Modification of thermoplastic vulcanizates using a statistical propylene copolymers

 

The invention relates to thermoplastic vulcanizates modified with the use of statistical propylene copolymers, and the way they are received, it can be used for the manufacture of various products, such as tires, hoses, belts, gaskets, casting and molded products. The composition includes (A) 20-85 wt. including rubber is dynamically vulcanized in the presence of vulcanizing chemicals rubber, B) 15-80 wt. including combinations 2-400 wt. including statistical propylene copolymer, the maximum melting temperature which is in the range from 25 to 105oWith 100 wt. including semi-crystalline polypropylene having a melting point which is at least 120oC. the Heat of fusion of statistical propylene copolymer is less than 75 j/g, and semi-crystalline polypropylene is greater than 80 j/g Rubber selected from ethylene-propylene-diene, natural rubber, butyl rubber, galobutilovomu, halogenated rubber copolymer of n-alkylthiol and other olefinic rubbers and combinations thereof. Method of preparation of thermoplastic vulcanizate composition includes mixing in any order (a) and (B) and dynamic volcanolike relative elongation at break and impact strength. 2 C. and 14 C.p. f-crystals, 13 tables.

The invention relates to thermoplastic vulcanizates modified with the use of statistical propylene copolymers, to the way they are received and can be used for the manufacture of various products, such as tires, hoses, belts, gaskets, casting and molded products. As a result of this modification improved properties such as elongation at break and impact strength.

Thermoplastic vulcanizates are composed of a thermoplastic phase and a crosslinked rubber phase. It makes sense that they possessed thermoplastic technological properties of thermoplastic phase and a substantial degree of elasticity due to the rubber phase. Hardness A/D shore a thermoplastic vulcanizate usually govern the relationship between a more rigid thermoplastic phase and a softer rubber phase.

Elongation at break of thermoplastic vulcanizate regulate with the help of many factors, including the compatibility of the two phases, the size of the phases, and add, giving compatibility agents. There is a need in the preparation of thermoplastic vulcanizate composition, which bladelet site area under the curve of stress-strain, when a sample of thermoplastic vulcanizate testing tensile stretched to rupture.

The closest analogue of the claimed invention is patent RU 2074868.

Summary of the invention thermoplastic vulcanizates of polypropylene thermoplastic phase and usually any rubber phase to improve the physical properties of thermoplastic vulcanizate can be modified statistical copolymers obtained by polymerization using a catalyst with a single active site, including metallocene catalyst. Statistical propylene copolymers can contain from about 5 to about 25 wt. %, more preferably from about 6 to about 20 wt.% links to other ethanobotany monomers. Preferred ethylenevinylacetate monomers are ethylene or other monoolefinic containing 4-20 carbon atoms. Preferred residues statistical propylene copolymers represent the repeating unit, derivateservlet in the polymerization of propylene. Acceptable recurring propylene units are units mainly either isotactic or indicacionesambien links, derivationally of propylene exceeds the 0oC. the Preferred content of statistical propylene copolymer relative to the amount of polypropylene thermoplastic material is from about 2 to about 400 wt.frequent. statistical propylene copolymer per 100 wt.frequent. polypropylene thermoplastic, more preferably from about 5 to about 150 wt.frequent. statistical copolymer per 100 wt. frequent. polypropylene thermoplastic. Acceptable propylene thermoplastic is an isotactic polypropylene with a high melting temperature, but can be any polypropylene, other than those referred to statistical copolymer. Taking into consideration the present invention, it is necessary to emphasize the difference between polypropylene thermoplastics, melting point which is at least 120oWith, and statistical propylene copolymer, melting point which is equal to less than 105oC. Rubbers can serve traditional hydrocarbon rubbers, such as ternary ethylene-propylene rubber with diene monomer (Sept), butyl rubber, holodnytskyy, copolymers of p-methylstyrene and isobutylene, natural nauczanie typically include from about 15 to about 75 frequent. thermoplastic phase and from about 25 to about 85 frequent. the rubber phase 100 frequent. thermoplastic and rubber phases in General.

A detailed description of the Statistical propylene copolymers used for the modification of thermoplastic vulcanizates in accordance with the present invention are copolymers of propylene with statistical inclusion in the polymer units of at least one of the co monomer other than propylene. The comonomers are ethylene and other alpha-olefins, containing 4-20 carbon atoms. Structure of propylene units is essentially isotactic or syndiotactic. Statistical propylene copolymers are characterized by a narrow molecular weight distribution with index polydispersity less than 4. They can now be obtained by using a catalyst with a single active site, including metallocene catalysts, although the object of the present invention rather than being the catalysts, and statistical propylene copolymer and thermoplastic vulcanizate composition with statistical propylene copolymer. Metallocene catalyst described in patent US 5017714, which is included in the present description the propylene copolymers are characterized by a low degree of crystallinity with a heat of fusion less than 65 or 75 j/,

To create a metallocene catalysts obtaining statistical propylene copolymers having a narrow molecular weight distribution with index polydispersity less than 4 or 5 when the content of the links of the second co monomer of more than about 3 or 6 wt.%, was associated with significant technological difficulties. Koutsokoumnis copolymers, such as Sept and epichlorhydrine rubber (SKAGG) are available materials. Currently, you can obtain thermoplastic random copolymers comprising from about 2 to about 16, or 20 wt.% parts of the second co monomer or comonomers. Famous first pseudotachylites propylene copolymer was obtained by polymerization of the propylene feedstock and the second source of olefin, typically containing from 2 or 4 to 8 or 12 carbon atoms, maintaining a relatively constant ratio between the source components. Used catalysts always have several different active sites, resulting in some areas cause more effective inclusion of the second olefin than others. Due to the presence of various sections of the length of the polymer chains can also be different. This is the reason for wide is the polymer.

Statistical propylene copolymer of the present invention is characterized by a narrow compositional distribution. Not limited to any particular theory, I believe that a narrow compositional distribution statistical propylene copolymer is important. There is a belief that a narrow compositional distribution is a result of the use of the catalyst with a single active site (such as metallocene), in which there is only one statistical variant of the accession of ethylene and propylene. I believe that this leads to a lack of statistically significant differences in composition between the two polymer chains of a particular polymer. Intermolecular composition distribution of the polymer determine thermal separation into fractions in the solvent. A typical solvent is a saturated hydrocarbon, such as hexane and heptane. This method of thermal separation into fractions described below. Typically, about 75 wt. %, more preferably 85 wt.%, the polymer is isolated in the form of one or two adjacent, soluble fractions, and the rest of the polymer in immediately preceding or succeeding fractions. Composition (relative to the than 20 wt.% from the average mass percentage content of ethylene units in the statistical propylene copolymer component. If statistical propylene copolymer corresponds to the results of the above test on fractionation, it is characterized by a narrow compositional distribution.

The number and distribution of ethylene residues in statistical propylene copolymer corresponds to the statistical polymerization of ethylene, propylene and some optional diene. In stereoblock structures the number of Monomeric residues of any type, related to each other, exceeds the forecasted based on the statistical distribution in statistical propylene copolymers of similar composition. Distribution of ethylene residues in formerly known polymers with stereoblock structure rather consistent with the distribution in these block structures than with the statistical distribution of the monomer residues in the polymer. Intramolecular composition distribution of the polymer can be determined by using the13C-NMR analysis, which indicates the location of the ethylene residues relative to neighboring propylene residue. Statistical distribution of sequences of ethylene and propylene units in the polymer is usually achieved if (1) it is obtained using K is m plot where there is only one statistical variant of the accession of ethylene and propylene, (2) it is produced in a polymerization reactor with a stirrer with a continuous flow thoroughly mixed Monomeric raw material, in which there is only one option polymerization for almost all polymer chains, and (3) the catalyst is characterized by the value of the product of coefficients of reactivity of ethylene and propylene is less than 1.2. These curing parameters necessary to obtain a statistical propylene copolymer.

The preferred statistical propylene copolymer is characterized by a single melting temperature. The melting temperature determined differential scanning calorimetry (DSC). Typically, the melting temperature of statistical propylene copolymer ranges from about 0 or 25, or 30 to 105oC. the Preferred melting temperature is from about 0 or 25, or 30, or 40 to 90 or 100oC. the Most preferred melting temperature is 40-90oC. To achieve presented in this description for the purpose of the graph determine the melting temperature of the DSC melting point is always the maximum. division (MMD), the value of which ranges from 1.5, 1.7 or 1.8 to about 3.5, about 4.0 or 5.0, and the preferred values of the mold ranges from about 1.5, 1.8 or 2.0 to about 2.8 or 3.2.

Acceptable statistical propylene copolymer includes able isotacticity to crystallize alpha-olefin sequences, i.e., preferably propylene sequences (according to NMR). Preferred crystallinity is from about 2 to about 65% gemostaticescoe polypropylene, more preferably from 5 to 40%, as determined by the melting heat annealed samples of the polymer.

Acceptable statistical propylene copolymer includes from about 75 or 80 to 95 wt.% repeating units from propylene and from about 5 to about 20 or 25 wt.% duplicate links of the linear or branched olefin other than propylene and containing 2 or 4 to 8, 12 or 20 carbon atoms, preferably from about 80 to about 94 wt.% repeating units from propylene and from about 6 to about 20 wt.% links of alpha-olefin, most preferably from about 80 or 82 to about 90 or 94 wt. % repeating units from propylene and from about 6 or 10 to about 18 or 20 wt.% links of alpha-olefin is repectfully alpha-olefin is ethylene.

Despite the above description statistical propylene copolymer, it may be worthwhile introducing a mixture of two (preferably) or two or more statistical propylene copolymers. It is necessary that each of these statistical propylene copolymers in a mixture of statistical propylene copolymers satisfy described the characteristics of individual statistical propylene copolymer. These statistical propylene copolymers can vary their srednevekovye or srednekislye molecular mass, and more preferably be of different compositions due to the presence of different quantities of parts of the co monomer introduced in the process of copolymerization with propylene, and a different degree of crystallinity. It is expedient, in particular, to the melting temperature of the first statistical propylene copolymer was 70oWith, and the number of repeating units of propylene in it was more than 93 wt.%, whereas the melting temperature of the second statistical propylene copolymer was less than 60oWith, and the content of repeating units of propylene was not more than 92 wt. %. In another embodiment, it is necessary, tolerabilty in the range from about 20 or 25 to about 65%, as it is determined by the melting heat annealed samples. It is preferable that the second statistical propylene copolymer had a lower crystallinity than the first. I think that the first statistical propylene copolymer, when used in combination with a second and a thermoplastic polypropylene, performs the function of the interfacial agent. Thus, the first statistical propylene copolymer leads to a morphology with a finer dispersion of the dispersed phase and all final properties, which is explained in this finer dispersion (smaller particles). The ratio between the first and second statistical propylene copolymers in the mixture can range from 95:5 to 5:95, preferably from 90:10 to 10:90.

I think that adding statistical propylene copolymers that include two or less, preferably more than two individual statistical propylene copolymers, which are described above, generally results in improved properties of the products and properties of thermoplastic vulcanizate. Under the improved product is usually assumed the possibility of introducing granules almost amorphous statistical propylene copolymer is thinned tensile strength, relative elongation at break and low-temperature impact strength exceeding those values that are achieved in the case of adding only the statistical propylene copolymer.

Any restrictions on the choice of method of obtaining statistical propylene copolymer component according to the invention are absent. Statistical propylene copolymers can be obtained by copolymerization of propylene and alpha-olefin containing from 2 or 4 to about 20 carbon atoms, preferably ethylene, in single-stage or multi-stage reactor. Methods of polymerization include polymerization under high pressure in the slurry, gas phase, in bulk, solution and their combinations in the presence of a catalyst of Ziegler-Natta or metallocene catalyst system with a single active site. In a preferred embodiment, use of the catalyst, which is characterized by isspecifically. The polymerization may be carried out by performing a continuous or periodic process, which may include the use of regulators of the degree of polymerization, cleansing agents, or other such additives, which are thought to be used.

In the General case ropranolol copolymer is as follows: (1) in a reactor with a stirrer injected liquid propylene, (2) through a nozzle or steam, or in the liquid phase is injected catalytic system, (3) gaseous ethylene served in the vapour phase reaction medium or bubbled into the liquid phase, as is well known in the art, (4) the reactor contains a liquid phase consisting essentially of propylene, together with the dissolved alpha-olefin, preferably ethylene, and a vapour phase comprising a pair of all monomers, (5) the temperature and pressure in the reactor can be adjusted by boiling under reflux with evaporation of propylene (self-cooling), and through coil coolers, shirts and so on, (6) the rate of polymerization can be controlled by the concentration of catalyst, temperature, (7) the content of units of ethylene or another alpha-olefin in the polymer product is determined by the ratio between ethylene and propylene in the reactor, which govern the variation of the relative flow introduced into the reactor source components.

So, for example, a typical method of polymerization in obtaining statistical propylene copolymer comprises polymerization in the presence of catalysts containing bicyclopentadiene compound of the metal and either 1) activate sterowanie of ethylene and propylene with a catalyst suitable for the polymerization diluent, moreover, for example, in accordance with the preferred catalyst contains a chiral metallocene catalyst, in particular bicyclopentadiene compound of the metal, as described in patent US 5198401, which according to the accepted practice in the US patent is incorporated into this description by reference, and activator. As the activator can be used alumoxane activator or activator with coordinationin compatible anion.

In a preferred embodiment, alumoxane activator is used in a quantity that provides the creation of a molar ratio between aluminum and metallocenes from about 1:1 to about 20,000:1 or higher. In a preferred embodiment, the activator with coordinationin compatible anion is used in a quantity that provides the creation of a molar ratio between bicyclopentadiene metal connection and coordinationin anion of from about 10:1 to about 1:1. The polymerization reaction carried out by the interaction of such monomers in the presence of such catalyst system at a temperature of from about -100 to about 300oWith in the period of time from about 1 to about 10 h to obtain copolymerisate molecular weight distribution is from about 1.8 to about 4.5.

Although some variants of the method include the use of a catalytic system in the liquid phase (slurry, solution, suspension, phase mass or a combination thereof), in accordance with the other options you can also use the polymerization in the liquid phase under high pressure or in the gas phase. When conducting the polymerization in the gas phase, slurry phase or slurry phase, the preferred catalytic systems are usually a catalytic system on the media (see, for example, patent US 5057475, which is in accordance with U.S. patenting practices included in the present description by reference). Such catalytic systems may also include other well-known additives, such as cleansing agents (see , for example, patent US 5153157, which is in accordance with U.S. patenting practices included in the present description by reference). These methods can be performed without restrictions types of reaction vessels and methods of conducting polymerization. As indicated above, while true for those cases in which use of the catalytic system on the media, the ways of carrying out liquid-phase processes include stage contact ethylenically catalytic system over a period of time and at a temperature sufficient to obtain an ethylene-propylene copolymer target molecular weight and composition.

Statistical propylene copolymer can 1) enter in the components used to obtain thermoplastic vulcanizate (TPV), 2) to mix with TPV composition before vulcanization of the rubber component, or 3) add after vulcanization TPV. The physical properties of the resulting mixture may vary or not to vary depending on, enter whether statistical propylene copolymer before or after vulcanization of the rubber phase. This statistical propylene copolymer can be considered as an addition to semi-crystalline polypropylene thermoplastic vulcanizate, or can be regarded as substitutable in a mass ratio of semi-crystalline polypropylene thermoplastic vulcanizate. When statistical propylene copolymer is injected before vulcanization, can be expected to be present mostly statistical propylene copolymer in thermoplastic phase of the resulting thermoplastic vulcanizate, though he may disproportionately to be on the border between the rubber phase and a thermoplastic phase. Statistical propylene SOP is GKO be mixed in the melt with thermoplastic vulcanizate or its components in normal thermoplastic vulcanizate temperature conditions technology blending.

The main part of the polymers in thermoplastic vulcanite+those are conventional polypropylene thermoplastic statistical propylene copolymer and is capable of crosslinked rubber. Examples of conventional semi-crystalline polypropylene is polypropylene and its copolymers and mixtures.

It is advisable that the total content of conventional semi-crystalline polypropylene and statistical propylene copolymer ranged from about 6 to about 85 wt.%, preferably from about 7 to about 75, more preferably from about 8 to about 60 wt.%, in terms of the prepared thermoplastic vulcanizer. The preferred content of the rubber is from about 5 to about 70, more preferably from about 10 to about 50, most preferably from about 15 to 45 wt. % based on thermoplastic vulcanizer. The preferred number of other conventional components, introduced in (for example fillers, oils, vulcanizing agents, substances to improve the processing properties, and so on, is from about 0, 1, 2, or 10 to about 87, 88 or 89 wt.% in terms of TPR, more preferably from about 0, 1, 2, or 15 to about 81, 82 or 83, it is most preferable from the modification of the flow characteristics or as additives, such as polymeric antioxidants. Polimernye materials such as oils, fillers, diluents and additives (described in the previous paragraph) can be stored in large quantities. In the majority of introduced into the mixture of components usually indicate either 1) based on 100 wt.frequent. a mixture of conventional semi-crystalline polypropylene, statistical propylene copolymer rubber, or 2) based on 100 wt.% rubber bracelet.

The preferred total content of the semi-crystalline polypropylene and statistical propylene copolymer is from about 15 to about 80 wt.often., more preferably from about 25 to about 75 wt. frequent. most preferably from about 25 to about 50 wt. frequent. 100 frequent. a mixture of semi-crystalline polypropylene, statistical propylene copolymer rubber. The preferred content of the rubber is from about 20 to about 85 wt.often., more preferably from about 25 to about 75 wt.often., most preferably from about 50 to about 75 wt.frequent. 100 frequent. the above-mentioned mixture. If the number of semi-crystalline polypropylene described in terms of rubber, the preferred content sostavlyayuscyeye from about 33 to about 200 wt.frequent. on 100 wt.frequent. rubber bracelet.

It is advisable to statistical propylene copolymer guests in amounts from about 2 to about 400 frequent. 100 frequent. conventional polypropylene thermoplastic vulcanizate, preferably in amounts from about 5 to about 150 frequent. 100 frequent. polypropylene, more preferably from about 10, or 25 to about 100 frequent. on 100 wt.frequent. conventional polypropylene and most preferably from about 25 to about 80 wt. frequent. on 100 wt.frequent. conventional polypropylene. For example, statistical propylene copolymer may be contained in amounts from about 4 to about 80, preferably from about 4, or about 20 to about 60 wt.% in terms of thermoplastic phase of thermoplastic vulcanizate. As the proportion of thermoplastic phase of thermoplastic vulcanizate can be from about 15 to about 75% of a mixture of thermoplastic and rubber phases (without fillers, oils and so on), the percentage of statistical propylene copolymer, calculated on the total weight of thermoplastic vulcanizate can be from 1 or 2 to about 40, 50 or 60 wt.% also in terms of the combined weight of conventional polypropylene, statistical propylene with the vulcanizer" in the present description used to refer to the mixture, ranging from small particles of crosslinked rubber, a well-dispersed in semi-crystalline polypropylene matrix, and to the joint in a continuous phase of semi-crystalline polypropylene and from partially to fully stitched rubber or combinations thereof. The term "thermoplastic vulcanizer" indicates that the rubber phase is at least partially vulcanized (crosslinked).

The term "thermoplastic vulcanizer" is used to refer to compositions that can possess the properties of thermosetting elastomer and recyclable in a closed mixer. When reaching a temperature exceeding the softening temperature or melting temperature semi-crystalline polypropylene phase, these compositions can be processed to obtain a continuous sheet materials and/or molded articles, which in appearance resemble the products of this Jersey or products made by melting a thermoplastic vulcanizate with conventional casting or molding of thermoplastics conditions.

It is advisable that after dynamic vulcanization (curing) the rubber phase of thermoplastic vulcanizate of content in the sample thermoplastic 20 or 50 wt.%. Methods for the determination of extractable fraction of rubber, which is shown in patent US 4311628 included in this description as a reference.

Conventional semi-crystalline polypropylene comprises a semicrystalline thermoplastic polymers polymerization process monoolefinic monomers (for example, with 2-10 carbon atoms) high pressure, low pressure or intermediate pressure in the presence of catalysts of the Ziegler-Natta or metallocene catalysts. It can be characterized any regularity of the molecular structure (e.g., isotactic and syndiotactic), or a copolymer such as polypropylene, modified to give impact resistance. The preferred content monoolefinic monomers, turned into a recurring propylene units is at least 80, 85 or 93%. The polypropylene may be a homopolymer, reactor propylene copolymer, polypropylene, modified to give impact resistance, isotactic polypropylene, syndiotactic polypropylene, high-impact copolymer polypropylene or other previously known polypropylene copolymer. Its maximum melting temperature preferably comprised the second rubber, which is able to react and be stapled in the conditions of formation of cross-links. Such rubbers include natural rubber, SKEPT, butyl rubber, holodnytskyy, halogenated (e.g. brominated) copolymers of p-alkylthiol and samanaleya containing 4-7 carbon atoms (e.g., isobutylene), butylketone comprising the repeating unit of divinylbenzene, Homo - or copolymers of at least one conjugated diene, and combinations thereof. Sept, butyl and holodnotsinkovye called rubbers with low content of residual unsaturated groups, which are preferred when it is necessary to vulcanizer had good resistance against heat aging or oxidative stability. It is advisable to rubbers with low content of residual unsaturated groups comprised less than 10 wt.% duplicate links with unsaturated groups. Of rubber, it is advisable to exclude acrylate rubber and epichlorhydrine rubber. Considering the purpose of the present invention, the term "copolymers" is usually used to determine polymers from two or more monomers and polymers, which may include links to one or more other Monomeric Sept represent ternary copolymers, derivateservlet polymerization of at least two different monoolefinic monomers containing 2-10 carbon atoms, preferably 2-4 carbon atoms, and at least one polyunsaturated olefin containing 5-20 carbon atoms. It is advisable that such monoolefinic answered the formula CH2= CH-R, where R denotes H or alkyl with 1-12 carbon atoms, preferably ethylene and propylene. It is advisable that the repeating unit of at least two monoolefins (preferably ethylene and propylene) are contained in the polymer in a weight ratio of from 25:75 to 75:25 (ethylene/propylene units) and ranged from about 90 to about a 99.6 wt. % based on the polymer. Polyunsaturated olefin can be remotemachine, branched, cyclic, cycles, connected by bridge, bicyclic, bicyclic connection with the condensed cycles and so forth, the preferred non-conjugate diene. It is advisable that the repeating unit unpaired polyunsaturated olefin ranged from about 0.4 to about 10 wt.% rubber bracelet.

As rubber may be used butyl rubber, holodnytskyy or halogenated (for example, commercially available brominated) copolymer of p-alkylsilane recurring units of isobutylene, but it contains a bit of repeating units of the monomer, which provides the introduction sections to obtain cross-linking. The monomers which provide the introduction sections to obtain the cross-links are polyunsaturated monomers such as conjugated diene and divinylbenzene. It is advisable that from approximately 90 to approximately 99.5 wt.% butyl rubber accounted for duplicate links, derivatizing in the polymerization of isobutylene and from about 0.5 to about 10 wt.% duplicate links, derivatizing of at least one polyunsaturated monomer containing 4-12 carbon atoms. Preferred polyunsaturated monomer is isoprene or divinylbenzene. The polymer may be halogenated to further increase reactivity when stitching. In a preferred embodiment, the halogen is contained in an amount of from about 0.1 to about 10 wt. %, more preferably from about 0.5 to about 3.0 wt. percent, calculated on the weight of the halogenated polymer and the preferred halogen is chlorine or bromine. It is advisable that the commercially available brominated copolymer of p-alkylthiol containing from about 9 to 12 carbon atoms, and samanaleya,) from about 92 to about 98 wt. %, and from about 1 to about 12 wt.% links p-alkylthiol, preferably from about 2 to about 8 wt.% in terms of the weight of the copolymer before galoidirovaniya. It is advisable to alkylthiols was p-methylsterol and somnolin represented isobutylene. The preferred percentage of bromine is from about 0.2 to about 8 wt.%, more preferably from about 0.2 to about 3 wt.%, in terms of the weight of the halogenated copolymer. This copolymer contained in the prevailing amount, i.e. from about 92 to about 99,8, more preferably from about 97 to 99.8 wt.%. Such polymers are commercially available products manufactured by Exxon Chemical Co.

In the dynamic vulcanizate can be used with other rubbers such as natural rubber and synthetic Homo - and copolymers of at least one conjugated diene. These rubbers more ninasimone than Sept and butyl rubber. Natural rubber and Homo - or copolymers of diene optionally partially hydrogensulfate to improve the resistance to thermal aging or oxidative stability. Depending on the comonomers synthetic rubber may be non-polar or polar. Selesai least one conjugated diene monomer, containing 4-8 carbon atoms. Can be used comonomers which include vinylaromatic(s) monomer(s) that contain(s) 8 to 12 carbon atoms, Acrylonitrile and alkyl substituted(s) - Acrylonitrile(s) monomer(s) that contain(s) 3-8 carbon atoms. Other comonomers that can be used, introducing the repeating unit, derivateservlet from monomers include unsaturated carboxylic acids, unsaturated dicarboxylic acids, unsaturated anhydrides of dicarboxylic acids; these include divinylbenzene, alkylacrylate and other monomers containing 3-20 carbon atoms. Examples of synthetic rubbers include branch, Rubezhnoe, Ukraine, polybutadiene rubbers, styrene-butadiene rubber, butadiene-Acrylonitrile rubber, etc. Can be used functionalized with amino groups, carboxyl functionalized groups and functionalized by epoxypropane synthetic rubbers, examples of which include molinerotary Sept and functionalized by epoxypropane natural rubbers. These materials are commercially available products.

Thermoplastic vulcanizates of the present invention is usually prepared by mixing in the melt in any order procris copolymer, rubber and other components (filler, plasticizer, lubricant, stabilizer and so on) in the mixer and heated to a temperature higher than the melting point of polypropylene thermoplastic. Optional fillers, plasticizers, additives, etc. can be entered at this stage or later. After mixing in the molten state to a degree sufficient for the formation of a well-mixed mixture, usually with added curing agents (also known as vulcanizing group or cross-linking agents). In some embodiments, curing substance is preferably in solution using a liquid such as softener for rubber, or masterbatches, which is compatible with other components. Over the course of the vulcanization process it is convenient to follow the values of torque mixing or energy of mixing required under stirring. Usually the schedule of values of torque or energy of the mixture passes through a maximum, after which mixing can continue a little longer to improve the technological properties of the mixture. If necessary, some components can be added upon completion of dynamic vulcanization. Statistical propylene copolymer can CC aucoc and thermoplastic you can grind, be subjected to rough grinding, ekstradiroval, be pelletized, to process by injection molding or any other necessary technology. Usually it is advisable to provide fillers and parts of plasticizer spontaneous distribution in rubber or semi-crystalline polypropylene phase to stitching this rubber phase or phases. Depending on the mixing temperature, shear forces and contained activators for curing substances cross-linked (vulcanized) rubber can occur within a few minutes or less. Acceptable temperature vulcanization is from about 120 or 150 to approximately 250oS, more preferably from about 150 or 170 to about 225 or 250oC. as the mixing equipment can be used mixers BunburyTMthe mixers BrabenderTM, multiple-roll mixing rolls and some mixing syringe machine.

Thermoplastic vulcanizer can contain many additives. Supplements include powdery fillers such as carbon black, silicon dioxide, titanium dioxide, colored pigments, clay, zinc oxide, stearic acid, stabilizers, protula improve adhesiveness, plasticizers, waxes, discontinuous fibers (such as drevesnoplitnye fiber) and oil filling rubber in the stage latex. When using oil for the filling rubber in the phase of the latex, it may be contained in amounts from about 5 to about 300 wt.frequent. on 100 wt. frequent. a mixture of semi-crystalline polypropylene with rubber. The oil content of filling rubber in the stage of latex (for example, hydrocarbon oils and ester plasticizers) can also be expressed in terms of 100 wt.frequent. rubber, and in this case it is from about 30 to 250 wt. often., preferably from about 70 to 200 wt.frequent. When used Nesseby the filler to impart compatibility in the boundary layer between this nesheim filler and polymers it is necessary to add the sizing. When using carbon soot, appropriate to its content ranged from about 5 to about 250 wt.frequent. on 100 wt.frequent. rubber bracelet.

Another feature introduced in dynamic vulcanizer is a vulcanizing agent, which knits or vulcanized stitched rubber phase. Type vulcanizing agents used in the present invention depends on the type of rubber that you want plastycznych of vulcanizates and in normal quantities. Curing substances include, but are not limited to, phenolic polymer curing substances, sulfur vulcanizing substances together with the accelerators, the accelerators individually, peroxide curing substances forming the silane curing compounds containing silicon hydride and platinum or peroxide catalyst, etc.,

Thermoplastic vulcanizate the composition of the invention can be used for manufacturing a variety of products, such as tires, hoses, belts, seals, castings and molded parts. They are particularly effective for the manufacture of products in extrusion, injection molding, blow molding and direct extrusion. They can also be used for modification of thermoplastic resins and primarily of polyolefin resins. The proposed composition can be mixed with thermoplastic resins using conventional mixing equipment for the preparation of modified rubber thermoplastic resin. Properties of the modified thermoplastic resin depend on the number of mixed thermoplastic vulcanizate composition.

Mechanical properties of the proposed compositino elongation tensile (PR), tensile strength at break (TD), stress at elongation of 50% (Uw50), stress at elongation of 100% (N) and elongation at break (El). The tear resistance is determined in accordance with ASTM D-623. The hardness is determined in accordance with ASTM D-2240 with a 5-second delay using either a scale And Shor or scale D Shor. Residual compression (OS) determine in accordance with the method of ASTM D-395 by compressing the sample for 22 h at 100oC. Expansion in oil (NM) (% weight change) is determined in accordance with ASTM D-471 by keeping the sample immersed in oil IRM 903 in all cases, unless otherwise indicated, for 24 h at 1252oC. Especially preferred compositions according to the invention are koutsokoumnis compositions, the values of the relative elongation at break of about 50% or less, and such compositions are within the scope of the rubber, formulated on page 756 volume 28 of the code of ASTM standards (D-1566). More preferred compositions include koutsokoumnis compositions, which are characterized by D hardness shore a 60 or less, the voltage at outlineview, which was used as comparative examples, are presented in tables I-III, were determined by mass percentage content of ethylene units in accordance with ASTM D-3900. The statistical propylene copolymer, are presented in tables I-III, were determined by mass percentage content of ethylene units in accordance with the following method. A thin uniform film of the copolymer, pressed at a temperature of about or above 150oWith that secured in the infrared spectrophotometer Perkin-Elmer PE 1760. Recorded the whole spectrum for a given sample within 600-400 cm-1and the mass percentage content of ethylene units was calculated by the following equation 1: ethylene units, wt.% = 82,585 - 111,987 X+30,045 X2(ur. 1) where X denotes the ratio between the peak height at 1155 cm-1and the peak height or at 722 cm-1or at 732 cm-1(depending on which one is higher).

The method of determining the molecular weight (mn and Mw) and molecular mass distribution (MMD) is described in the patent US 4540753 (in the name of Cozewith, Ju and Verstrate), which with all of the designated links in accordance with U.S. patenting practices included in which all of the links in accordance with U.S. patenting practices included in the present description by reference.

Below test method differential scanning calorimetry, the results of which are shown in tables I-III. Of the punching stamp remove approximately 6-10-milligrammes a sample sheet of the polymer pressed at approximately 200-230oC. release It at room temperature for 80-100 hours At the end of this period the sample is placed in a differential scanning calorimeter (instrument for systems thermal analysis Perkin Elmer 7 Series Thermal Analysis System) and cooled to a temperature of from about -50 to about -70oC. the Sample is heated for 20 minutes to achieve a final temperature of from about 200 to about 220oC. Thermal performance record as the area under the peak melting of the sample, which, as a rule, differentiate in the range of from about 30 to about 175oWith, and the process occurs in the temperature range from approximately 0 to approximately 200oWith, and measure the heat of fusion is expressed in joules. The melting temperature is fixed as the maximum temperature of the adsorption heat in the melting range of the sample. In these conditions, the melting point of the statistical propylene copolymer and the heat of melting is lower than that of propylene what about the following method. About 30-gram sample statistical propylene copolymer cut into small cubes with a side of approximately 1/8 inch. They were placed in a thick-walled glass bottle closed by a threaded cap, together with 50 mg of the product Irganox 1076 (antioxidant, produced by Ciba-Geigy Corporation). Next to the content of the bottles was added 425 ml of hexane (main mix normal and branched isomers) and tightly closed bottle kept at approximately 23oWith within 24 hours Upon completion of this period the solution decantation and the residue was treated with an additional amount of hexane for another 24 hours At the end of this period both hexane solution were combined and evaporated to obtain a residue soluble in the 23oWith polymer. To this residue was added hexane in a quantity sufficient to bring the volume up to 425 ml, and the bottle kept at the 31oC for 24 h in a closed bath with circulating water. Soluble polymer decantation and added an additional amount of hexane for further processing for another 24 h at approximately 31oWith subsequent decantation. According to this method, when the temperature at the transition from one stage to another has increased by approximately 8oWith, instead of the hexane used heptane, you could provide the possibility of increasing the temperature to 95oC. Soluble polymers were dried, weighed, and in accordance with the above-described IR method was analyzed for composition, determining the mass percentage content of ethylene units. Soluble fraction, which was obtained by interconnecting the growth temperature, represented in accordance with the above description of the related faction.

Samples with ARR-1 ARR-5 was prepared in accordance with those described in the present description for the case of polymerization with statistical propylene copolymer. Table I presents the results of GPC analysis on the composition, ML - and DSC-analyses of these polymers and some comparative polymers (tables I - XIII, see the end of the description). Qualified electronic signature certificate was a product VistalonTM457 (ethylene-propylene copolymer manufactured by EXXON Chemical Co. ), and exp. PP was an experimental propylene copolymer containing an 11.7 wt.% ethylene units, but without the isotactic propylene sequences (i.e., he was fully amorphous). Along with some conventional propylene copolymers and homop And M-PP-D and M-PP Z. Table II shows the temperature and the percentage of each copolymer, at a certain temperature soluble in hexane.

Due to the lack of drying of the polymer fractions the sum of the fractions exceeds 100%.

Table III presents the fractions propylene copolymers obtained in accordance with table II. Analyzed the composition of only those fractions, which accounted for over 4% of the total weight of the polymer.

In table IV is characterized by the composition of thermoplastic vulcanizates (TPV), which is indicated in the following tables. TPV also include lateral connections through cross-linking agent, and in the preferred embodiment, and fillers, oils, substances to improve the processing properties, and so on,

In table V are mapped unmodified TDI polypropylene, SKEPT with the same (modified 1) polypropylene homopolymer (a product of Lyondell 51S07A), 2) four different statistical propylene copolymers (a-D) and 3) conventional propylene copolymer.

Suppose that the error in the experiment when determining the content of ethylene units is about 0.4 wt.% from the absolute values.

Table VI presents the properties of the four who demonstrate the impact of adding in four different statistical quantities propylene copolymer, thermoplastic vulcanizates (TPV). The amount of the applied statistical propylene copolymer exceed those listed in the previous tables. As follows from the data of this table by reading them from left to right, experimental polypropylene copolymer increases the elongation at break increases impact strength and increases the tear resistance of the compositions. Due to the fact that thermoplastic statistical propylene copolymer increases the relative proportion of thermoplastic phase in these examples, with increasing number of statistical propylene copolymer he usually increases the hardness And the shore and the module.

In table VIII presents the data for test cases that illustrate the impact of adding polypropylene homopolymers. With increasing shock strength increases more precisely the function module than the increase in the relative elongation at break.

In table IX illustrates the impact of adding a traditional propylene copolymers in TPV. Again, as in the case of propylene homopolymers, the increase in impact strength is primarily due to the increase of the module.

The data in table X show that statistical Propylenediamine).

In table XI are mapped 1) product TPV-3 (9,4% by weight polypropylene) 2) product TPV-3 with a statistical propylene copolymer and 3) with the product of TPR-1, which contains a 13.4 wt. % polypropylene. The increase in impact strength in examples 54 and 55 is more likely a result of the influence of statistical propylene copolymers, than the percentage of polypropylene.

The data in table XII illustrate the impact of adding statistical propylene copolymer before or after curing (vulcanizing) rubber phase.

The data in table XIII illustrate the influence of statistical propylene copolymer products TPV-4 and -5, which are used respectively nitrile rubber and butyl rubber (not Sept, which is used in products with TPR-1 to -3, listed in the previous tables).

Although the above invention is described on the example of the preferred variants of its execution, its scope is not limited to this option, as defined by the attached claims.

Claims

1. Thermoplastic vulcanizate composition, including:

A) from 20 to 85 wt. including rubber is dynamically vulcanized in the presence of vulcanizing substances the second melting temperature which is in the range from 25 to 105With 100 wt. including semi-crystalline polypropylene having a melting point which is at least 120From where the heat is melting semi-crystalline polypropylene is greater than 80 j/g, and statistical propylene copolymer has a heat of fusion less than 75 j/g and comprises from 80 to 95 wt.% repeating units of propylene and from 5 to 20 wt.% recurring units of one or more other olefinic unsaturated monomers containing 2 or from 4 to 12 carbon atoms, in terms of the statistical weight propylene copolymer, and where the rubber is selected from ethylene-propylene-diene rubber, natural rubber, butyl rubber, galobutilovomu, halogenated rubber copolymer of p-alkylthiol and at least one4-C7samanaleya, copolymer of isobutylene and divinylbenzene, rubber homopolymer paired With4-C8the diene rubber copolymer comprising at least 50 wt.% duplicate links of the at least one paired With4-C8diene, and combinations thereof.

2. Composition under item 1, in which the rubber is dynamically vulcanized in the presence of semi-crystalline polypropylene statistikaametite under item 1, in which the maximum temperature melting statistical propylene copolymer is from 30 to 105C.

4. Composition under item 1, the maximum melting temperature of which ranges from 40 to 100C.

5. Composition under item 1, which further includes at least one oil, at least one filler and at least one other additives.

6. Composition under item 1, in which statistical propylene copolymer includes from 5 to 20 wt.% duplicate links of the at least one monoolefins containing from 4 to 8 carbon atoms.

7. Composition under item 1, in which statistical propylene copolymer comprises from 80 to 90 wt.% repeating units of propylene and from 10 to 20 wt.% duplicate links of the at least one monoolefins containing 2 or from 4 to 8 carbon atoms.

8. Composition under item 1, in which the rubber is an ethylene-propylene-diene rubber.

9. Composition under item 1, in which the rubber is a butyl rubber, halobutilic or halogenated rubber copolymer of p-alkylthiol and isobutylene.

10. Composition under item 1, in which the rubber is a natural rubber.

11. The composition according to p. 1,different atoms, or rubber copolymer comprising at least 50 wt.% recurring units of at least one conjugated diene containing from 4 to 8 carbon atoms, or a combination thereof.

12. Composition under item 1, in which statistical propylene copolymer includes first and second statistical propylene copolymers when the mass ratio of the first copolymer and the second copolymer of from 95:5 to 5:95, where the melting temperature of the first copolymer exceeds 70C and the melting point of the second copolymer is less than 60C.

13. Method of preparation of thermoplastic vulcanizate composition comprising (A) mixing in any order (a) from 20 to 85 wt. including rubber, b) from 15 to 80 wt. including combinations 2-400 wt. including statistical propylene copolymer, the maximum melting temperature which is in the range from 25 to 105With 100 wt.h. semi-crystalline polypropylene having a melting point which is at least 120From where the heat is melting semi-crystalline polypropylene is greater than 80 j/g, and statistical propylene copolymer has a heat of fusion less than 75 j/g, vkiki other olefinic unsaturated monomers, containing 2 or from 4 to 12 carbon atoms, in terms of the statistical weight propylene copolymer, and where the rubber is selected from ethylene-propylene-diene rubber, natural rubber, butyl rubber, galobutilovomu, halogenated rubber copolymer of p-alkylthiol and at least one4-C7samanaleya, copolymer of isobutylene and divinylbenzene, rubber homopolymer paired With4-C8the diene rubber copolymer comprising at least 50 wt.% duplicate links of the at least one paired With4-C8diene, and combinations thereof, and B) the dynamic vulcanization of the rubber in the presence of vulcanizing chemicals rubber after mixing with semi-crystalline polypropylene, statistical propylene copolymer or combination thereof.

14. The method according to p. 13, in which the maximum temperature of the melting statistical propylene copolymer is from 30 to 105C.

15. The method according to p. 13, in which the maximum temperature of the melting statistical propylene copolymer is from 40 to 100C.

16. The method according to p. 13, in which statistical propylene copolymer to relax

 

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