that the compositions were processable with melt, each load was placed in a paint box mold at room temperature and molded with Sk compression on a 2.0 mm blade. of thickness in a hydraulic press, both tables of which had been preheated to 200 ° C. The press was heated for an additional 5 minutes. The molded sheet was then rapidly cooled under pressure to room temperature and removed from the press. The test specimens were cut with molded sheet matrix and used after 24 hours of storage at room temperature. The molded sheet samples were processable and re-meltable.

The stress-strain properties of the composition were determined according to established procedures ^^. in the ASTM D-412 standard. The test specimens are pulled with an Instron tester at 20.0 inches per minute at failure. The properties are shown in Table 1. The true tension to break (TSB) is the tensile strength to the break multiplied by the proportion also to the break. The length extension ratio of a tension test specimen to the crack divided by the original unstressed length of the test specimen. Alternatively, the extension ratio is 1.00 plus 1/100 of the last elongation percentage.

The mixed compositions are prepared containing the ingredients in Table 1. The load A is a control containing modified polypropylene. The load B is a control containing unmodified polyethylene. The charges C and D illustrate improved compositions of the invention. The data show that J = the incorporation of a functionalized olefin polymer results in a substantial improvement in elongation. The true tension to the break, TSB, shows an increase of 2 to 3 times over the controls.

TABLE I ? B C D Rubber * 60 60 60 60 * ppb 40 __ 15 15 PE ° - 40 S (EB) Sd - - 25 EVAe - - - 25 Hardness Shoref 46D 42D 23D 26D f Tension at Break *, psi 1249 1177 760 825 Elongation at break *,% 25 35 241 221 M100 *, psi 550 610 TBbh 1561 1589 592 2648 • Rubber = Passenger car tires ground, average particle size 0.5 mm.

• PP = Polypropylene PE = Polyethylene d S (EB) S = triblock copolymer consisting of styrene end blocks and half poly (ethylene / butylene) blocks, (29 percent styrene). e EVA = Ethylene vinyl acetate copolymer, (25 percent VA) f ASTM D-2240 «ASTM D-2240 • TSB = True breaking stress Example 2 By the same procedure of Example 1, the following compositions were mixed (the values are in one percent by weight). This example serves to illustrate the effect of adding a functionalized olefin polymer containing reactive functional groups, such as carboxylic acids. The load A is a control containing unmodified polyethylene. The charge C contains an unmodified triblock copolymer consisting of styrene end blocks and half poly (ethylene / butylene) blocks. The filler B contains a copolymer of ethylene and methacrylic acid. The filler D contains a triblock functionalized maleic anhydride copolymer consisting of styrene end blocks and poly (ethylene / butylene) blocks. The data (Table II) show a substantial improvement in the mechanical properties by incorporating there a functionalized olefin polymer of carboxylic acid. In addition, it was also noted that during the Instron stress test that the specimens containing the unmodified copolymer began to tear in several places well before the break while the specimens containing the functionalized olefin polymer of carboxylic acid had their integrity much better, which also indicates a high degree of compatibility.

TABLE II A B C D Hule1 60 60 80 80 ppb - - 10 10 S (EB) Se 10 S (EB) S / 2% MAf 10 Shore hardness 42D 26D 64A 64A Tension to breaking, psi 1177 1263 491 719 Elongation at Break,% 35 227 142 173 • MlOO, psi 899 458 614 Stress Setting *,% 35 TSB 1589 4130 1188 1963 • Rubber = rims for passenger cars ground, average particle size of 0.5 mm.

PP = Polypropylene c PE - Polyethylene d EMAA = Methacrylic acid / ethylene copolymer (20 percent MAA). e S (EB) S = triblock copolymer consisting of styrene end blocks and half poly (ethylene / butylene) blocks (29 percent styrene). f S (EB) S / 2% MA = Functionalized triblock copolymer of maleic acid anhydride consisting of styrene end blocks # and half blocks of poly (ethylene / butylene), (2 percent MA, 28 percent styrene).

* ASTM D-412 Example 3 By the same procedure of Example 1, the following compositions were mixed (values are in percent by weight). This example serves to illustrate the effect of changing the relative proportion of the rubber, the functionalized olefin polymer and the polyolefin resin (Table III).

TABLE III PPD 50 25 40 15 20 10 5 S (EB) s / 2% MAC «•» • 25 __ 25 10 35 Hardness Shore 50D 32D 46D 23D 75A 64A 61A Breaking strain, psi 1395 1332 1249 951 538 719 1019 at% 25 185 25 245 82 173 317 - 1208 - 681 - 614 484 TSB 1744 3796 1561 3281 939 1963 4249 * Rubber = rims for ground passenger cars, average particle size of 0.5 mm. b PP = Polypropylene - ^^ c S (EB) S / 2% MA = Functionalised triblock copolymer of maleic acid anhydride consisting of styrene end blocks and poly (ethylene / butylene) half blocks, (2 percent MA, 28 percent styrene ).

Comparative Example 4 By the identical procedure as in Example 1, the following compositions were mixed (values are in percent by weight). Fillers B, D and F were prepared using 1.0 percent CARBOWAX 4000 according to Example 1 of United States Patent No. 4,386,182. The results show that the mixtures produced with CARBOWAX 4000 have lower mechanical properties (Table IV). TABLE IV B E P Rubber * 60 60 60 60 60 60 ppb 40 39 30 30 30 15 'CARBOWAX 4000c 1.0 1.0 1.0 S (EB) Sd 10 9 25 24 , Durezc phore 46D 46D 39D 40D 23D 23D Tension at break, psi 1249 1141 985 871 760 706 Elongation at break,% 25 29 81 79 241 213 MlOO, psi 550 524 TSB 1561 1472 1783 1559 2592 2209 * Rubber = Tires for cars of ground passengers, average particle size of 0.5 mm. f b PP = Polypropylene c CARBOWAX 4000 = Nonionic surfactant of the polyethylene oxide type of Union Carbide. d S (EB) S = triblock copolymer consisting of styrene end blocks and half poly (ethylene / butylene) blocks, (29 percent styrene).

Example 5 By the same procedure of Example 1, the following compositions were mixed (values in percent by weight). This example serves to illustrate the effect of adding compound ingredients such as lubricants (Table V). i ABLA V ppb 15 15 15 S (EB) S / 2% MAC 25 24 23.9 Zincd stearate - 1 1 AC629e - - 0.1 Extrusion rate, extruder 4 41100 620 640 4 inches, pounds / hour * Rubber = passenger car tires ground, particle size of an average of 0.5 mm.

PP = Polypropylene c S (EB) S / 2% MA = Functional triblock copolymer of maleic acid anhydride consisting of styrene end blocks and poly (ethylene / butylene) half blocks (2 percent MA, 28 percent styrene). d Zinc stearate lubricant. e AC629 = Release lubricant of ethylene oxide metal.

Fillers A, B and C were prepared and pelleted in a Farrel continuous mixer at 180 ° C to 190 ° C. The blended compositions were fed to a 4 inch diameter (10.2 cm) extruder with a single screw. The barrel temperatures were controlled to obtain a melting temperature of 180 ° C. The material was extruded through a sheet matrix. Fillers B and C showed a better surface appearance than load A as a result of better dispersion of the rubber particles. In addition, the extrusion rate increased significantly and the matrix accumulation that was present in load A was virtually eliminated.

In order to illustrate the versatility of the composition of the present invention, the filler D of Example 3 was prepared in an internal 9B Banbury mixer at 180 ° C to 190 ° C for five minutes. The blended composition was pelleted and fed to a 1 1/2 inch diameter (4.8 cm) Davis Standard extruder with a single phase screw and a diameter length ratio of 24: 1. The barrel temperatures were controlled to obtain a melting temperature of 180 ° C. The material was extruded through a sheet matrix. This composition in 2 & Pellet form was also injection molded in a reciprocating injection molding machine, with all areas of the barrel heated to 170 ° C and the mold at 25 ° C. Using 100 psi injection pressure, the melted material filled the cavity of the plate mold in 1.5 seconds and was allowed to cool for an additional 20 seconds before the mold opened and the finished part was expelled.

The injection molding and extrusion demonstrations described above show that compositions within the scope of this invention can be processed in standard thermoplastic processing equipment and used to manufacture such articles as extruded profiles, tubes, hoses, sheets, etc. or miscellaneous injection molded seals, gaskets, automotive parts or rubber goods.

Example 6 They were mixed by the same procedure as # Example 1, the following compositions, (the values in percent by weight). This example serves to illustrate the effect of adding compositional ingredients to such phenolic resins (Table VI). TABLE VI A B C D Rubber * 70 70 70 70 PEb 30 27.5 15 15 EVAC - 15 12.5 SP-1045d 2.5 - 2.5 Hardness Shore 91A 90A 80A 81A Tension at Breakdown psi 833 833 668 1124 Elongation to breaking, psi 34 35 120 230 MlOO, psi 612 729 TSB 1116 1192 470 3709 * Rubber - Passenger car tires ground, average particle size 0.5 mm. f b PE = Polyethylene ? VA = Ethylene vinyl acetate copolymer (25 percent VA) d SP-1045 = Phenolic dimethylol resin.

Suitable phenolic resins include halogenated substituted or unsubstituted alkyl dimethylol phenolic resins.

The load A is a control containing an unmodified polyethylene. Charge B contains unmodified polyethylene and a dimethylol phenolic resin (SP-1045). The charge C contains a functionalized olefin vinyl acetate polymer (EVA). The filler D contains a functionalized olefin polymer of acetate ^. of vinyl (EVA) and a phenolic dimethylol resin (SP-1045). - The data (Table VI) show a substantial improvement in the mechanical properties by the incorporation of a functionalized olefin polymer of vinyl acetate and a phenolic dimethylol resin.

Even though the invention has been illustrated by typical examples, it is not limited thereto. For example, it is understood that the use of functionalized olefins containing functional groups which are derivatives of carboxylic acids such as acid anhydrides, maleamic acids, acid halides, ester, metal salts and the like, will improve the compatibility between the particles of ground vulcanized rubber and polyolefin resin. The changes and modifications of the examples of the invention chosen herein for the purpose of the description can be made without constituting a departure from the spirit and scope of the invention. ".- 'i

Claims (28)

Claims Having described the invention, it is considered as a # novelty, and therefore the content of the following clauses is claimed as property:

1. A thermoplastic composition mixture having a ground vulcanized rubber component, characterized in that the mixture includes 1-90 parts by weight of the ground vulcanized rubber in the form of dispersed small particles of essentially 1.5 mm. of average or lower number, wherein said rubber is selected from the group consisting of natural rubber, synthetic polymer or copolymer rubber derived from alkadienes or mixtures thereof, and correspondingly, 90-1 parts by weight of a polyolefin resin and at least 0.5 parts by weight of one or more functionalized olefin polymers per 100 parts by weight of polyolefin resin wherein said functionalized olefin polymer is a copolymer of at least one olefin and at least one ethyethically unsaturated organic monomer; wherein said organic monomer is selected from the group consisting of unsaturated mono or dicarboxylic acids having from 3 to 20 carbon atoms; acid anhydride, maleamic acid, acid halide, ester and metal salt derivatives of said unsaturated mono or dicarboxylic acids; vinyl esters of saturated carboxylic acids wherein the acidic constituent of said saturated carboxylic acid has from 2 to 18 carbon atoms; vinyl alkyl ethers wherein said alkyl constituent has from 1 to 18 carbon atoms; vinyl halides; vinylidene halides; acrylonitrile; methacrylonitrile; and styrene.

2. The composition as claimed in clause 1, characterized in that the ground vulcanized rubber is obtained by grinding scrap tires, coated tire scrapers, tire tubes and miscellaneous waste thermocracked rubber articles with the subsequent removal of the F Ferrous constituents or any other contaminants.

3. The composition as claimed in clause 1, characterized in that 0-300 parts per percent by weight are incorporated based on the composition of one or more additives, selected from the group consisting of carbon black, clay, silica, alumina, calcium carbonate, titanium dioxide, pigments, flame retardants, antioxidants, • Antidegradants, adhesives, reinforcing materials, processing aids and plasticizers.

4. The composition as claimed in clause 1, characterized in that the polyolefin resin is selected from the group consisting of polyethylene, polypropylene, polybutadiene, polybutylene, polyisoprene, or mixtures thereof.

5. The composition as claimed in clause 4, characterized in that the polyolefin resin is f polyethylene.

6. The composition as claimed in clause 1, characterized in that the functionalized olefin polymer is a copolymer of at least one olefin, including butadiene or hydrogenated isoprene, and one or more ethylenically unsaturated organic monomers selected from the group consisting of mono or unsaturated carboxylic diacids of 3-20 carbon atoms, acid anhydrides of said unsaturated mono- or dicarboxylic acids, acid halides of said unsaturated mono- or dicarboxylic acids, esters of said unsaturated mono- or dicarboxylic acids, maleamic acid derivatives of said acids unsaturated mono or dicarboxylics, vinyl esters of saturated carboxylic acids wherein said acid group has 2-18 carbon atoms, alkyl vinyl ethers wherein the alkyl group has 1-18 carbon atoms, -2? vinyl halides or vinylidene, acrylonitrile, methacrylonitrile and styrene.

7. The composition as claimed in clause 6, characterized in that the functionalized olefin polymer contains at least one functional group selected from the group consisting of mono or dicarboxylic acids and their derivatives selected from the group consisting of acid anhydrides, maleamic acids , acid halides, esters and metal salts, in an amount of 0.5 to 30 parts by weight per 100 parts by weight of the functionalized Jβ olefin polymer.

8. A process for making thermoplastic compositions comprising mixing a combination of about 1-90 parts by weight of ground vulcanized rubber in the form of dispersed small particles essentially of an average number of 1.5 mm or less, wherein said rubber is selected of the group consisting of natural rubber, S w- synthetic polymer or rubber copolymer derived from alkadienes, or mixtures thereof, and correspondingly, 90-1 parts by weight of polyolefin resin and at least 0.5 parts by weight of one or more olefin polymers functionalized by 100 parts by weight of polyolefin resin at a sufficiently high temperature to soften or melt the polymers, and for a sufficient time to obtain a homogeneous mixture wherein said functionalized olefin polymer is a copolymer of minus one olefin and at least one ethylenically unsaturated organic monomer; wherein said organic monomer is selected from the group consisting of unsaturated mono or dicarboxylic acids having from 3 to 20 carbon atoms; acid anhydride, maleamic acid, acid halide, ester and metal salt derivatives of said unsaturated mono or dicarboxylic acids; vinyl esters of saturated carboxylic acids wherein the acidic constituent of said unsaturated carboxylic acid has from 2 to 18 carbon atoms; vinyl alkyl ethers wherein said alkyl constituent has from 1 to 18 carbon atoms; vinyl halides; vinylidene halides; acrylonitrile; methacrylonitrile; # and styrene.

9. The process as claimed in clause 8, characterized in that the ground vulcanized rubber is obtained by grinding scrap tires, coated tire scrapers, tire tubes and miscellaneous waste thermosetting rubber articles with the subsequent removal of the constituents ferrous or any other contaminants.

10. The process as claimed in clause 8, characterized in that 0-300 parts per percent by weight are incorporated based on the composition of one or more additives, selected from the group consisting of carbon black, clay, silica, alumina, calcium carbonate, titanium dioxide, pigments, flame retardants, antioxidants, anti-degradants, adhesives, reinforcing materials, processing aids and plasticizers.

11. The process as claimed in clause 8, characterized in that the polyolefin resin is selected from the group consisting of polyethylene, polypropylene, polybutadiene, polybutylene, or polyisoprene or mixtures thereof.

12. The process as claimed in clause 11, characterized in that the polyolefin resin is polyethylene.

13. The process as claimed in clause 8, characterized in that the functionalized olefin polymer is a copolymer of at least one olefin, including butadiene or hydrogenated isoprene, and one or more ethylenically unsaturated organic monomers selected from the group consisting of acids unsaturated mono- or dicarboxylics of 3-20 carbon atoms, acid anhydrides of said unsaturated mono- or dicarboxylic acids, acid halides of said unsaturated mono- or dicarboxylic acids, esters of said unsaturated mono- or dicarboxylic acids, maleamic acid derivatives of said acids unsaturated mono or dicarboxylic acids, metal salts of said unsaturated mono or dicarboxylic acids, vinyl esters of the saturated carboxylic acids wherein said acid group has 2-18 carbon atoms, vinyl alkyl ethers wherein the alkyl group has 1- 18 carbon atoms, halides It is vinyl or vinylidene, acrylonitrile, methacrylonitrile, and styrene.

14. The process as claimed in clause 13, characterized in that the functionalized olefin polymer contains at least one functional group selected from the group consisting of mono or dicarboxylic acids and their derivatives selected from the group consisting of mono or dicarboxylic acids and its derivatives selected from the group consisting of acid anhydrides, maleamic acids, acid halides, esters and metal salts in an amount of 0.5 to 30 parts by weight per 100 parts by weight of functionalized olefin polymer.

15. A thermoplastic composition mixture containing a vulcanized ground rubber component characterized in that the mixture includes from 1-90 parts by weight of the ground vulcanized rubber in the form of small ground dispersed particles essentially of an average number of 1.25 mm or more F under, wherein said rubber is selected from the group consisting of natural rubber, synthetic copolymer rubber polymer derived from alkadienes, or mixtures thereof, and correspondingly, 90-1 parts by weight of a functionalized olefin wherein said polymer Functionalized olefin is a copolymer of at least one olefin and at least one ethylenically unsaturated organic monomer; wherein said organic monomer is selected from the group consisting of unsaturated mono or dicarboxylic acids having from 3 to 20 carbon atoms; acid anhydrides, maleamic acid, acid halide, ester and metal salt derivatives of said unsaturated mono or dicarboxylic acids; vinyl esters of saturated carboxylic acids wherein the acidic constituent of said saturated carboxylic acids has from 2 to 18 carbon atoms; alkyl vinyl esters wherein said alkyl constituent has from 1 to 18 carbon atoms; vinyl halides; vinylidene halides; acrylonitrile; methacrylonitrile; and styrene.

• 16. A process for making a thermoplastic composition blend characterized in that the process includes mixing 1-90 parts by weight of ground vulcanized rubber in the form of small dispersed particles essentially of an average number of 1.5 mm or less, in wherein said rubber is selected from the group consisting of natural rubber, synthetic polymer or copolymer rubber derived from alkadienes or mixtures thereof, and wt correspondingly, 90-1 parts by weight of one or more functionalized olefin polymers at a sufficiently high temperature to soften or melt the polymers, and for a sufficient time to obtain a homogeneous one wherein said functionalized olefin polymer is a copolymer of at least one olefin and at least one ethylenically unsaturated organic monomer; wherein said organic monomer is selected from the group consisting of unsaturated mono or dicarboxylic acids # having from 3 to 20 carbon atoms; acid anhydride, maleamic acid, acid halide, metal salt derivatives and ester of said unsaturated mono or dicarboxylic acids; vinyl esters of unsaturated carboxylic acids wherein the acidic constituent of said saturated carboxylic acids has from 2 to 18 carbon atoms, vinyl alkyl ethers wherein said alkyl constituent has from 1 to 18 carbon atoms; vinyl halides, vinylidene halides; acrylonitrile; methacrylonitrile and styrene.

17. The composition as claimed in clause 1, characterized in that 0.5 to 10 parts per percent by weight are incorporated based on the composition of a phenolic resin.

18. The composition as claimed in clause 17, characterized in that the phenolic resin is a phenol dimethylol resin.

19. The process as claimed in the clause, ?? M 8, characterized in that 0.5 to 10 parts per percent by weight are incorporated based on the composition of a phenolic resin.

20. The process as claimed in clause 19, characterized in that the phenolic resin is a phenol dimethylol resin.

21. The composition as claimed in clause 15, characterized in that 0.5 to 10 parts per percent by weight are incorporated based on the composition of a phenolic resin.

22. The composition as claimed in clause 21, characterized in that the phenolic resin is a phenol dimethylol resin.

23. The process as claimed in clause 16, characterized in that 0.5 to 10 parts per percent by weight are incorporated based on the composition of a phenolic resin.

24. The process as claimed in clause 23, characterized in that the phenolic resin reactive to heat is a dimethylenol fendly resin.

25. The composition as claimed in wt clause 18, characterized in that the functionalized olefin polymer is an ethylene vinyl acetate.

26. The process as claimed in clause 20, characterized in that the functionalized olefin polymer is ethylene vinyl acetate.

27. The composition as claimed in clause 22, characterized in that the functionalized olefin polymer is ethylene vinyl acetate.

28. The process as claimed in clause 24, characterized in that the functionalized olefin polymer is ethylene vinyl acetate. In testimony of which I sign the present in Mexico, D.F., on January 27, 1995. SYNESIS COMPANY Attorney #