PL126439B1 - Elastoplastic composition - Google Patents

Description

The subject of the invention is an elasto-plastic composition containing olefin rubber and polyolefin resins. It is known that vulcanization of EPMD rubber with a phenolic vulcanizing agent gives it good mechanical properties, but vulcanization of EPDM rubber with a phenolic vulcanizing agent has not been widely used. industry. Thermoplastic, elastometric (elastoplastic) compositions consisting of mixtures of polyolefin resin and vulcanized EPDM rubber, exhibiting good physical properties, including tensile strength, are known from the Belgian patent description No. 840,318. Mentioned above. New, improved compositions are economically attractive because they can be filled with oil and carbon black, which improve properties, including processability and oil resistance, while reducing costs. However, there is a need for compositions that are more resistant to oil and meet the requirements posed by exposure to oil. the action of organic solvents or oil at high temperature. Surprisingly, it was found that mixtures of polyolefin resin and EPDM rubber, vulcanized with a phenolic vulcanizing agent, exhibit better properties, including greater resistance to the action of oil, than compositions identical except for 10 15 20 25 30 in that the EPDM rubber contained therein is vulcanized with other agents. Therefore, the essence of the invention is the statement that elastoplastic compositions containing polyolefin resin and EPDM rubber vulcanized with a phenolic vulcanizing agent are elastomeric compositions with a high strength, can be processed like thermoplastic materials and that they have better properties than similar compositions in which the rubber component is vulcanized with sulfur or peroxides. The compositions according to the invention have increased resistance to oil and are less deformed when compressed, and the articles made from them have a smoother surface, free from turbidity. The use of phenolic vulcanizing agents reduces unpleasant odors during production and processing and produces end products with a more pleasant odor. The compositions according to the invention can be processed more easily, especially by extrusion, and the surfaces of the articles made from them bond better with the paint. These and other advantages are discussed in more detail later in the description. The elastoplastic composition according to the invention, containing a thermoplastic, crystalline polyolefin resin and fully vulcanized EPDM rubber in the form of dispersed particles with dimensions of an average of 50 micrometers or less, is characterized in that per 100 parts of the sum of both components, it contains about 25-75 parts of polyolefin resin and about 75-2)5 parts of EPDM rubber vulcanized with a phenolic vulcanizing agent and containing a phenolic vulcanizing resin and an activator. vulcanize while doing so vulcanized rubber - contains not more than about 3% by weight of unvulcanized rubber, extractable into cyclohexane at a temperature of 23°C or not more than about 5% by weight of unvulcanized rubber, extractable into boiling xylene The relative proportion of polyolefin resin and EPDM rubber is dependent on a number of factors, including the type, molecular weight and molecular weight distribution of the polyolefin resin or EPDM rubber and the absence or presence of other ingredients in the composition. For example, inert fillers such as carbon black or silica limit the range of acceptable proportions, while filler oil and plasticizers increase it. Preferred compositions contain polyolefin resin in an amount not exceeding 50% by weight of the sum of its components. In the composition according to the invention, EPDM rubber is fully vulcanized. A convenient way to assess the state of vulcanization is to determine the amount of rubber soluble in cyclohexane. Rubber is considered completely vulcanized when no more than about 3% of its mass passes into cyclohexane at 23°C. The procedure taking into account the presence of soluble components other than rubber is presented later in the description. An alternative method of assessing the vulcanization state is to determine the amount of rubber soluble in xylene at the boiling point of this solvent. Rubber is considered to be completely vulcanized when no more than about 5%, preferably not more than about 3%, and more preferably not more than about 1% of its weight is transferred to the boiling xylene. It should be noted that the compositions of the invention consist essentially of blends of polyolefin resin and vulcanized EPDM rubber and contain only negligible amounts or no graft copolymer of polyolefin resin and EPDM rubber. Therefore, the compositions of the invention should not be confused with the graft copolymers described in the US patents. America's no. 3 862 Q56 and 3 909 463, author Hartman. The absence of the graft copolymer in the compositions according to the invention is confirmed by the insolubility of the rubber in boiling xylene and the possibility of separating it from the polyolefin resin contained in the mixture. Hartmann graft copolymers are substantially completely soluble in boiling xylene. In the preferred compositions of the invention, substantially all of the polyolefin resin is soluble, and not more than about 3% of the rubber is extractable into boiling xylene. Infrared analysis of the isolated polyolefin resin fraction (soluble in boiling xylene but insoluble in xylene at room temperature) shows that it is essentially free from grafted EPDM rubber, i.e. that the content of this component is no more than about 2% by weight. Vulcanizable rubbers, although thermoplastic in the unvulcanized state, are normally classified as thermosets because they undergo irreversible transformation to a point where they cannot be processed. The products of the invention, although processed, irreversibly contain terinocured rubber (although of very small particle size), because they are made from mixtures of rubber and polyolefin resin treated with a phenolic vulcanizing agent, in the amount, time and temperature giving completely vulcanized products and the rubber actually gels (becomes insoluble in organic solvents) to a state characterized by such a degree of vulcanization. In the case of the composition according to the invention, thermosetting of the mass of the composition can be counteracted by simultaneous mastication and vulcanization of the mixture. Thus, the thermoplastic, elastometric (eiastoplastic) compositions of the invention can be prepared by mixing EPDM rubber, a softened or molten polyolefin resin and a phenolic vulcanizing agent and then masticating the mixture at a temperature at which the mixture remains molten. and which promotes vulcanization until its complete completion. Conventional masticating equipment may be used for this purpose, e.g. Banfoury mixers, Brabender mixers or certain injection molding mixing machines. The ingredients, except the vulcanizing agent, are mixed at a temperature sufficient to soften the polyolefin resin or, more often, after higher than its melting point if the resin is crystalline at normal temperature. After thoroughly mixing the molten resin with EPDM rubber, a phenolic vulcanizing agent (ie phenolic vulcanizing agent and vulcanization activator) is added. Heating and mastication at the vulcanization temperature are usually sufficient to complete the crosslinking reaction in a few minutes or less. The time necessary to complete the cross-linking reaction varies depending on the vulcanization temperature and the type of EPDM rubber and phenolic vulcanizing system. A suitable vulcanization temperature range is from about the melting point of the polyolefin resin (about 120°C in the case of polyethylene and about 175°C in the case of polypropylene) to 250°C or higher, and a typical range is from about 150° to 225°C. C The preferred range of vulcanization temperature is approximately 170-200°C. To obtain thermoplastic compositions, it is important that mixing during vulcanization is carried out without interruption. If vulcanization is continued after mixing is stopped, a non-processable thermoset composition can be obtained. The results obtained in the dynamic vulcanization process described above are a function of the system selected for vulcanization of the rubber. Currently, it has been found that using phenolic vulcanizing systems, improved compositions are obtained, which have not been obtained before. Similarly, the process using phenolic vulcanizing systems is only suitable for rubber of the polyolefin terpolymer type of two monoolefins and at least one diolefin, e.g. ethylene, propylene and non-conjugated diene with residual unsaturation in the side chain, usually called "EPDM rubber". EPM rubbers, which are substantially free of unsaturation sites, are not suitable because they are not sufficiently cross-linked by phenolic vulcanizing agents. Furthermore, a content of mixture of at least about 25% by weight of polyolefin resin. Thus, it is possible to obtain non-processable, dynamically vulcanized compositions even with complete gelation or to obtain only a slight improvement in tensile strength by vulcanization. It is understood, however, that no one will wanted to obtain unusable results and that no one would be misled by the fact that the interaction of the variables influencing the result is not fully understood. A few simple experiments, routine in this field of technology, using available rubbers and phenolic vulcanizing systems, will suffice to determine their suitability in the production of improved products according to the invention. All new products are processable in a closed mixer into products which, when transferred , at a temperature above the softening or crystallization points of the resin phases, continuous sheets are formed on the rotating rolls of the rolling mill. The sheets can be reprocessed in a closed mixer in which, after reaching a temperature above the softening or melting points of the polyolefin phase of the resin, they change into a plastic state (melted state of the resin phase), but passing the product through the rolling mill causes a continuous sheet to be formed again. A sheet of thermoplastic composition according to the invention can be cut into pieces and pressure formed to obtain a single, smooth sheet with the fragments completely bonded or fused. It is in this sense that the term "thermoplastic" is to be understood herein. Moreover, the elastoplastic compositions of the invention are further processable to the extent that they can be formed into articles by extrusion, injection molding, blow molding, etc. forming, thermoforming, etc. The degree of vulcanization is measured by the amount of rubber extractable from the mixture. Improved elastoplastic compositions according to the invention are prepared by vulcanizing the mixtures to such an extent that the vulcanized composition contains no more than about 3 % by weight of vulcanized rubber extracted from cyclohexane at 23°C or not more than about 5% by weight of rubber extracted with boiling xylene. Generally, the lower the extractable content, the better the properties. and even more preferred are compositions containing substantially no rubber extractable with organic solvents (less than 1.0% by weight). The percentage of soluble rubber in the vulcanized composition is determined by soaking a sample with a nominal thickness of 2 mm in cyclohexane at 2-3°C for 48 hours or keeping a thin film sample in reflux boiling xylene for half an hour, weighing the dried residues and make appropriate corrections according to knowledge of the composition. The corrections consist in subtracting from the initial and final weight solvent-soluble components other than vulcanizable rubber, such as filler oils, plasticizers, low molecular weight polymers and cyclohexane-soluble polyolefin resin components. Insoluble pigments, fillers, etc. are subtracted from both the initial and final weight. Currently, in unvulcanized rubber, materials soluble in acetone are considered non-crosslinkable ingredients and their amounts are subtracted when calculating the percentage of soluble rubber in the vulcanized composition. Up to 5%, typically 0.5-2.0%, by weight of EPDM rubber dissolves in acetone. It is obvious that a sufficient amount of phenolic vulcanizing agent must be used to fully vulcanize the rubber. The minimum amount of phenolic vulcanizing agent necessary to vulcanize the rubber depends on the type of rubber, the phenolic vulcanizing agent, the type of vulcanization promoter and the vulcanization conditions, such as temperature. Typically, the amount of phenolic vulcanizing agent used to completely vulcanize the EPDM rubber is about 5 to 20 parts by weight per 100 parts by weight of the rubber. Preferably, the phenolic vulcanizing agent is used in an amount of about 7 to 14 parts by weight per 100 parts by weight of rubber. Moreover, to ensure complete vulcanization of the rubber, an appropriate amount of vulcanization activator is added. A suitable amount of vulcanization activator is from 0.01 to 10 parts by weight per 100 parts by weight of EPDM rubber, although, if desired, this ingredient can be used in larger amounts to achieve a satisfactory degree of vulcanization. The term "phenolic vulcanizing agent" means collectively a phenolic vulcanizing agent (resin) and a vulcanizing activator. From the fact that the amount of phenolic vulcanizing agent is selected depending on the EPDM rubber content in the mixture, it should not be concluded that the phenolic the vulcanizing agent does not react with the polyolefin resin or that there is no reaction between the polyolefin resin and EPDM rubber. Such reactions can take place, but to a limited extent, so that there is no significant formation of copolymers grafted between the resin and the ¬ liolefin and EPDM rubber. In principle, all of the vulcanized EPDM rubber and polyolefin resin can be separated and separated from the mixture by extraction with a high-temperature solvent, e.g. boiling xylene, and infrared analysis of the isolated fractions shows the formation only small amounts or complete 10 15 20 25 M 15 40 45 50 55 60126 439 7 8 no grafted copolymer of EPDM rubber with polyolefin resin. Any EPDM rubber that can be completely vulcanized is suitable for the implementation of the invention. A suitable monoolefin, ter-polymer rubber comprises a substantially non-crystallized, rubber-like terpolymer of two or more α-monoolefins, preferably copolymerized with at least one polyene, usually a non-conjugated diene, which rubber is referred to as "rubber" in the present specification and claims EPDM" Suitable EPDM rubbers contain polymerization products of two olefin monomers, usually ethylene and propylene, and a smaller amount of unconjugated diene. The amount of unconjugated diene is usually 2-10% by weight of the rubber. Typically, any EPDM rubber that is sufficiently reactive with the phenolic vulcanizing agent to achieve complete vulcanization is suitable for carrying out the invention. The reactivity of EPDM rubber varies depending on the degree and type of polymer unsaturation. For example, EPDM rubbers containing ethylidenenorbornene are more reactive to phenolic vulcanizing agents than EPDM rubbers containing dicyclopentadiene, and rubbers containing hexadiene-1,4 are less reactive than those containing dicyclopentadiene. . However, the differences in reactivity can be compensated by introducing larger amounts of the less reactive diene into the rubber molecule. For example, 2.5% by weight of ethylidenenorbornene or dicyclopentadiene is used, while hexadiene-1,4 must be used in an amount of at least 3% by weight. Suitable α-monoolefins are compounds of the formula CH2~CHR, where R is a hydrogen atom or an alkyl radical with 1-12 carbon atoms, e.g. -1, 3,3-dimethylbutene-1, 2,4,4-trimethylpentene-1, 3-methylhexene-1, 1,4-dimethylhexene-1 and others. Suitable unconjugated dienes are straight-chain (acyclic) dienes such as 1,4-hexadiene, 2-methylpentadiene-1,4, 1,4,9-decatriene and 11-ethylridecadiene-1,11; single-ring dienes such as cyclooctadiene-1,5, cycloheptadiene-1,4 and 1-mephylcyclooctadiene-1,5; bridged two-ring dienes such as 5-ethylidene-norbornene, 5-methylene-2-norbornene, 54-sopropylidene-2-norbornene, and 2-methylbicyclo[2.2.1]heptadiene-2,5; fused two-ring compounds, such as bicyclo[4.3.0] nonadiene-3,7, 5-methylbicyclo[-4.3.0] nonadiene-3,7, 5,6- d/wumethylbicyclo[4.3.0] nonadiene-3 .7 and bicyclo[3.2.0]heptadiene-2,6; single-ring compounds with an alkenyl substituent, such as 4-vinylcyclohexene, 1,2-divinylcyclobutane and 1,2,4-trivinylcyclohexane, and three-ring compounds, such as dicyclopentadiene. EPDM rubber grades suitable for carrying out the invention are commercially available; Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 406-410. Suitable thermoplastic polyolefin resins include crystalline, high molecular weight, solid polymerization products of one or more monoolefins, at high or low pressure. Examples of such resins are isotactic and syndiotactic monoolefin polymers, which are commercially available. Examples of suitable olefins are ethylene, propylene, butene-1, pentene-1, hexene-1, 2-methylpentene-1, 3-methylpentene-1, 4-methylpentene-1, 5-methylhexene-1 and their mixtures. Commercially available thermoplastic polyolefin resins, such as polyethylene and especially polypropylene, may advantageously be used in the invention. Any phenolic vulcanizing system which completely vulcanizes EPDM rubber is suitable for the invention. The basic ingredient of such a system is a vulcanizing phenolic resin, obtained by condensation of substituted or unsubstituted phenol with an aldehyde in a basic medium or by condensation of difunctional phenol dialcohols. Particularly suitable are vulcanizing resins based on halogenated phenol. It is particularly recommended to use vulcanizing systems containing a phenolic resin, a halogen donor and a metal compound. Details of such systems are provided by Giller in the St. Pat. United No. 3,287,440 and Gerstin et al. in St. Patent No. 3,287,440 United No. 3,709,840. Halogenated, usually brominated, phenolic resins containing 2-1.0% bromine by weight do not usually require a halogen donor, but are used in conjunction with a hydrogen halide binder, e.g. such as iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and especially zinc oxide, the presence of which promotes the cross-linking function of the phenolic resin. However, in the case of rubbers that are resistant to vulcanization by phenolic resins, the combined use of a halogen donor and zinc oxide is recommended. The preparation of halogenated phenolic resins 40 and their use in vulcanizing systems with zinc oxide are described in US patents. United Americas No. 2972 600 and No. 3 093 6|1|3. Examples of suitable halogen donors are stannous chloride, ferric chloride or halogen-donating polymers such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). The term "activator" herein means any material that increases the cross-linking efficiency of a phenolic vulcanizing resin and includes both metal oxides and halogen donors. For further details regarding phenolic vulcanizing systems, see "Vulcanization and Vulcanizing Agents", W. Hoffman , Palmerton Publishing Company. Suitable phenolic and brominated phenolic vulcanizing resins are commercially available, e.g., SP-1045, CRJ-352, SP-1055 60, and SP-1056 resins from Schenectady Chemicals, Inc. Similar, functionally equivalent Phenolic vulcanizing resins can also be obtained from other manufacturers. As explained above, the vulcanizing agents are used in such quantities as to obtain substantially complete vulcanization of the rubber.126 439 9 10 The properties of the elasto-plastic compositions of the invention may be modified. , before or after vulcanization, adding ingredients conventionally used in the production of EPDM rubber, semi-olefin resin and mixtures thereof. Examples of such ingredients are carbon black, silica, titanium dioxide, color pigments, clay, zinc oxide, stearic acid, stabilizers, anti-degradation agents, flame inhibitors, processing aids, adhesives, plasticizers, wax, discontinuous fibers, Such as wood cellulose fibers and filling oils. It is especially recommended to add carbon black, oil or both, preferably before dynamic vulcanization. Carbon black increases tensile strength and promotes phenolic vulcanizing agents. Oil filler can improve the oil swelling resistance, thermal stability, hysteresis, cost and permanent deformation of the elasto-plastic composition. Aromatic, naphthenic and paraffin oils are suitable. The addition of oil can also improve processability. Suitable filler oils are presented in the above-quoted Rubber World Blue Book, pages 145-190. The amount of oil additive depends on the desired properties, and the upper limit depends on the ability of the oil to combine with the ingredients of the mixture. This limit is exceeded when excessive discharge of fill oil occurs. Typically, 5-300 parts by weight of oil are added to 100 parts by weight of the mixture of olefin rubber and semi-olefin resin. Typically, this amount is in the range of about 30 to 250 parts by weight of oil per 100 parts by weight of rubber present in the mixture, and the preferred content is about 70 to 20) parts by weight per 100 parts by weight of rubber. The amount of filling oil depends, at least to some extent, on the type of rubber. Rubbers with high viscosity absorb more oil. When preparing compositions according to the invention that are to be colored, colorless or white pigments (fillers or reinforcing pigments) are used instead of carbon black. Silica, aluminum silicate, magnesium silicate and titanium dioxide are suitable for these purposes. Typically, the white pigment is added to the mixture in an amount of 5-100 parts by weight per 100 parts by weight of rubber. The typical addition of carbon black is 40-2.50 parts by weight per 100 parts by weight of EPDM rubber, and usually about 20-100 parts by weight of carbon black are added per 100 parts by weight of the sum of EPDM rubber and filler oil. The amount of carbon black that can be used depends, at least to some extent, on its type and on the amount of oil used. Methods other than dynamic vulcanization of rubber/polyolefin resin mixtures may be used to prepare the compositions of the invention. For example, the rubber can be completely vulcanized in the absence of the semi-olefin resin, dynamically or statically, pulverized and mixed with the polyolefin resin at a temperature above its melting or softening point. If the particles of the cross-linked rubber are small, carefully distributed and used in the appropriate concentration, the compositions of the invention can be easily obtained by mixing the cross-linked rubber with a polyolefin resin. Thus, "blend" herein means a mixture of finely distributed, small particles of cross-linked rubber. A mixture which does not fall within the scope of the invention because the rubber particles are not properly distributed or are too large may be milled. cold, to reduce the particles below 50 μm, preferably below 20 μm, and especially below 5 μm. After appropriate grinding or powdering, the composition according to the invention is obtained. Often, poor distribution or too large size of carbon particles rubber particles are visible to the naked eye and noticeable in the formed sheet. This is especially the case in the absence of pigments and fillers. In this case, pulverization and re-forming produce a sheet in which aggregates of rubber particles or large rubber particles are not visible to the naked eye. eye or much less noticeable and which have much better mechanical properties. The elastoplastic compositions of the invention are useful in the production of many articles, such as tires, hoses, belts, gaskets and various types of shapes. They are particularly useful in the production of articles by extrusion, injection molding and compression. They can also be used to modify thermoplastic resins, especially polyolefin resins. Conventional equipment is used to blend the compositions with thermoplastic resins. The properties of the modified resin depend on the amount of elasto-plastic composition introduced. Typically, the amount of the elastoplastic composition is such that the modified resin contains about 5 to 25 parts by weight of EPDM rubber for about 95 to 75 parts of the total weight of the resin. The strength properties of the composition are determined according to ASTM D-638 and ASTM D -1'566. The term "elasphomeric" in the present specification and claims means a composition which, in a given period of time (1 or 10 minutes), shrinks to less than 100% of its original length when expanded at room temperature to twice its original length and held in a stretched state for the same time (1 or 10 minutes). Compression deformation is determined according to ASTM D-319\5, method B, by compressing the sample for 22 hours at 100°C. Swelling in oil (percentage change in weight) is determined according to ASTM D-471, by immersion in ASTM-3 oil, for $ days at 121° C. Particularly preferred compositions of the invention are rubber compositions having a compressive strain value of about 5G% or less, these compositions meet the definition of rubber according to ASTM Standards, Volume 28, page 756, rubber compounds having a Shore D hardness of 60 or less, a 100% modulus of 17 MPa or less, or a Young's modulus of less than 245 MPa. To illustrate in this invention, a masterbatch containing EPDM rubber , paraffinic filler oil, carbon black, zinc oxide, stearic acid 10 15 20 25 30 95 40 45 50 55 60126 439 11 12 and optionally an anti-degradation agent (all ingredients in parts by weight) are mixed with polypropylene. Mixing is carried out for 2.5 minutes at a speed of 80 revolutions per minute in a Brabender mixer placed in an oil bath at a temperature of 180°C. The polypropylene melts and a homogeneous mixture is obtained. In the following, when talking about the temperature of the Brabender mixer, we mean the temperature of the oil bath. The phenolic vulcanizing agent is added and mixing is continued for a further 4 minutes, during which time the maximum Brabender consistency value is reached. After being removed from the mixer, the composition is pressed into shape at 210°C. Before removing from the mold, the samples are cooled below 100°C. The properties of the formed samples are determined and recorded. Data for the various compositions are summarized in Table I. Batches 1-3 and 4-6 contain different EPDM rubbers, which shown in the references. Compositions 1 and 4 are control and do not contain a vulcanizing agent. Compositions 2 and 5 illustrate the invention and are vulcanized with a phenolic vulcanizing agent. Compositions 3 and 6, included for comparison, are vulcanized with a sulfur system. The rubber used in compositions 2, 3, 5 and 6 is completely vulcanized, i.e. less than 3% by weight of the rubber (based on the total rubber contained in the composition) is extracted into the cyclohexane at room temperature or into boiling xylene. Vulcanized compositions are elastomeric, processable like thermoplastic materials and can be reprocessed without regeneration, unlike statically vulcanized compositions which are thermosetting and cannot be processed like thermoplastic materials The data presented in Table I show that compositions prepared from EPDM with a high ethylene content have greater hardness. Compositions made with phenolic vulcanizing resin have essentially the same strength properties, but the sulfur vulcanizing system is more effective in compositions containing EPDM rubber with low polydispersity. Compositions vulcanized with phenolic vulcanizing resin have two significant advantages over compositions vulcanized with sulfur agents, namely greater resistance to oil (low swelling) and less deformation under compression. Compositions containing EPDM rubber as the main ingredient are presented in Table II. Composition 1 does not contain vulcanizing agents. Composition 2 is a composition according to the invention, a vulcanized phenolic vulcanizing resin. Compositions 3 and 4, included for comparison, are vulcanized with a sulfur vulcanizing system and a peroxide agent, respectively. Polypropylene is the same as in Table I. EPDM rubber is a terpolymer of 69% by weight of ethylene, 8.3% by weight of ethylidene norbornene, the remainder polypropylene; polydispersity 2.2, viscosity Composition EPDM rubber Polypropylene 8 Oil. filler Carbon black Zinc oxide Stearic acid Flectol-H4, antidegradation agent SP-10565 Sulfur vulcanizing agent6 Hardness, Shore D 100% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Set in oil ASTM-3, % Compressive deformation, % 1 361 64 30.6 28.8 1.8 0.36 0.7l2 3.24 — 43 8.4 10.78 460 131 —f Table 2 361 64 30.6 28.8 1.8 0.36 0.72 — — 47 11,.27 17.2 390 67 — I 3 361 64» 30.6 28„8 1.8 0.36 0.72 — 1.31 47 9.9 18.6 490 88 — ¦ 4,362 64 30.6 28.8 1.8 0.36 — — — 35 6.8 7.6 460 88 68 5,362 64 . . 30.6 28.8 1.8 0.36 — 3.24 — 40 11.1 17.5 30Q 53' 39 fl 1 36» 64 30^6 28.8. 1.8 0.38 — — 1.31 39 8.5 13.6 390 7^ 52 1 73 ethylene by weight, 4.4% ethylidenenorbornene by weight, poly dispersity 2.1, specific gravity 0.86, Mooney viscosity 55 (ML+121°C) 8 55% ethylene by weight, 4.4% ethylidenenorbornene by weight, polydispersity 5.2, specific gravity 0.86, Mooney viscosity 40 (ML 1+8 121°C) and low fluidity, general use", specific gravity 0.902, elongation 11% 1 polymerized 1,2-dihydrogen-2,2,4-trimethylquinoline * brominated methylolphenol vulcanizing resin 6 sulfur 17.2 parts, zinc methyl dithiocarbamate 10.3 parts tetraethylthiuram disulfide 10.3 parts , 2-bis(benzothiazolyl) disulfide 34.5 parts and dipentamethylenethiuram hexasulfide 27.7 parts13 126 439 14 T a b 1 and c a II Composition EPDM rubber Polypropylene SP-1056 Zinc oxide tetraethylthiuram disulfide 2-bis-(benzothiazolyl) disulfide u) Sulfur 2 ,5-dimethyl-2,5-di- (III-butylperoxy) hexane Hardness, Shore D 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation ,, % Specification in ASTM-3 oil, % Part of the sample soluble in cyclohexane at room temperature, % by weight Part of the rubber soluble in cyclohexane at room temperature (without correction for rubber components soluble in acetone), % by weight 1 GO 40 — ¦'¦' — — — — —1 36 5.9 — 6.27 300 38 91 133 48 , 80 2 6i0 40 6.75 1.25 — — ¦ — — 42 9.9 21 .6 23.9 310 aa 24 10.9 0 0 3 60 40 — 3.0 0.6 0.3 0.9 — 43 10.78 17.5 21.2 370 34 43 194 0 0 4 1 60 40 — —» | — — , 1.2 39 8.03 11.9 16.07 420 35 32 ¦ ¦¦ 225 ¦ 1 '¦ 1.7 Mooney'a 51 (ML 8, Ui00°C). Procedure as in Table I, except for composition 2, zinc oxide is added one minute after adding the phenolic vulcanizing resin, and in composition 4, after reaching the maximum Brabender consistency, 0.6 parts by weight of trinonylphenyl phosphite, an agent, are added. scavenging free radicals. The data show that the vulcanized phenolic vulcanizing resin composition has greater resistance to oil (swells less) and less deformation under compression. Table III shows soft compositions with a high proportion of rubber and oil fill ¬ cego. The procedure is the same as in Table I, except that after adding the vulcanizing agents, mixing is continued for 5 minutes. Composition: 1 is a control and does not contain any vulcanizing agents. Compositions 2, 4 and 6 are compositions according to the invention, vulcanized with phenolic vulcanizing resins. Compositions 3, 5 and 7 are vulcanized with sulfur vulcanizing systems. Data show that compositions vulcanized with phenolic vulcanizing resins have less compressive deformation and greater oil resistance. In addition, compositions vulcanized with phenolic vulcanizing resin provide smoother surfaces after extrusion or injection molding. The surfaces of moldings and parts formed from compositions vulcanized with phenolic vulcanizing resins are free from efflorescence and do not stick. Composition 6* with a high proportion of rubber has favorable elastomeric properties, such as low tensile deformation and low compression deformation. Tests on the influence of the amount of vulcanizing agent 30 35 45 50 65 are presented in Table IV. The procedure and ingredients 8a are the same as in Table III. As can be seen from the data presented, increasing the amount of vulcanizing agent has a smaller impact on the strength properties in the case of the sulfur vulcanizing system than in the case of the phenolic resin system. The tensile strength in both systems does not change substantially with changes in the concentration of the vulcanizing agent. As the concentration of the phenolic resin increases, the modulus increases and the elongation decreases, while both of these parameters do not change substantially with changes in the amount of sulfur vulcanizing agent. At all tested concentrations, compositions vulcanized with phenolic resins show lower compressive deformations and higher oil resistance. Compositions according to the invention vulcanized with non-halogenated phenolic vulcanizing resins are shown in Table V. The procedure is the same as before. . Composition L is a control one and does not contain any vulcanizing additives. Composition 2 is a control containing a phenolic vulcanizing resin but no vulcanizing activator. Composition 5 is another control, containing a sulfur vulcanizing agent. Control 3 contains dimethylol-p-nonylphenol (phenolic vulcanizing resin of the commercial brand SP-1045). Compositions 3 and 4 contain stannous chloride and chlorosulfonated polyethylene as halogen donors, respectively. The data show that the use of a vulcanization activator in conjunction with a non-halogenated phenolic vulcanizing agent is not critical for complete vulcanization of the rubber. The presence of a halogen donor (vulcanization activator) causes13 126 439 16 Composition EPDM and oil-filled rubber1 Polypropylene2 Filling oil Flectol-H8 carbon black, anti-degradation agent Zinc oxide Stearic acid SP-10502 Sulfur vulcanizing agent Hardness Shore A 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at | breaking strain, % and Tensile strain, % Compression strain* % ASTM-3 oil setting, % 1 91.2 54.4 36.4; 36.4 Q.91 2928 0.46 — — 8H 2.9 — 4.3 500 — — 167 2 9U 54.4 36.4 36.4 0.91 2.28 0.46 M — 83 5y2 10, 78 13.8 410 14 30 52 Table 3 91.2 54.4 3(6.4 36.4 0.91 2.28 0.46 — 1.65 84 4.5 8.5 1^4.7 550 14 47 69 III 4 100.6 49.7 23.9 ^8.9 0.90 2.41 0.49 4.43 — 82 4.5 9.9 13.1 390 12 2a 52 5 100.6 49 .7 28.9 28.3 0.96 2„41 0.49 — 1.80 81 4.3 8.4 14.7 560 ) 11 49 84 6 124.4 37.8 31.1 18.66 — 1.16 0„62 6,W —? 71 3.3 — 8.9 290 6 20 59 7 124.4 37.8 311.1 1 18.66 — 3.11 0.62 —< 2.25 71 2.3 59 6.76 350 17 34 91 1 63% by weight of ethylene, 3.7% by weight of ethylidenenorbornene, polydispersity 2.6, specific gravity 0.90, Mooney viscosity (ML-4, 125°C) 50, terpolymer filled with 100 phr of non-corrosive naphthenic oil 8 polypropylene and agents vulcanizing As in table I, significant increase in tensile strength and reduction of compressive deformations, and increases resistance to oil. The high spec in the oil of composition 2 indicates that the rubber is only partially vulcanized. The data also show that compositions vulcanized with a phenolic vulcanizing system containing a halogen donor have lower compressive deformability and greater oil resistance than similar vulcanized compositions. treated with a sulfur agent. Compositions 3 and 4 show particularly high retention of tensile strength after oil curing. The tests shown in Table VI further demonstrate that complete vulcanization of the rubber requires the presence of an activator (zinc oxide). The procedure is the same as in Table I, but no masterbatch is used because the compositions do not contain carbon black or filler oil. Compositions 1 and 2 are the same except that composition 2 does not contain zinc oxide. The data for composition 2 shown in Table VI are the average of two tests. 45 S5 60 65 In order to determine the degree of vulcanization of the rubber, the compositions are extracted with boiling xylene (vulcanized rubber is insoluble in boiling xylene). Samples are extracted in the form of a thin film (about 0.06 mm thick). After 30 minutes the film usually disintegrates. Then the suspension in xylene is filtered through a glass fiber filter with a pore size of 0.3 (im. It is assumed that all ingredients, except polypropylene, are part of the vulcanized rubber. The filtrate is cooled to room temperature, which causes precipitation of the polypropylene (or crystalline graft copolymer), which material is filtered off. The second filtrate is evaporated to recover material that is soluble in xylene at room temperature. (Ataxic polypropylene, low molecular weight polypropylene, amorphous ethylene-propylene copolymer, unvulcanized EPDM rubber or non-crystalline grafted polypropylene-EPDM rubber copolymer). The weight percentage of the recovered material is given in parentheses together with the calculated theoretical value. Table IV Composition EPDM rubber with oil fill1 Polypropylene2 Filling oil Oxide zinc Stearic acid Flectol-H, antidegradant SP-10562 Sulfur vulcanizing agent2 Hardness, Shore A 1/00% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation, % Oil setting ASTM-3, % 1 Q1 * R4 4. ^fi, 4 00(,,t 36 4 2 28 0 46 - 0 91 - —! — 81) 2.8 4.0, 630 52 78 162 2 4.05 — 84 4.99 13.1 430 14 31, 52 3 5.07 : 85 5.58 13.9 370 14 3H 49 4 6.08 — 85 6.56 18.8 290 12 24 43 5 7.96 — 85 6.86 13.8 280 13 26 41 6 — 1.24 84 4.3 H5 550 14 45 73 ' — 1.66 85 4.3 14, 8 590 14 38 74 » —* 2.07 85 4.6 15.0 560 13 48 71 9 —. 2.48 85 4.8 14.8 530 13 47 67 - ¦¦ ¦V ¦ - ¦- 1 as in Table II 1 as in Table IIfr 126 439 2* Table V Composition Rubber EPDM1 Polypropylene* Filling oil Soot | Zinc oxide 1 Stearic acid SP-1045* SnCl3 Chlorosulfonated polyethylene Sulfur vulcanizing agent* Hardness, Shore D 100% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation, % Oil setting ASTM -3.% Oil tensile strength limit, MPa % strength retention | tensile limit 1 36 04 ao,e 28.8 U* 0.35 — — — ¦ — 37 7.0 9.3 510 48 — | / TO 3.7 40.0 * 1 3G $4 30.6 2&S\ 1.8 0.36 4.33 — — — 42 10.0 16.6 450 aa 57 86 v - 8.1 48.8 3 36 64 30.6 28.8 V* 0.36 4.3fc 0.70 — — 45 H3 22.1 260 27 36 44 15.4 69.6 4 36 G4 30.6 28.8 13 Q.36 4.32 — 1.8 — 45 12.6 21.8 380 29 30 55 14,p 1 64.0 5 1 36 04 30.6 28.8 1.8 0.36 —* —i — 1*06 43 11, 1 20.67 410 32 49 ' 66 H,0 53.7 69% by weight of ethylene, 8.3% by weight of ethylidenerbofnene, polydispersity 2.1, specific gravity 0.86, Mooney viscosity 50 (ML-8, 100° C) as in Table I, dimethylol-p-nonylphenol (non-halogenated) for vulcanized EPDM rubber. The court makes a correction to the calculated value for vulcanized rubber to take into account materials present in the vulcanized rubber which remain soluble in boiling xylene after vulcanization. The correction (1.6% by weight of rubber) is the sum of the part of the unvulcanized rubber soluble in acetone, 0.9% by weight, and the part insoluble in cyclohexane at room temperature, 07% by weight. The material soluble in acetone is considered non-crosslinkable, and the material soluble in cyclohexane at room temperature is considered a polyolefin copolymer. For example, in the case of composition 1, the calculated value in parentheses for the insoluble rubber is 39.3% by weight, which would be 39.3% by weight without the above correction. Similar corrections were made to the calculated values given in tables VII-IX (in brackets). The data presented show that composition 1, containing zinc oxide, has less deformation under tension and compression and swells less in oil, and that the rubber contained therein is not extracted into boiling xylene at all. This proves the complete vulcanization of the rubber and confirms the absence of the transplanted copolymer. From a composition containing no zinc oxide, 32% of rubber passes into boiling xylene. This indicates the presence of a graft copolymer or only partial vulcanization of the rubber. The above data demonstrate that in order to obtain the compositions of the invention with a fully vulcanized rubber, it is critical to use a vulcanization activator which promotes the reaction essentially exclusively between the EPDM rubber and the phenolic vulcanizing resin. The compositions of the invention have high hardness, contain carbon black and have a high degree of ¬ polypropylene values are presented in table VII. The masterbatch of EPDM rubber, carbon black, zinc oxide and stearic acid is mixed with polypropylene in a Brabender mixer at a speed of 80 rpm, at 180°C, until the polypropylene melts to obtain a homogeneous mixture. The phenolic vulcanizing resin is added and mixing continues until the maximum Brabender consistency is achieved, then mixing continues for 3 minutes. The compositions are removed, rolled into sheets, returned to the Brabender mixer and mixed for 2 minutes at 180°C. The data show that the compositions are harder and stiffer than the compositions in the previous tables, containing more rubber. Tensile strain values indicate that the compositions have reduced elasticity. 2V 126 439 22 Table VI Table VII Composition Rubber EPDM1 Polypropylene2 Stearic acid Zinc oxide Flectol-H, anti-degradation agent2 SP 10562 Hardness Shore D 100% modulus, MPa 300% modulus MPa; I Ultimate tensile strength, MPa Elongation at break, % Tensile strain, % Compressive strain, % Settling in oil - ASTM-3, % Part of the sample insoluble in boiling xylene, % by weight Part of the soluble rubber ¬ soluble in boiling xylene, % by weight Part of the sample insoluble in xylene at room temperature, % by weight Part of the sample insoluble in xylene at room temperature, % by weight Total, % 36 34 0.36 1, 8 0.72 4.05 53 13.8 15.4 1^7.5 590 42 51 105 40.2 (39.3) ; 0 5.5.0 (60.4) <7 | 99.9 36 64 0.36 Q.72 4.05 5V 13.0 16.1 530 52 67 15iV 2Q.3 (38,a) 32.0 a6.7 (61.4) 17.8 ioo,a JO 15 20 25 30 35 55% by weight of ethylene, 4.4% of nene, polydispersity 2.5, Mooney's 70 (ML 1 + 8, 121°C) as in Table I by weight of ethylidenenorborbor - specific gravity 0.86, viscosity However, the solubility data show that the rubber is completely vulcanized and is not soluble in boiling xylene at all. The order in which the ingredients are added is important, especially vulcanization activators, such as; zinc oxide. It is especially important when adding large amounts of zinc oxide in the absence of a filler. An illustration of the above is provided in Table VIII. The procedure is the same as in Table I, but no masterbatch is used because the composition does not contain soot and filler oil. The ingredients are added in the given order. In the case of compositions 1-5, zinc oxide is added before the phenolic vulcanizing resin, while in the case of compositions 6-9, the order of adding these ingredients is reverse. The presented data show that the strength properties deteriorate with increasing amounts of 40 45 50 55 60 65, Composition Rubber EPDM1 Polypropylene1 Carbon black Stearic acid Zinc oxide SP-10561 Hardness Shore A Shore D 100% modulus, MPa 300% modulus , MPa Ultimate tensile strength, MPa Elongation at break, % Compressive deformation, % Parts of the sample insoluble in | boiling xylene, 1% by weight 1 25 75 20 0.25 1.25 2.75 97 60 19.2 23.0 26.9 440 54 40<}1 (39.3) Z 30 70, 24 ' 0.3 1.5 3.3 99 60 17.9 22.9 23.5 320 54 45.4 (45.4) 3 I 35 65 28 0.35 1.75 3.85 99 59 17.5 24.1 25 ,1 350 47 51.9 51.0 1 as in Table VI of zinc oxide, when zinc oxide is added before the phenolic vulcanizing resin, while the effect of the amount of zinc oxide on the strength properties is small when it is added last. Such compositions exhibit greater compressive and tensile strength, less deformation under tension and compression, and greater resistance to oil. Solubility data indicate that the order in which zinc oxide is added has a significant effect on the degree of vulcanization of the rubber. The amount of rubber soluble in boiling xylene varies from 0 to 23%, depending on the amount of zinc oxide in the composition, if zinc oxide is added before the phenolic vulcanizing resin, if zinc oxide is added last. , as in composition 6-9, the amount of rubber soluble in boiling xylene is 1% or less. A correction of 0.9% by weight was introduced to the determined solubility of rubber in cyclohexane, taking into account the part of the vulcanized rubber soluble in acetone. The correction should probably be larger to take into account stearic acid, which may also be extracted into cyclohexane. Tests for varying the proportions of EPDM rubber and polypropylene are shown in Table IX. The compositions contain only EPDM rubber, polypropylene, phenolic vulcanizing resin and zinc oxide. The amounts of zinc oxide and phenolic vulcanizing agent are varied to maintain a constant ratio of vulcanizing agent to rubber - 2 parts by weight of zinc oxide and 10 parts by weight of phenolic vulcanizing resin per 100 parts by weight of rubber. EPDM rubber and polypropylene are loaded into a Brabender mixer maintained at 180°C and mixed at a speed of 100 rpm. In 3 minutes after melting the polypro-Table VIII Composition no. Rubber EPDM1 Polypropylene1 Stearic acid Zinc oxide SP-10561 1 Zinc oxide 1 1/00% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Hardness, Shore D Tensile strain, % Compression strain, % Oil setting, wt.% Part of the sample insoluble in boiling xylene, wt.% Part of the rubber soluble in boiling xylene, wt.% % by weight Part of the rubber soluble in cyclohexane at temperature | room temperature, % by weight 1 50 2 3 4 5 « ? 8 9 v~ 50 .. . . ... . . .... . . . ... .. .. ^ 1 0 5 — q.05 5 65 11.3 21.9 22.5 320 45 25 31 iai 52.5 (52.2) 0 0.29 0 0.75 — 10, 5 15.5 22.3 46/0 43 27 39 145 50.5 (52.5) 4.0 V 2,» 1.5 -u 10.0 14.0 19.1 480 43 30 41 149 46, 4 (53.V 13.4 2.3 4.0 2.25 — 9.7 13.0 17.7 500 43 32 41 152 45.5 (53.5) 16.0 2.2 3.9 3 ,0 — 9.4 11.9 1*6 480 43 35 45 164 42.3 (53.8D 23.0 2.5 4.6 0.75 10.7 18.9 25.5 380 44 25 34 106 54.0 (52.5) 0 0.9(3 1.1 ._ | 1.5 10.6 17.3 23.8 390 45 26 35 im 53.7 (53.1) 0 0.71 Q .6 -. 2.25 10.5 17.0 16.5 430 44 25 33 110 53.0 (53.5) 1.0 1.03 1.3 7" w. r* r- 3.0 10 ,3 16.6 25.6 440 44 Z5 38 110 54.0 (53.8) o 0.71 0.6 \ as in table VI.126 439 25 26 Table IX [ Composition Rubber EPDM1 Polypropylene1 SP-10561 Zinc oxide 100% modulus, MPa Ultimate breaking strength, MPa E, MPa Elongation at break, % Hardness Shore A Shore D Tensile strain, % Part of the sample insoluble in boiling xylene, % by weight Part of the rubber soluble in boiling xylene, | % by weight 1 6Q 40 6 in 9.7 215.6 48.6 3|80 8.9 44 18 62.8 (61.7) 0 Z 50 5Q 5 1.0 11.8 23.6 77.1, 430 92 48 27 51.7 (52.0) | 0.6 3 40 eo 4 0.8 13.8 27.8 237.8 460 98. 52 43 44.0 (42.2) 0 4 30 70 3 0.6 16.6 24.3 349.5 440 95 60 49 31.4 (31.5) 0.3 5 20 80 2 0.4 1.7.6 25.9 477.4 510 97 65 60 6 10 90 1 ¦ 0.2 210.0 22, 9 742.5t 57:0 97 71 85 (overweight) 21.7 (21.6) 0.5 12.0 (11.0) 0 | 1, as in Table VI, the phenolic vulcanizing resin is added to the dust and stirring is continued for 4 minutes. The compositions are removed from the mixer, rolled into sheets, returned to the mixer and mixed for a further 2 minutes. The compositions are again removed from the mixer, formed into sheets and compressed at 220°C. All compositions are thermoplastic and compositions 1-4 are elastomeric. Compositions 5 and 6, with a high proportion of polypropylene, are non-elastomeric. When stretched, they become narrower, i.e. they go through a state that makes it impossible to return to their initial form. In the entire range of proportions, the rubber is completely vulcanized; the amount of rubber soluble in boiling xylene is less than 1% by weight of the rubber present in the composition. Dyeable compositions according to the invention, containing a white pigment (magnesium silicate) and a composition according to the invention containing polyethylene, are shown in table The preparation method is the same as in Table VIII, except that the magnesium silicate is completely dissolved before adding the phenolic vulcanizing agent. In the presence of magnesium silicate, the addition of zinc oxide is not required. Solubility data in cyclohexane indicate that the rubber is completely vulcanized. Composition 2 contains (all parts by weight): 40 parts of EPDM rubber, 60 parts of polyethylene, 0.4 parts of stearic acid, 0.8 parts of zinc oxide and 4.5 parts of phenolic vulcanizing resin SP-1056. The rubber and polyethylene are loaded into a Brabender mixer, maintained at 180°C, and masticated at 80 rpm until the polyethylene melts. Stearic acid and phenolic vulcanizing agent are added and mixing is continued until a homogeneous mass is obtained. Tin oxide is added - Table Tensile strain, % Compressive strain, % Part of the sample insoluble in boiling xylene, wt.% Soluble rubber, wt.% Part of the sample soluble in cyclohexane at room temperature, wt.% 1 | 50 50 — 40 0.5 —» 5.6 46 13),0 16.3 18.6 420 26 28 64.0 (64.0) 0 0.1 2 40 — 60 — 0.4 0.88 4 ,5 44 10.0 1.5.5 18.6 370 3(3 27 46.8 (4A6) 0 0.2 1 as in Table VI 1 polyethylene with average molecular weight distribution, ASTM D-1248-72, type III, class A, melting index 0.3 g/i0 minutes, specific gravity 0950 g/cm*126 439 27 28 ku and continue mixing until maximum consistency is obtained (3-4 minutes) and for another 2 minutes. The resulting composition is thermoplastic. tangential and elastomeric. The solubility data indicate that the rubber is completely vulcanized. The compositions of the invention, in which various activators are used, are presented in Table XI. EPDM rubber contains 55% by weight of ethylene, 40.6% by weight of propylene and 4.4% by weight of dicyclopentadiene and has a polydispersity of 6.0i. Polypropylene is the same as in Table I. The phenolic vulcanizing resin is added at the end. Composition 1, control, does not contain a vulcanization activator. ¬ assume that it is not fully vulcanized (possibly a copolymer was formed). These conclusions are confirmed by the solubility data in cyclohexane. Compositions 2, 3 and 4 contain zinc oxide, zinc stearate or stannous chloride as vulcanization activator, respectively. The data indicate that the rubber in the blends is substantially completely vulcanized. The percentage of cyclohexane-soluble rubber is corrected by a value of 1.38% by weight to include unvulcanized acetone-soluble rubber. The corrected value is marked with an asterisk. Compositions 4 and 5 show that if stannous chloride is used as the activator, a non-halogenated phenolic vulcanizing resin can be used instead of the halogenated one, obtaining an elasto-plastic composition with essentially the same properties. What is important is the presence of the vulcanization activator(s) and the appropriate its concentration. Without a vulcanization activator or with an inappropriate concentration, the rubber is not completely vulcanized, which results in a deterioration of the properties of the mixture. It is assumed that a high concentration of the activator, especially when added before the phenolic vulcanizing resin, causes reactions within the resin itself (homopolymerization), depriving the system of the vulcanizing agent. The appropriate concentration of the activator depends on its type and the type of phenolic activating resin and rubber, the order in which the phenolic vulcanizing resin and activator are added, and the processing temperature. These values can be easily determined experimentally. The compositions of the invention in which the EPDM rubber contains various monomers are shown in Table XII. Compositions 1 and 2 contain EPDM rubber in which the unsaturation comes from ethylidene norbornene (ENB). In compositions 3-6, the source of unsaturation of EPDM rubber is hexadiene-1,4 (1,4 HD), and in composition 7, dicyclopentadiene (DCPD). The compositions are prepared according to the method from Table I, except that in the case of composition 1, the temperature of the Brabender mixer is - Table XI Composition EPDM rubber Polypropylene Stearic acid ZnO Zinc stearate SnCl2-2H20 Phenolic resin; vulcanizing Hardness, Shore D 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile strain, % Compressive strain, % Pressure in ASTM-3 oil, % Part of the sample dissolved | na in cyclohexane at room temperature, % by weight. Part of the rubber soluble in cyclohexane at room temperature, % by weight | |__1 50 50 0.5 — — — 5.631 29 7.0 -^ 6.9 100 57 83 m ¦ 21 40 38.6* 2 50 50 0.5 0.5 —» ¦ ¦ — 5.63i 41 9 .3 14.5 21„0 450 32 38 133 2.2 4.2 2.8* and 3 50 50 0.5 — . Q.2 - 5.631 .411 9.1 113.7 20.8 . .470 32 39 134 1.6 3.0 1.6* ' 50 50 0.5 — — 1 5.631 41 9.8 ;4.4 21.6 480 30 46 140 '¦$ 0.4 0.8 8 * 5 50 50 0.5 — — 1 5.63* 44 10.0 13.4 18.6 470 32 45 147 0 0 0 1 halogenated phenolic vulcanizing resin as in Table I 1 non-halogenated phenolic vulcanizing resin as in Table IV126 439 29 30 Table XII Composition ' | EPDM rubber Ethylene, wt.% Monomer type Monomer, wt.% Polydispersity Mooney viscosity (ML, 1 + 8, 100°C) EPDM rubber Polypropylene Stearic acid -.'" Zinc oxide SnCl2-2H20 Phenolic resin Vulcanizing compound SP-10581 SP-1045* Hardness, Shore D 100% modulus, MPa 300% modulus, MPa: Ultimate tensile strength, MPa Elongation at break, % Strain at tensile, % Strain at compression, % Specification in oil ASTM-3,, % Part of the sample insoluble in boiling xylene, wt.%: Part of the rubber soluble in boiling xylene, wt.% Part of the sample insoluble in xylene at room temperature, wt.% l 56 ENB 4.4 5.2 60 50 50 -- 0.5 - 1 — 5,.63i 46 10.3 16.3 22.0 390 29 36 1114 51.8 (53.3) 2.8 42, 9 2 59 ENB 2.6 — 90 1, -^ 5.631 44 9.6 15.0 24.2 480 27 36 123 52.7 (53.3) 1.1 42.1 3 65 *.4HD 3.7 2.5 80 4 55 1.4HD 5.0 2)0 90 parts by weight - 1 5.63* 44 10.6 17.4 23.5 440 28 37 im 52.9 (53.3) 0.8 44 .7 —' 1 5.63* 44 9.9 13.0 20.5 500 34 30 116 50.3 (53.3) 51.4* 5.6 2.1* 42.5 5 56 1.4HD 3.7 19.4 39 — 1 5.63* 44 10.2 15.7 li8.2 370 29 34 130 51.3 (53.3) 3.a 4R.1 6 70 1.4HD 3.7 8 33 — 1 5.63^ 49 13.0 17.3 24.5 460 54 41 129 49.8 (53.8) 521.2* 6.6 4.6* 4.6.5 7 1 55 DOPD 4.4 6.0 45 w ^ r- 0.5 1 A,63i 44 10.8 16.5 24.0 430 30 37 122 50.2 (53.5) 52.9* 6.2 5.i * 43.6126 439 31 12 table XII cont'd Part of the sample soluble in xylene at room temperature, % by weight Part of the sample soluble in cyclohexane at room temperature, % by weight Part of the rubber soluble in cyclohexane at room temperature, % by weight and | a 5,.0 0.8 1.5 4.8 0.8 1.5 a 3.7 0.9. 1.7 4 7.6 3.1 5.8 1.7* 5 6.5 0.9 1.7 6 4.7 2.4 T U3 2.4s Table XIII 1 Cylinder temperature Type of vulcanizing agent Temperatures of the extruded mass, ° C Capacity, g/min Pipe dimensions, extrusion speed 381 cm/min Outer diameter, mm Inner diameter, mm Appearance Pipe dimensions at maximum extraction 1 Outer diameter, mm Inner diameter, mm Surface ratio Appearance Odor 193°C phenolic 197 199 .5 12*815 9.91 smooth 7.7 5.94 3.0 smooth mild sulfur 203 201.8 1A9 9.91 rough 9.68 7.54 1.9 very rough cracked mild 216°C phenolic 2181 186, 0 12.7 9.91 smooth 5.46 437 6.8* smooth mild sulfur 218 189.0 112.37 9.53 smooth 6.115 4.52 4l rough odor H^ 232°C | phenolic 232 182.5 12.7 9.91 smooth 5.46 4.37 6.8 smooth mild sulfuric 234 171f2 12.1? 9.53 smooth 7.U 5.56 3.7 very rough sharp * end of the machine range, no breakage is 170°C. In compositions 1-6, the vulcanization activator is added at the end. In composition 7, stannous chloride is first added, and then the phenolic vulcanizing resin and zinc oxide are added. Uncorrected values for the insoluble part of rubber are given without brackets, and in brackets are values calculated assuming that after vulcanization all components, except polypropylene, become insoluble. Values marked with an asterisk are corrected as follows: In compositions 4 and 7, 4.13 and 1.3-8% by weight of unvulcanized rubber are dissolved in acetone, respectively. The unvulcanized EPDM rubber used in composition 6 does not contain acetone-soluble material, but 2.52% by weight of the unvulcanized rubber does not dissolve in cyclohexane at 50°C, indicating the presence of a significant amount of polyolefin that is not cross-linking. The data show that all compositions have good strength properties and that the polydispersity of the rubber does not have a significant impact on the degree of vulcanization. All 50 compositions exhibit satisfactory oil swelling and compression deformation. The solubility data show that the rubber is completely vulcanized in all compositions. The better processability of the compositions according to the invention results from the comparison of the extrusion characteristics of blends vulcanized with phenolic agents and blends vulcanized with sulfur agents. For example, a pipe with an external diameter of 12.7 mm is prepared by extrusion33 126 439 34 Table ,,2 rough-nodular, many projections 0.13—0.25 mm 210—220°C phenolic 4^.5 smooth sulfuric 34.1 rough-nodular, many projections 0.13—0.25 mm compositions similar to 2 and 3 from Table I through a ring die with an outer diameter of 12.7 mm and an inner diameter of 9.53 mm (20:1 L/D), at a take-up speed of 381 cm/min, using a Davis-Standard extruder with a diameter 3.81 cm, equipped with a general-purpose screw, rotated at a speed of 70 revolutions per minute. The dimensions of the tube are maintained by slight internal air pressure and water cooling. The barrel temperature varies within the practical processing range: from 193°C, sufficient to completely melt the polypropylene, to 232°C, at which temperature excessive smoke occurs. Intermediate temperature conditions are also tested, i.e. 216°C. Another variable of interest is the ratio of the ring cross-sectional area of the pipe when the pipe is drawn in its diameter, measured at the moment of rupture due to the gradual increase in the withdrawal rate. This variable is a measure of the consistency of the composition, expressed in terms of extensibility at processing temperature. The test results are summarized in Table XIII. The data show that the composition prepared with the phenolic vulcanizing agent is more easily processed than the composition with the sulfur vulcanizing agent. Phenolic resin vulcanized compositions can be extruded over a wide range of temperatures and tube dimensions, as demonstrated by area ratio. The improved processability of the compositions of the invention is further illustrated by a comparison of the extrusion characteristics of compositions similar to 6 and 7 in Table III. For example, a 5 mm diameter rod is prepared by extruding the above compositions through 5.08 mm diameter dies using a 2.54 cm diameter NRM extruder equipped with a 16:1 L/D general purpose screw, rotated at a speed of 60 revolutions per minute. The temperature of the cylinder varies in the range from 180-190°C to 2! 10-220°C. The results are presented in Table XIV. They show that compositions prepared with a phenolic vulcanizing agent can be extruded at a higher speed, obtaining pipes with a smoother surface than compositions prepared with a sulfur vulcanizing agent. The compositions according to the invention contain mixtures of polyolefin resins and dispersed, suitably small resins. particles of cross-linked rubber, which components give them high strength and thermoplasticity. A suitable rubber particle size is about 50 µm, and more preferred compositions use rubber with a particle size of 5 µm or less. 15 20 25 30 35 40 45 50 55 60 patent reservations! 1. An elastoplastic composition containing a thermoplastic, crystalline polyolefin resin and fully vulcanized EPDM rubber in the form of dispersed particles with an average size of 50 micrometers or less, characterized in that per 100 parts by weight of the sum of both components it contains about 25-75 parts by weight of polyolefin resin and about 75-25 parts by weight of EPDM rubber vulcanized with a phenolic vulcanizing agent and containing phenolic vulcanizing resin and vulcanization activator, the vulcanized rubber containing not more than about 3)% by weight of unvulcanized ka feelings ku, extractable into cyclohexane at 23°C or not more than about 5% by weight of unvulcanized rubber, extractable into boiling xylene. 2. The composition according to claim I, characterized in that the polyolefin resin contains polypropylene. 3. The composition according to claim 2, characterized in that it contains about 30-250 parts by weight of filling oil per 100 parts by weight of rubber. 4. The composition according to claim. 3, characterized in that it contains about 2^250 parts by weight of carbon black per 100 parts by weight of rubber. 5. The composition according to claim. 2, characterized in that the phenolic vulcanizing resin contains non-halogenated dimethylol-p-alkylphenol, in which the alkyl radical contains 5-10 carbon atoms. 6. The composition according to claim. 5", characterized in that it contains a metal halide or a halogen-donating polymer as a vulcanization activator. 7. The composition according to claim. 6, characterized in that the halogen-donating polymer contains chlorosulfonated polyethylene. 8. The composition according to claim. 7, characterized in that it contains zinc oxide as a vulcanization activator. 9. The composition according to claim. 2, characterized in that the phenolic vulcanizing agent contains a brominated phenolic vulcanizing resin and a metal oxide as a vulcanization activator. The composition according to claim 9, characterized in that the metal oxide contains zinc oxide. 11, The composition according to claim 11. 1, characterized in that the polyolefin resin is polyethylene.Ii2. The composition according to claim 2, characterized in that the EPDM rubber contains a terpolymer of ethylene, propylene and ethylidene ions. The composition of claim 1, wherein the rubber is vulcanized to such an extent that not more than about 3% by weight of the rubber is extractable into boiling xylene and the rubber has an average particle size of about 5 micrometers or less. 14. The composition according to claim. 2, characterized in that it contains about 30-70 parts by weight of polypropylene, about 3-70 parts by weight of EPDM rubber and 5-300 parts by weight of filling oil per l0-10 parts by weight of the sum of polypropylene and rubber. and 1-100 parts by weight of the crushed filler per 100 parts by weight of the sum of rubber and filler oil. 15. A composition according to claim 14, characterized in that the crushed filler contains carbon black. 16. A composition according to claim 14, characterized in that 17. Composition according to claim 16, characterized in that the filler contains kaolin clay. IB. Composition according to claim 17, characterized in that it contains a silane coupling agent. 19. The composition according to claim 1, characterized in that the phenolic vulcanizing resin is dimethyl-p-octylphenol. 20. The composition according to claim 1 or 2, characterized in that it contains rubber vulcanized with a phenolic vulcanizing agent, which contains 20 parts by weight of phenolic vulcanizing resin and approximately 0.01-10 parts by weight of vulcanization activator per 100 parts by weight of EPDM rubber. 21" The composition according to claim 20, characterized in that it contains a phenolic vulcanizing agent in an amount of 7-14 parts by weight per 100 parts of the total weight of EPDM rubber. 2B. The composition according to claim 21, characterized in that it contains rubber vulcanized with dimethylol-p-oct4ylphenol. 23. A method for producing elasto-plastic compositions, characterized by masticating approximately 25-75 parts by weight of EPDM rubber, 75-25 parts by weight of thermoplastic, crystalline polyolefin resin per 100 parts by weight of the sum of these ingredients and a phenolic vulcanizing agent. , in an amount sufficient to vulcanize the rubber, at a temperature sufficient to soften or melt the polyolefin resin and for a time sufficient to obtain a homogeneous mixture in which the rubber is in the form of small, dispersed particles with an average size of approximately 50 micrometers or less, the vulcanization activator is then added and the mixture is continued to be masticated at the vulcanization temperature until the rubber is vulcanized to such an extent that no more than about 5°C of the rubber is extractable into the boiling xylene. ,24. The method according to claim 23. characterized in that the phenolic vulcanizing agent is a brominated phenolic vulcanizing resin. 25. The method according to claim 24, characterized in that zinc oxide is used as the vulcanization activator. 26. The method according to claim 23, characterized in that the phenolic vulcanizing resin is non-halogenated dimethyl-p-alkylphenol, in which the alkyl radical contains 5-10 carbon atoms. 27. The method according to claim 26, characterized in that chlorosulfonated polyethylene and zinc oxide are used as curing activator. 28. The method according to claim 27, characterized in that the phenolic vulcanizing resin is dimethylol-p-octylphenol. 29. The method according to claim 23, characterized in that polypropylene is used as the polyolefin resin. 10 15 20 25 30 ZGK 0761/1131/5 - 80 copies. Price PLN 100 PL PL PL

Claims (9)

1. is referred to in the claims as "EPDM rubber". Suitable EPDM rubbers contain polymerization products of monomers of two olefins, usually ethylene and propylene, and a smaller amount of unconjugated diene. The amount of unconjugated diene is usually 2-10% by weight of the rubber. Generally, any EPDM rubbers that exhibit sufficient reactivity with the phenolic vulcanizing agent to achieve complete vulcanization are suitable for carrying out the invention. The reactivity of EPDM rubber varies depending on the degree and type of unsaturation of the polymer. For example, EPDM rubbers containing ethylidene norbornene are more reactive towards phenolic vulcanizing agents than EPDM rubbers containing dicyclopentadiene, and rubbers containing hexadiene-1,4 are less reactive than those containing dicyclopentadiene. However, the differences in reactivity can be compensated by introducing rubber molecules larger amounts of the less reactive diene. For example, 2.5% by weight of ethylidenenorbornene or dicyclopentadiene is used, while hexadiene-1,4 must be used in an amount of at least 3% by weight. Suitable α-monoolefins are compounds of the formula CH2~CHR, in which R is a hydrogen atom or an alkyl radical with 1-12 carbon atoms, e.g. ethylene, propylene, butene-1, pentene-1, hexene-112 | -methylpropen-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, 2,4,4-trimethylpentene-1, 3-methylhexene-1, 1,4-dimethylhexene -l and others. Suitable unconjugated dienes are straight-chain (acyclic) dienes such as 1,4-hexadiene, 2-methylpentadiene-1,4, 1,4,9-decatriene and 11-ethylridecadiene-1,11; single-ring dienes such as cyclooctadiene-1,5, cycloheptadiene-1,4 and 1-mephylcyclooctadiene-1,5; bridged two-ring dienes such as 5-ethylidene-norbornene, 5-methylene-2-norbornene, 54-sopropylidene-2-norbornene, and 2-methylbicyclo[2.2.1]heptadiene-2,5; fused two-ring compounds, such as bicyclo[4.3.0] nonadiene-3,7, 5-methylbicyclo[-4.3.0] nonadiene-3,7, 5,6- d/wumethylbicyclo[4.3.0] nonadiene-3 .7 and bicyclo[3.2.0]heptadiene-2,6; single-ring compounds with an alkenyl substituent, such as 4-vinylcyclohexene, 1,2-divinylcyclobutane and 1,2,4-trivinylcyclohexane, and three-ring compounds, such as dicyclopentadiene. EPDM rubber grades suitable for carrying out the invention are commercially available; Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 406-410. Suitable thermoplastic polyolefin resins include crystalline, high molecular weight, solid polymerization products of one or more monoolefins, at high or low pressure. Examples of such resins are isotactic and syndiotactic monoolefin polymers, which are commercially available. Examples of suitable olefins are ethylene, propylene, butene-1, pentene-1, hexene-1, 2-methylpentene-1, 3-methylpentene-1, 4-methylpentene-1, 5-methylhexene-1 and their mixtures. Commercially available thermoplastic polyolefin resins, such as polyethylene and especially polypropylene, may advantageously be used in the invention. Any phenolic vulcanizing system which completely vulcanizes EPDM rubber is suitable for the invention. The basic ingredient of such a system is a vulcanizing phenolic resin, obtained by condensation of substituted or unsubstituted phenol with an aldehyde in a basic medium or by condensation of difunctional phenol dialcohols. Particularly suitable are vulcanizing resins based on halogenated phenol. It is particularly recommended to use vulcanizing systems containing a phenolic resin, a halogen donor and a metal compound. Details of such systems are provided by Giller in the St. Pat. United No. 3,287,440 and Gerstin et al. in St. Patent No. 3,287,440 United No. 3,709,840. Halogenated, usually brominated, phenolic resins containing 2-1.0% bromine by weight do not usually require a halogen donor, but are used in conjunction with a hydrogen halide binder, e.g. such as iron oxide, titanium oxide, magnesium oxide, magnesium silicate, silicon dioxide and especially zinc oxide, the presence of which promotes the cross-linking function of the phenolic resin. However, in the case of rubbers which are resistant to vulcanization by phenolic resins, it is recommended to use a halogen donor and zinc oxide together. The production of halogenated phenolic resins 40 and their use in zinc oxide vulcanizing systems are described in the St. Pat. United Americas No. 2972 600 and No. 3 093 6|1|3. Examples of suitable halogen donors are stannous chloride, ferric chloride or halogen-donating polymers such as chlorinated paraffin, chlorinated polyethylene, chlorosulfonated polyethylene and polychlorobutadiene (neoprene rubber). The term "activator" herein means any material that increases the cross-linking efficiency of a phenolic vulcanizing resin and includes both metal oxides and halogen donors. For further details on phenolic vulcanizing systems, see "Vulcanization and Vulcanizing Agents", W. Hoffman, Palmerton Publishing Company. Suitable phenolic and brominated phenolic vulcanizing resins are commercially available, e.g., SP-1045, CRJ-352 resins. , SP-1055 60 and SP-1056 from Schenectady Chemicals, Inc. Similar, functionally equivalent phenolic vulcanizing resins can also be obtained from other manufacturers. As explained above, the vulcanizing agents are used in an amount to obtain substantially complete vulcanization of the rubber.126 439 9 10 The properties of the elastoplastic compositions of the invention may be modified, before or after vulcanization, by the addition of ingredients conventionally used in the production of EPDM rubber, semi-olefin resin and blends thereof. Examples of such ingredients are carbon black, silica, titanium dioxide, color pigments, clay, zinc oxide, stearic acid, stabilizers, anti-degradation agents, flame inhibitors, processing aids, adhesives, plasticizers, wax, discontinuous fibers, such as wood cellulose fibers and oils filling. It is especially recommended to add carbon black, oil or both, preferably before dynamic vulcanization. Carbon black increases tensile strength and promotes phenolic vulcanizing agents. Oil filler can improve the oil swelling resistance, thermal stability, hysteresis, cost and permanent deformation of the elasto-plastic composition. Aromatic, naphthenic and paraffin oils are suitable. The addition of oil can also improve processability. Suitable filler oils are presented in the above-quoted Rubber World Blue Book, pages 145-190. The amount of oil additive depends on the desired properties, and the upper limit depends on the ability of the oil to combine with the ingredients of the mixture. This limit is exceeded when excessive discharge of fill oil occurs. Typically, 5-300 parts by weight of oil are added to 100 parts by weight of the mixture of olefin rubber and semi-olefin resin. Typically, this amount is in the range of about 30 to 250 parts by weight of oil per 100 parts by weight of rubber present in the mixture, and the preferred content is about 70 to 20) parts by weight per 100 parts by weight of rubber. The amount of filling oil depends, at least to some extent, on the type of rubber. Highly viscous rubbers absorb more oil. When preparing compositions according to the invention that are to be colored, colorless or white pigments (fillers or reinforcing pigments) are used instead of carbon black. Silica, aluminum silicate, magnesium silicate and titanium dioxide are suitable for these purposes. Typically, the white pigment is added to the mixture in an amount of 5-100 parts by weight per 100 parts by weight of rubber. The typical addition of carbon black is 40-2.50 parts by weight per 100 parts by weight of EPDM rubber, and usually about 20-100 parts by weight of carbon black are added per 100 parts by weight of the sum of EPDM rubber and filler oil. The amount of carbon black that can be used depends, at least to some extent, on the type of carbon black and the amount of oil used. Methods other than dynamic vulcanization of rubber/polyolefin resin mixtures may be used to prepare the compositions according to the invention. For example, the rubber can be completely vulcanized in the absence of the semi-olefin resin, dynamically or statically, pulverized and mixed with the polyolefin resin at a temperature above its melting or softening point. If the particles of the cross-linked rubber are small, carefully distributed and used in the appropriate concentration, the compositions of the invention can be easily obtained by mixing the cross-linked rubber with a polyolefin resin. Thus, "blend" herein means a mixture of finely distributed, small particles of cross-linked rubber. A mixture which does not fall within the scope of the invention because the rubber particles are not properly distributed or are too large may be milled. cold, to reduce the particles below 50 μm, preferably below 20 μm, and especially below 5 μm. After appropriate grinding or powdering, the composition according to the invention is obtained. Often, poor distribution or too large size of carbon particles rubber particles are visible to the naked eye and noticeable in the formed sheet. This is particularly the case in the absence of pigments and fillers. In this case, pulverization and re-forming produce a sheet in which aggregates of rubber particles or large rubber particles are not visible to the naked eye. eye or much less noticeable and which have significantly better mechanical properties. The elasto-plastic compositions of the invention are useful in the production of many articles, such as tires, hoses, belts, gaskets and various types of fittings. They are particularly useful in the production of articles by extrusion, injection molding and compression. They can also be used to modify thermoplastic resins, especially polyolefin resins. Conventional equipment is used to blend the compositions with thermoplastic resins. The properties of the modified resin depend on the amount of elasto-plastic composition introduced. Typically, the amount of the elastoplastic composition is such that the modified resin contains about 5 to 25 parts by weight of EPDM rubber for about 95 to 75 parts of the total weight of the resin. The strength properties of the compositions are determined according to ASTM D-638 and ASTM D-1'566. The term "elasphomeric" in the present specification and claims means a composition which, in a given period of time (1 or 10 minutes), shrinks to less than 100% of its original length when expanded at room temperature to twice its original length and held in a stretched state for the same time (1 or 10 minutes). Compression deformation is determined according to ASTM D-319\5, method B, by compressing the sample for 22 hours at 100°C. Swelling in oil (percentage change in weight) is determined according to ASTM D-471, by immersion in ASTM-3 oil, for $ days at 121° C. Particularly preferred compositions of the invention are rubber compositions having a compressive strain value of about 5G% or less, these compositions meet the definition of rubber according to ASTM Standards, Volume 28, page 756, rubber compounds having a Shore D hardness of 60 or less, a 100% modulus of 17 MPa or less, or a Young's modulus of less than 245 MPa. To illustrate in this invention, a masterbatch containing EPDM rubber , paraffinic filler oil, carbon black, zinc oxide, stearic acid 10 15 20 25 30 95 40 45 50 55 60126 439 11 12 and optionally an anti-degradation agent (all ingredients in parts by weight) are mixed with polypropylene. Mixing is carried out for 2.5 minutes at a speed of 80 revolutions per minute in a Brabender mixer placed in an oil bath at a temperature of 180°C. The polypropylene melts and a homogeneous mixture is obtained. In the following, when talking about the temperature of the Brabender mixer, we mean the temperature of the oil bath. The phenolic vulcanizing agent is added and mixing is continued for a further 4 minutes, during which time the maximum Brabender consistency value is reached. After being removed from the mixer, the composition is pressed into shape at 210°C. Before removing from the mold, the samples are cooled to below 100°C. The properties of the formed samples are determined and recorded. Data for the various compositions are summarized in Table I. Batches 1-3 and 4-6 contain different EPDM rubbers, as shown in the references. Compositions 1 and 4 are control and do not contain a vulcanizing agent. Compositions 2 and 5 illustrate the invention and are vulcanized with a phenolic vulcanizing agent. Compositions 3 and 6, included for comparison, are vulcanized with a sulfur system. The rubber used in compositions 2, 3, 5 and 6 is completely vulcanized, i.e. less than 3% by weight of the rubber (based on the total rubber contained in the composition) is extracted into the cyclohexane at room temperature or into boiling xylene. Vulcanized compositions are elastomeric, processable like thermoplastic materials and can be reprocessed without regeneration, unlike statically vulcanized compositions which are thermosetting and cannot be processed like thermoplastic materials . The data presented in Table I show that compositions prepared from EPDM with a high ethylene content have greater hardness. Compositions made with phenolic vulcanizing resin have essentially the same strength properties, but the sulfur vulcanizing system is more effective in compositions containing EPDM rubber with low polydispersity. Compositions vulcanized with phenolic vulcanizing resin have two significant advantages over compositions vulcanized with sulfur agents, namely greater resistance to oil (low swelling) and less deformation under compression. Compositions containing EPDM rubber as the main ingredient are presented in Table II. Composition 1 does not contain vulcanizing agents. Composition 2 is a composition according to the invention, a vulcanized phenolic vulcanizing resin. Compositions 3 and 4, included for comparison, are vulcanized with a sulfur vulcanizing system and a peroxide agent, respectively. Polypropylene is the same as in Table I. EPDM rubber is a terpolymer of 69% by weight of ethylene, 8.3% by weight of ethylidene norbornene, the remainder polypropylene; polydispersity 2.2, viscosity Composition EPDM rubber Polypropylene 8 Oil. filler Carbon black Zinc oxide Stearic acid Flectol-H4, antidegradation agent SP-10565 Sulfur vulcanizing agent6 Hardness, Shore D 100% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Set in oil ASTM-3, % Compressive deformation, % 1 361 64 30.6 28.8 1.8 0.36 0.7l2 3.24 — 43 8.4 10.78 460 131 —f Table 2 361 64 30.6 28.8 1.8 0.36 0.72 — — 47 11,.27 17.2 390 67 — I 3 361 64» 30.6 28„8 1.8 0.36 0.72 — 1.31 47 9.9 18.6 490 88 — ¦ 4,362 64 30.6 28.8 1.8 0.36 — — — 35 6.8 7.6 460 88 68 5,362 64 . . 30.6 28.8 1.8 0.36 — 3.24 — 40 11.1 17.5 30Q 53' 39 fl 1 36» 64 30^6 28.8. 1.8 0.38 — — 1.31 39 8.5 13.6 390 7^ 52 1 73 ethylene by weight, 4.4% ethylidenenorbornene by weight, poly dispersity 2.1, specific gravity 0.86, Mooney viscosity 55 (ML+121°C) 8 55% ethylene by weight, 4.4% ethylidenenorbornene by weight, polydispersity 5.2, specific gravity 0.86, Mooney viscosity 40 (ML 1+8 121°C) and low fluidity, general use", specific gravity 0.902, elongation 11% 1 polymerized 1,2-dihydrogen-2,2,4-trimethylquinoline * brominated methylolphenol vulcanizing resin 6 sulfur 17.2 parts, zinc methyl dithiocarbamate 10.3 parts tetraethylthiuram disulfide 10.3 parts , 2-bis(benzothiazolyl) disulfide 34.5 parts and dipentamethylenethiuram hexasulfide 27.7 parts13 126 439 14 T a b 1 and c a II Composition EPDM rubber Polypropylene SP-1056 Zinc oxide tetraethylthiuram disulfide 2-bis-(benzothiazolyl) disulfide u) Sulfur 2 ,5-dimethyl-2,5-di- (III-butylperoxy) hexane Hardness, Shore D 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation ,, % Specification in ASTM-3 oil, % Part of the sample soluble in cyclohexane at room temperature, % by weight. Part of the rubber soluble in cyclohexane at room temperature (without correction for rubber components soluble in acetone), % by weight 1 GO 40 — ¦'¦' — — — — —1 36 5.9 — 6.27 300 38 91 133 48 , 80 2 6i0 40 6.75 1.25 — — ¦ — — 42 9.9 21.6 23.9 310 aa 24 10.9 0 0 3 60 40 — 3.0 0.6 0, 3 0.9 — 43 10.78 17.5 21.2 370 34 43 194 0 0 4 1 60 40 — —» | — — , 1.2 39 8.03 11.9 16.07 420 35 32 ¦ ¦¦ 225 ¦ 1 '¦ 1.7 Mooney'a 51 (ML 8, Ui00°C). Procedure as in Table I, except for composition 2, zinc oxide is added one minute after adding the phenolic vulcanizing resin, and in composition 4, after reaching the maximum Brabender consistency, 0.6 parts by weight of trinonylphenyl phosphite, an agent, are added. scavenging free radicals. The data show that the vulcanized phenolic vulcanizing resin composition has greater oil resistance (less swelling) and less compressive deformation. Table III shows soft compositions with a high proportion of rubber and filling oil. The procedure is the same as in Table 1, except that after adding the vulcanizing agents, mixing is continued for 5 minutes. Composition: 1 is control and does not contain vulcanizing agents. Compositions 2, 4 and 6 are compositions according to the invention, vulcanized with phenolic vulcanizing resins. Compositions 3, 5 and 7 are vulcanized with sulfur vulcanizing systems. Data show that compositions vulcanized with phenolic vulcanizing resins have less compressive deformation and greater oil resistance. In addition, compositions vulcanized with phenolic vulcanizing resin provide smoother surfaces after extrusion or injection molding. The surfaces of moldings and parts formed from compositions vulcanized with phenolic vulcanizing resins are free from efflorescence and do not stick. Composition 6* with a high proportion of rubber has favorable elastomeric properties, such as low tensile deformation and low compression deformation. Tests on the influence of the amount of vulcanizing agent 30 35 45 50 65 are presented in Table IV. The procedure and ingredients 8a are the same as in Table III. As can be seen from the data presented, increasing the amount of vulcanizing agent has a smaller impact on the strength properties in the case of the sulfur vulcanizing system than in the case of the phenolic resin system. The tensile strength in both systems does not change substantially with changes in the concentration of the vulcanizing agent. As the concentration of the phenolic resin increases, the modulus increases and the elongation decreases, while both of these parameters do not change substantially with changes in the amount of sulfur vulcanizing agent. At all tested concentrations, the phenolic resin vulcanized compositions show less compressive deformation and greater oil resistance. Compositions according to the invention vulcanized with non-halogenated phenolic vulcanizing resins are presented in Table V. The procedure is the same as before. Composition L is a control one and does not contain any vulcanizing additives. Composition 2 is a control containing a phenolic vulcanizing resin but no vulcanizing activator. Composition 5 is another control containing a sulfur vulcanizing agent. Control 3 contains dimethylol-p-nonylphenol (phenolic vulcanizing resin of the commercial brand SP-1045). Compositions 3 and 4 contain stannous chloride and chlorosulfonated polyethylene as halogen donors, respectively. The data show that the use of a vulcanization activator in conjunction with a non-halogenated phenolic vulcanizing agent is not critical for complete vulcanization of the rubber. The presence of a halogen donor (vulcanization activator) causes13 126 439 16 Composition EPDM and oil-filled rubber1 Polypropylene2 Filling oil Flectol-H8 carbon black, anti-degradation agent Zinc oxide Stearic acid SP-10502 Sulfur vulcanizing agent Hardness Shore A 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at | breaking strain, % and Tensile strain, % Compression strain* % ASTM-3 oil setting, % 1 91.2 54.4 36.4; 36.4 Q.91 2928 0.46 — — 8H 2.9 — 4.3 500 — — 167 2 9U 54.4 36.4 36.4 0.91 2.28 0.46 M — 83 5y2 10, 78 13.8 410 14 30 52 Table 3 91.2 54.4 3(6.4 36.4 0.91 2.28 0.46 — 1.65 84 4.5 8.5 1^4.7 550 14 47 69 III 4 100.6 49.7 23.9 ^8.9 0.90 2.41 0.49 4.43 — 82 4.5 9.9 13.1 390 12 2a 52 5 100.6 49 .7 28.9 28.3 0.96 2„41 0.49 — 1.80 81 4.3 8.4 14.7 560 ) 11 49 84 6 124.4 37.8 31.1 18.66 — 1.16 0„62 6,W —? 71 3.3 — 8.9 290 6 20 59 7 124.4 37.8 311.1 1 18.66 — 3.11 0.62 —< 2.25 71 2.3 59 6.76 350 17 34 91 1 63% by weight of ethylene, 3.7% by weight of ethylidenenorbornene, polydispersity 2.6, specific gravity 0.90, Mooney viscosity (ML-4, 125°C) 50, terpolymer filled with 100 phr of non-corrosive naphthenic oil 8 polypropylene and agents vulcanizing As in table I, significant increase in tensile strength and reduction of compressive deformations, and increases resistance to oil. A large speck in the oil of composition 2 indicates that the rubber is only partially vulcanized. The data also demonstrate that compositions vulcanized with a phenolic vulcanizing system containing a halogen donor have less compressive deformability and greater oil resistance than similar compositions vulcanized with a sulfur agent. Compositions 3 and 4 show particularly high retention of tensile strength after oil setting. The tests presented in Table VI further demonstrate that complete vulcanization of the rubber requires the presence of an activator (zinc oxide). The procedure is the same as in Table I, but no masterbatch is used because the compositions do not contain carbon black or filler oil. Compositions 1 and 2 are the same except that composition 2 does not contain zinc oxide. The data for composition 2 presented in Table VI are the average values of two trials. 45 S5 60 65 In order to determine the degree of vulcanization of the rubber, the compositions are extracted with boiling xylene (vulcanized rubber is insoluble in boiling xylene). Samples are extracted in the form of a thin film (about 0.06 mm thick). After 30 minutes the film usually disintegrates. Then the suspension in xylene is filtered through a glass fiber filter with a pore size of 0.3 (im. It is assumed that all ingredients, except polypropylene, are part of the vulcanized rubber. The filtrate is cooled to room temperature, which causes precipitation of the polypropylene (or crystalline graft copolymer), which material is filtered off. The second filtrate is evaporated to recover material that is soluble in xylene at room temperature. (Ataxic polypropylene, low molecular weight polypropylene, amorphous ethylene-propylene copolymer, unvulcanized EPDM rubber or non-crystalline grafted polypropylene-EPDM rubber copolymer). The weight percentage of the recovered material is given in parentheses together with the calculated theoretical value. Table IV Composition EPDM rubber with oil fill1 Polypropylene2 Filling oil Oxide zinc Stearic acid Flectol-H, antidegradant SP-10562 Sulfur vulcanizing agent2 Hardness, Shore A 1/00% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation, % Oil setting ASTM-3, % 1 Q1 * R4 4. ^fi, 4 00(,,t 36 4 2 28 0 46 - 0 91 - —! — 81) 2.8 4.0, 630 52 78 162 2 4.05 — 84 4.99 13.1 430 14 31, 52 3 5.07 : 85 5.58 13.9 370 14 3H 49 4 6.08 — 85 6.56 18.8 290 12 24 43 5 7.96 — 85 6.86 13.8 280 13 26 41 6 — 1.24 84 4.3 H5 550 14 45 73 ' — 1.66 85 4.3 14, 8 590 14 38 74 » —* 2.07 85 4.6 15.0 560 13 48 71 9 —. 2.48 85 4.8 14.8 530 13 47 67 - ¦¦ ¦V ¦ - ¦- 1 as in Table II 1 as in Table IIfr 126 439 2* Table V Composition Rubber EPDM1 Polypropylene* Filling oil Soot | Zinc oxide 1 Stearic acid SP-1045* SnCl3 Chlorosulfonated polyethylene Sulfur vulcanizing agent* Hardness, Shore D 100% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile deformation, % Compressive deformation, % Oil setting ASTM -3.% Oil tensile strength limit, MPa % strength retention | tensile limit 1 36 04 ao,e 28.8 U* 0.35 — — — ¦ — 37 7.0 9.3 510 48 — | / TO 3.7 40.0 * 1 3G $4 30.6 2&S\ 1.8 0.36 4.33 — — — 42 10.0 16.6 450 aa 57 86 v - 8.1 48.8 3 36 64 30.6 28.8 V* 0.36 4.3fc 0.70 — — 45 H3 22.1 260 27 36 44 15.4 69.6 4 36 G4 30.6 28.8 13 Q.36 4.32 — 1.8 — 45 12.6 21.8 380 29 30 55 14,p 1 64.0 5 1 36 04 30.6 28.8 1.8 0.36 —* —i — 1*06 43 11, 1 20.67 410 32 49 ' 66 H,0 53.7 69% by weight of ethylene, 8.3% by weight of ethylidenerbofnene, polydispersity 2.1, specific gravity 0.86, Mooney viscosity 50 (ML-8, 100° C) as in Table I, dimethylol-p-nonylphenol (non-halogenated) for vulcanized EPDM rubber. The court makes a correction to the calculated value for vulcanized rubber to take into account materials present in the vulcanized rubber which remain soluble in boiling xylene after vulcanization. The correction (1.6% by weight of rubber) is the sum of the part of the unvulcanized rubber soluble in acetone, 0.9% by weight, and the part insoluble in cyclohexane at room temperature, 07% by weight. The material soluble in acetone is considered non-crosslinkable, and the material soluble in cyclohexane at room temperature is considered a polyolefin copolymer. For example, in the case of composition 1, the calculated value in parentheses for the insoluble rubber is 39.3% by weight, which would be 39.3% by weight without the above correction. Similar corrections were made to the calculated values given in tables VII-IX (in brackets). The data presented show that composition 1, containing zinc oxide, has less deformation under tension and compression and swells less in oil, and that the rubber contained therein is not extracted into boiling xylene at all. This proves the complete vulcanization of the rubber and confirms the absence of the transplanted copolymer. From a composition containing no zinc oxide, 32% of rubber passes into boiling xylene. This indicates the presence of a graft copolymer or only partial vulcanization of the rubber. The above data demonstrate that in order to obtain the compositions of the invention with a fully vulcanized rubber, it is critical to use a vulcanization activator that promotes reactions essentially only between the EPDM rubber and the phenolic vulcanizing resin. Compositions according to the invention with high hardness, containing carbon black and with a high degree of polypropylene content are shown in Table VII. The masterbatch of EPDM rubber, carbon black, zinc oxide and stearic acid is mixed with polypropylene in a Brabender mixer at a speed of 80 rpm, at 180°C, until the polypropylene melts to obtain a homogeneous mixture. The phenolic vulcanizing resin is added and mixing continues until the maximum Brabender consistency is achieved, then mixing continues for 3 minutes. The compositions are removed, rolled into sheets, returned to the Brabender mixer and mixed for 2 minutes at 180°C. The data show that the compositions are harder and stiffer than the compositions from the previous tables, containing more rubber. Tensile strain values indicate that the compositions have reduced elasticity.2V 126 439 22 Table VI Table VII Composition Rubber EPDM1 Polypropylene2 Stearic acid Zinc oxide Flectol-H, antidegradant2 SP 10562 Hardness Shore D 100% modulus, MPa 300% modulus MPa; I Ultimate tensile strength, MPa Elongation at break, % Tensile strain, % Compressive strain, % Settling in oil - ASTM-3, % Part of the sample insoluble in boiling xylene, % by weight Part of the soluble rubber ¬ soluble in boiling xylene, % by weight Part of the sample insoluble in xylene at room temperature, % by weight Part of the sample insoluble in xylene at room temperature, % by weight Total, % 36 34 0.36 1, 8 0.72 4.05 53 13.8 15.4 1^7.5 590 42 51 105 40.2 (39.3) ; 0 5.5.0 (60.4) <7 | 99.9 36 64 0.36 Q.72 4.05 5V 13.0 16.1 530 52 67 15iV 2Q.3 (38,a) 32.0 a6.7 (61.4) 17.8 ioo,a JO 15 20 25 30 35 55% by weight of ethylene, 4.4% of nene, polydispersity 2.5, Mooney's 70 (ML 1 + 8, 121°C) as in Table I by weight of ethylidenenorborbor - specific gravity 0.86, viscosity However, the solubility data show that the rubber is completely vulcanized and is not soluble in boiling xylene at all. The order in which the ingredients are added is important, especially vulcanization activators, such as; zinc oxide. It is especially important when adding large amounts of zinc oxide in the absence of a filler. An illustration of the above is provided in Table VIII. The procedure is the same as in Table I, but no masterbatch is used because the composition does not contain soot and filler oil. The ingredients are added in the given order. In the case of compositions 1-5, zinc oxide is added before the phenolic vulcanizing resin, while in the case of compositions 6-9, the order of adding these ingredients is reverse. The presented data show that the strength properties deteriorate with increasing amounts of 40 45 50 55 60 65, Composition Rubber EPDM1 Polypropylene1 Carbon black Stearic acid Zinc oxide SP-10561 Hardness Shore A Shore D 100% modulus, MPa 300% modulus , MPa Ultimate tensile strength, MPa Elongation at break, % Compressive deformation, % Parts of the sample insoluble in | boiling xylene, 1% by weight 1 25 75 20 0.25 1.25 2.75 97 60 19.2 23.0 26.9 440 54 40<}1 (39.3) Z 30 70, 24 ' 0.3 1.5 3.3 99 60 17.9 22.9 23.5 320 54 45.4 (45.4) 3 I 35 65 28 0.35 1.75 3.85 99 59 17.5 24.1 25 ,1 350 47 51.9 51.0 1 as in Table VI of zinc oxide, when zinc oxide is added before the phenolic vulcanizing resin, while the effect of the amount of zinc oxide on the strength properties is small when it is added last. Such compositions have higher compressive and tensile strength, lower deformability when stretched and compressed, and greater resistance to oil. The solubility data indicate that the order of zinc oxide addition has a significant impact on the degree of vulcanization of the rubber. The amount of rubber soluble in boiling xylene varies from 0 to 23%, depending on the amount of zinc oxide in the composition, if zinc oxide is added before the phenolic vulcanizing resin, if zinc oxide is added last. , as in composition 6-9, the amount of rubber soluble in boiling xylene is 1% or less. A correction of 0.9% by weight was introduced to the determined solubility of rubber in cyclohexane, taking into account the part of the vulcanized rubber soluble in acetone. The correction should probably be larger to take into account stearic acid, which may also be extracted into cyclohexane. Tests involving changes in the proportion of EPDM rubber and polypropylene are presented in Table IX. The compositions contain only EPDM rubber, polypropylene, phenolic vulcanizing resin and zinc oxide. The amounts of zinc oxide and phenolic vulcanizing agent are varied to maintain a constant ratio of vulcanizing agent to rubber - 2 parts by weight of zinc oxide and 10 parts by weight of phenolic vulcanizing resin per 100 parts by weight of rubber. EPDM rubber and polypropylene are loaded into a Brabender mixer maintained at 180°C and mixed at a speed of 100 rpm. In 3 minutes after melting the polypro-Table VIII Composition no. Rubber EPDM1 Polypropylene1 Stearic acid Zinc oxide SP-10561 1 Zinc oxide 1 1/00% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Hardness, Shore D Tensile strain, % Compression strain, % Oil setting, % wt. Part of the sample insoluble in boiling xylene, % by weight. Part of the rubber soluble in boiling xylene, % by weight. Part of the sample soluble in cyclohexane at room temperature, % by weight Part of the rubber soluble in cyclohexane at room temperature | room temperature, % by weight 1 50 2 3 4 5 « ? 8 9 v~ 50 .. . . ... . . .... . . . ... .. .. ^ 1 0 5 — q.05 5 65 11.3 21.9 22.5 320 45 25 31 iai 52.5 (52.2) 0 0.29 0 0.75 — 10, 5 15.5 22.3 46/0 43 27 39 145 50.5 (52.5) 4.0 V 2,» 1.5 -u 10.0 14.0 19.1 480 43 30 41 149 46, 4 (53.V 13.4 2.3 4.0 2.25 — 9.7 13.0 17.7 500 43 32 41 152 45.5 (53.5) 16.0 2.2 3.9 3 ,0 — 9.4 11.9 1*6 480 43 35 45 164 42.3 (53.8D 23.0 2.5 4.6 0.75 10.7 18.9 25.5 380 44 25 34 106 54.0 (52.5) 0 0.9(3 1.1 ._ | 1.5 10.6 17.3 23.8 390 45 26 35 im 53.7 (53.1) 0 0.71 Q .6 -. 2.25 10.5 17.0 16.5 430 44 25 33 110 53.0 (53.5) 1.0 1.03 1.3 7" w. r* r- 3.0 10 ,3 16.6 25.6 440 44 Z5 38 110 54.0 (53.8) o 0.71 0.6 \ as in table VI.126 439 25 26 Table IX [ Composition Rubber EPDM1 Polypropylene1 SP-10561 Zinc oxide 100% modulus, MPa Ultimate breaking strength, MPa E, MPa Elongation at break, % Hardness Shore A Shore D Tensile strain, % Part of the sample insoluble in boiling xylene, % by weight Part of the rubber soluble in boiling xylene, | % by weight 1 6Q 40 6 in 9.7 215.6 48.6 3|80 8.9 44 18 62.8 (61.7) 0 Z 50 5Q 5 1.0 11.8 23.6 77.1, 430 92 48 27 51.7 (52.0) | 0.6 3 40 eo 4 0.8 13.8 27.8 237.8 460 98. 52 43 44.0 (42.2) 0 4 30 70 3 0.6 16.6 24.3 349.5 440 95 60 49 31.4 (31.5) 0.3 5 20 80 2 0.4 1.7.6 25.9 477.4 510 97 65 60 6 10 90 1 ¦ 0.2 210.0 22, 9 742.5t 57:0 97 71 85 (overweight) 21.7 (21.6) 0.5 12.0 (11.0) 0 | 1, as in Table VI, the phenolic vulcanizing resin is added to the dust and stirring is continued for 4 minutes. The compositions are removed from the mixer, rolled into sheets, returned to the mixer and mixed for a further 2 minutes. The compositions are again removed from the mixer, formed into sheets and compressed at 220°C. All compositions are thermoplastic and compositions 1-4 are elastomeric. Compositions 5 and 6, with a high proportion of polypropylene, are non-elastomeric. When stretched, they become constricted, i.e. they go through a state that makes it impossible to return to their initial form. In the entire range of proportions, the rubber is completely vulcanized; the amount of rubber soluble in boiling xylene is less than 1% by weight of the rubber present in the composition. The dyeable compositions according to the invention, containing a white pigment (magnesium silicate) and the composition according to the invention containing polyethylene, are shown in Table X. Composition 1 contains (all parts by weight): 50 parts EPDM rubber, 50 parts polypropylene , 40 parts of magnesium silicate (filler), 0.5 parts of stearic acid and 5.6 parts of phenolic vulcanizing agent SP-1056. The preparation method is the same as in Table VIII, except that the magnesium silicate is completely dissolved before adding the phenolic vulcanizing agent. In the presence of magnesium silicate, the addition of zinc oxide is not required. Solubility data in cyclohexane indicate that the rubber is completely vulcanized. Composition 2 contains (all parts by weight): 40 parts of EPDM rubber, 60 parts of polyethylene, 0.4 parts of stearic acid, 0.8 parts of zinc oxide and 4.5 parts of phenolic vulcanizing resin SP-1056. The rubber and polyethylene are loaded into a Brabender mixer, maintained at 180°C, and masticated at 80 rpm until the polyethylene melts. Stearic acid and phenolic vulcanizing agent are added and mixing is continued until a homogeneous mass is obtained. Tin oxide is added - Table Tensile strain, % Compressive strain, % Part of the sample insoluble in boiling xylene, wt.% Soluble rubber, wt.% Part of the sample soluble in cyclohexane at room temperature, wt.% 1 | 50 50 — 40 0.5 —» 5.6 46 13),0 16.3 18.6 420 26 28 64.0 (64.0) 0 0.1 2 40 — 60 — 0.4 0.88 4 ,5 44 10.0 1.5.5 18.6 370 3(3 27 46.8 (4A6) 0 0.2 1 as in Table VI 1 polyethylene with average molecular weight distribution, ASTM D-1248-72, type III, class A, melting index 0.3 g/i0 minutes, specific gravity 0950 g/cm*126 439 27 28 ku and continue mixing until maximum consistency is obtained (3-4 minutes) and for another 2 minutes. The resulting composition is thermoplastic. tangential and elastomeric. The solubility data indicate that the rubber is completely vulcanized. The compositions according to the invention, in which various activators are used, are presented in Table XI. EPDM rubber contains 55% by weight of ethylene, 40.6% by weight of propylene and 4.4% by weight of dicyclopentadiene and has a polydispersity of 6.0i. Polypropylene is the same as in Table I. The phenolic vulcanizing resin is added at the end. Composition 1, control, does not contain a vulcanization activator. ¬ assume that it is not fully vulcanized (possibly a copolymer was formed). These conclusions are confirmed by the solubility data in cyclohexane. Compositions 2, 3 and 4 contain zinc oxide, zinc stearate or stannous chloride, respectively, as vulcanization activator. The data indicate that the rubber in the blends is substantially completely vulcanized. The percentage of cyclohexane-soluble rubber is corrected by a value of 1.38% by weight to include unvulcanized acetone-soluble rubber. The corrected value is marked with an asterisk. Compositions 4 and 5 show that if stannous chloride is used as the activator, a non-halogenated phenolic vulcanizing resin can be used instead of the halogenated one, obtaining an elasto-plastic composition with essentially the same properties. The presence of the vulcanization activator(s) and its appropriate concentration are important. Without a vulcanization activator or with an inappropriate concentration, the rubber is not completely vulcanized, which results in a deterioration of the properties of the mixture. It is assumed that a high concentration of the activator, especially when added before the phenolic vulcanizing resin, causes reactions within the resin itself (homopolymerization), depriving the system of the vulcanizing agent. The appropriate concentration of the activator depends on its type and the type of phenolic activating resin and rubber, the order in which the phenolic vulcanizing resin and activator are added, and the processing temperature. These values can be easily determined experimentally. The compositions according to the invention in which the EPDM rubber contains various monomers are presented in Table XII. Compositions 1 and 2 contain EPDM rubber in which the unsaturation comes from ethylidene norbornene (ENB). In compositions 3-6, the source of unsaturation of EPDM rubber is hexadiene-1,4 (1,4 HD), and in composition 7, dicyclopentadiene (DCPD). The compositions are prepared according to the method from Table I, except that in the case of composition 1, the temperature of the Brabender mixer is - Table XI Composition EPDM rubber Polypropylene Stearic acid ZnO Zinc stearate SnCl2-2H20 Phenolic resin; vulcanizing Hardness, Shore D 100% modulus, MPa 300% modulus, MPa Ultimate tensile strength, MPa Elongation at break, % Tensile strain, % Compressive strain, % Pressure in ASTM-3 oil, % Part of the sample dissolved | na in cyclohexane at room temperature, wt. Part of the rubber soluble in cyclohexane at room temperature % by weight | |__1 50 50 0.5 — — — 5.631 29 7.0 -^ 6.9 100 57 83 m ¦ 21 40 38.6* 2 50 50 0.5 0.5 —» ¦ ¦ — 5.63i 41 9 .3 14.5 21„0 450 32 38 133 2.2 4.2 2.8* and 3 50 50 0.5 — . Q.2 - 5.631 .411 9.1 113.7 20.8 . .470 32 39 134 1.6 3.0 1.6* ' 50 50 0.5 — — 1 5.631 41 9.8 ;4.4 21.6 480 30 46 140 '¦$ 0.4 0.8 8 * 5 50 50 0.5 — — 1 5.63* 44 10.0 13.4 18.6 470 32 45 147 0 0 0 1 halogenated phenolic vulcanizing resin as in Table I 1 non-halogenated phenolic vulcanizing resin as in Table IV126 439 29 30 Table XII Composition ' | EPDM rubber Ethylene, wt.% Monomer type Monomer, wt.% Polydispersity Mooney viscosity (ML, 1 + 8, 100°C) EPDM rubber Polypropylene Stearic acid -.'" Zinc oxide SnCl2-2H20 Phenolic resin Vulcanizing compound SP-10581 SP-1045* Hardness, Shore D 100% modulus, MPa 300% modulus, MPa: Ultimate tensile strength, MPa Elongation at break, % Strain at tensile, % Strain at compression, % Specification in oil ASTM-3,, % Part of the sample insoluble in boiling xylene, wt.%: Part of the rubber soluble in boiling xylene, wt.% Part of the sample insoluble in xylene at room temperature, wt.% l 56 ENB 4.4 5.2 60 50 50 -- 0.5 - 1 — 5,.63i 46 10.3 16.3 22.0 390 29 36 1114 51.8 (53.3) 2.8 42, 9 2 59 ENB 2.6 — 90 1, -^ 5.631 44 9.6 15.0 24.2 480 27 36 123 52.7 (53.3) 1.1 42.1 3 65 *.4HD 3.7 2.5 80 4 55 1.4HD 5.0 2)0 90 parts by weight - 1 5.63* 44 10.6 17.4 23.5 440 28 37 im 52.9 (53.3) 0.8 44 .7 —' 1 5.63* 44 9.9 13.0 20.5 500 34 30 116 50.3 (53.3) 51.4* 5.6 2.1* 42.5 5 56 1.4HD 3.7 19.4 39 — 1 5.63* 44 10.2 15.7 li8.2 370 29 34 130 51.3 (53.3) 3.a 4R.1 6 70 1.4HD 3.7 8 33 — 1 5.63^ 49 13.0 17.3 24.5 460 54 41 129 49.8 (53.8) 521.2* 6.6 4.6* 4.6.5 7 1 55 DOPD 4.4 6.0 45 w ^ r- 0.5 1 A,63i 44 10.8 16.5 24.0 430 30 37 122 50.2 (53.5) 52.9* 6.2 5.i * 43.6126 439 31 12 table XII cont. Part of the sample soluble in xylene at room temperature, % by weight. Part of the sample soluble in cyclohexane at room temperature, % by weight. Part of the rubber soluble in cyclohexane at room temperature, % by weight and | a 5,.0 0.8 1.5 4.8 0.8 1.5 a 3.7 0.9. 1.7 4 7.6 3.1 5.8 1.7* 5 6.5 0.9 1.7 6 4.7 2.4 T U3 2.4s Table XIII 1 Cylinder temperature Type of vulcanizing agent Temperatures of the extruded mass, ° C Capacity, g/min Pipe dimensions, extrusion speed 381 cm/min Outer diameter, mm Inner diameter, mm Appearance Pipe dimensions at maximum extraction 1 Outer diameter, mm Inner diameter, mm Surface ratio Appearance Odor 193°C phenolic 197 199 .5 12*815 9.91 smooth 7.7 5.94 3.0 smooth mild sulfur 203 201.8 1A9 9.91 rough 9.68 7.54 1.9 very rough cracked mild 216°C phenolic 2181 186, 0 12.7 9.91 smooth 5.46 437 6.8* smooth mild sulfur 218 189.0 112.37 9.53 smooth 6.115 4.52 4l rough odor H^ 232°C | phenolic 232 182.5 12.7 9.91 smooth 5.46 4.37 6.8 smooth mild sulfuric 234 171f2 12.1? 9.53 smooth 7.U 5.56 3.7 very rough sharp * end of the machine range, no breakage is 170°C. In compositions 1-6, the vulcanization activator is added at the end. In composition 7, stannous chloride is first added, and then the phenolic vulcanizing resin and zinc oxide are added. Uncorrected values for the insoluble part of rubber are given without brackets, and in brackets are values calculated assuming that after vulcanization all components, except polypropylene, become insoluble. Values marked with an asterisk are corrected as follows: In compositions 4 and 7, 4.13 and 1.3-8% by weight of unvulcanized rubber are dissolved in acetone, respectively. The unvulcanized EPDM rubber used in composition 6 does not contain acetone-soluble material, but 2.52% by weight of the unvulcanized rubber does not dissolve in cyclohexane at 50°C, indicating the presence of a significant amount of polyolefin that is not cross-linking. The data show that all compositions have good strength properties and that the polydispersity of the rubber does not have a significant impact on the degree of vulcanization. All 50 compositions exhibit satisfactory oil swelling and compression deformation. The solubility data show that the rubber is completely vulcanized in all compositions. The better processability of the compositions according to the invention results from the comparison of the extrusion characteristics of blends vulcanized with phenolic agents and blends vulcanized with sulfur agents. For example, a pipe with an external diameter of 12.7 mm is prepared by extrusion33 126 439 34 Table ,,2 rough-nodular, many projections 0.13—0.25 mm 210—220°C phenolic 4^.5 smooth sulfuric 34.1 rough-nodular, many projections 0.13—0.25 mm compositions similar to 2 and 3 from Table I through a ring die with an outer diameter of 12.7 mm and an inner diameter of 9.53 mm (20:1 L/D), at a take-up speed of 381 cm/min, using a Davis-Standard extruder with a diameter 3.81 cm, equipped with a general-purpose screw, rotated at a speed of 70 revolutions per minute. The dimensions of the pipe are maintained by slight internal air pressure and water cooling. The barrel temperature varies within the practical processing range: from 193°C, sufficient to completely melt the polypropylene, to 232°C, at which temperature excessive smoke occurs. Intermediate temperature conditions are also tested, i.e. 216°C. Another variable of interest is the ratio of the ring cross-sectional area of the pipe when the pipe is drawn in its diameter, measured at the moment of rupture due to the gradual increase in the withdrawal rate. This variable is a measure of the consistency of the composition, expressed in terms of extensibility at processing temperature. The test results are summarized in Table XIII. The data show that the composition prepared with the phenolic vulcanizing agent is more easily processed than the composition with the sulfur vulcanizing agent. Phenolic resin vulcanized compositions can be extruded over a wide range of temperatures and pipe dimensions, as demonstrated by area ratios. The improved processability of the compositions of the invention is further illustrated by a comparison of the extrusion characteristics of compositions similar to 6 and 7 in Table III. For example, a 5 mm diameter rod is prepared by extruding the above compositions through 5.08 mm diameter dies using a 2.54 cm diameter NRM extruder equipped with a 16:1 L/D general purpose screw, rotated at a speed of 60 revolutions per minute. The temperature of the cylinder varies in the range from 180-190°C to 2! 10-220°C. The results are presented in Table XIV. They demonstrate that compositions prepared with a phenolic vulcanizing agent can be extruded at a higher rate, obtaining pipes with a smoother surface than compositions prepared with a sulfur vulcanizing agent. The compositions according to the invention contain mixtures of polyolefin resins and dispersed, suitably small particles of cross-linked rubber, which components give them high strength and thermoplasticity. A suitable rubber particle size is about 50 µm, and more preferred compositions use rubber with a particle size of 5 µm or less. 15 20 25 30 35 40 45 50 55 60 patent reservations! 1. Elastoplastic composition containing a thermoplastic, crystalline polyolefin resin and fully vulcanized EPDM rubber in the form of dispersed particles with an average size of 50 micrometers or less, characterized in that per 100 parts by weight of the sum of both components it contains about 25-75 parts by weight of polyolefin resin and about 75-25 parts by weight of EPDM rubber vulcanized with a phenolic vulcanizing agent and containing phenolic vulcanizing resin and vulcanization activator, the vulcanized rubber containing not more than about 3)% by weight of unvulcanized ka feelings ku, extractable into cyclohexane at 23°C or not more than about 5% by weight of unvulcanized rubber, extractable into boiling xylene. 2. The composition according to claim I, characterized in that the polyolefin resin contains polypropylene. 3. The composition according to claim 2, characterized in that it contains about 30-250 parts by weight of filling oil per 100 parts by weight of rubber. 4. The composition according to claim. 3, characterized in that it contains about 2^250 parts by weight of carbon black per 100 parts by weight of rubber. 5. The composition according to claim. 2, characterized in that the phenolic vulcanizing resin contains non-halogenated dimethylol-p-alkylphenol, in which the alkyl radical contains 5-10 carbon atoms. 6. The composition according to claim. 5", characterized in that it contains a metal halide or a halogen-donating polymer as a vulcanization activator. 7. The composition according to claim. 6, characterized in that the halogen-donating polymer contains chlorosulfonated polyethylene. 8. The composition according to claim. 7, characterized in that it contains zinc oxide as a vulcanization activator. 9. The composition according to claim. 2, characterized in that the phenolic vulcanizing agent contains a brominated phenolic vulcanizing resin and a metal oxide as a vulcanization activator. W. The composition according to claim 9, characterized in that the metal oxide contains zinc oxide. 11, The composition according to claim 11. 1, characterized in that the polyolefin resin is polyethylene. IIi2. The composition according to claim 2, characterized in that the EPDM rubber contains a terpolymer of ethylene, propylene and ethylidene ions. The composition of claim 1, wherein the rubber is vulcanized to such an extent that not more than about 3% by weight of the rubber is extractable into boiling xylene and the rubber has an average particle size of about 5 micrometers or less. 14. The composition according to claim 1. 2, characterized in that it contains about 30-70 parts by weight of polypropylene, about 3-70 parts by weight of EPDM rubber and 5-300 parts by weight of filling oil per l0-10 parts by weight of the sum of polypropylene and rubber. and 1-100 parts by weight of the crushed filler per 100 parts by weight of the sum of rubber and filler oil. 15. A composition according to claim 14, characterized in that the crushed filler contains carbon black. 16. A composition according to claim 14, characterized in that 17. Composition according to claim 16, characterized in that the filler contains kaolin clay. IB. Composition according to claim 17, characterized in that it contains a silane coupling agent. 19. The composition according to claim 1, characterized in that the phenolic vulcanizing resin is dimethyl-p-octylphenol. 20. The composition according to claim 1 or 2, characterized in that it contains rubber vulcanized with a phenolic vulcanizing agent, which contains 20 parts by weight of phenolic vulcanizing resin and approximately 0.01-10 parts by weight of vulcanization activator per 100 parts by weight of EPDM rubber. 21" The composition according to claim 20, characterized in that it contains a phenolic vulcanizing agent in an amount of 7-14 parts by weight per 100 parts of the total weight of EPDM rubber. 2B. The composition according to claim 21, characterized in that it contains rubber vulcanized with dimethylol-p-oct4ylphenol. 23. A method for producing elasto-plastic compositions, characterized by masticating approximately 25-75 parts by weight of EPDM rubber, 75-25 parts by weight of thermoplastic, crystalline polyolefin resin per 100 parts by weight of the sum of these ingredients and a phenolic vulcanizing agent. , in an amount sufficient to vulcanize the rubber, at a temperature sufficient to soften or melt the polyolefin resin and for a time sufficient to obtain a homogeneous mixture in which the rubber is in the form of small, dispersed particles with an average size of approximately 50 micrometers or less, the vulcanization activator is then added and the mixture is continued to be masticated at the vulcanization temperature until the rubber is vulcanized to such an extent that no more than about 5°C of the rubber is extractable into the boiling xylene. ,24. The method according to claim 23. characterized in that the phenolic vulcanizing agent is a brominated phenolic vulcanizing resin. 25. The method according to claim 24, characterized in that zinc oxide is used as the vulcanization activator. 26. The method according to claim 23, characterized in that the phenolic vulcanizing resin is non-halogenated dimethyl-p-alkylphenol, in which the alkyl radical contains 5-10 carbon atoms. 27. The method according to claim 26, characterized in that chlorosulfonated polyethylene and zinc oxide are used as curing activator. 28. The method according to claim 27, characterized in that the phenolic vulcanizing resin is dimethylol-p-octylphenol. 29. The method according to claim 23, characterized in that the polyolefin resin is polypropylene. 10 15 20 25 30 ZGK 0761/1131/5 — 80 copies Price PLN 100 PL PL PL