HU189266B - Process for production of thermoplastic elastomers and elastomer-compositions - Google Patents

Abstract

The invention relates to a process for producing thermoplastic elastomer compositions by vulcanising … … a) 1 or more polypropylene(s) … b) 1 or more rubber(s) and, if appropriate, … c) at most 20 parts by weight of 1 or more monomer(s) and/or oligomer(s) and in addition … d) at most 5 parts by weight of 1 or more peroxide(s) and, if appropriate, … e) at most 300 parts by weight of 1 or more filler(s), reinforcing filler(s), plasticiser(s), stabiliser(s), lubricant(s), pigment(s) and/or other polymer(s) and/or thermoplastic elastomer(s) and/or auxiliary(ies), … in which … … a) as polypropylene(s), ÄanÜ atactic polypropylene(s), at least 50 % by weight of which has a number average molecular mass of Mn / 5 x 10<3> and a weight average molecular mass of Mm / 8 x 10<4>, in amounts of 35 to 85 parts by weight and … b) 15 to 65 parts by weight of one or more rubber(s) … are used. …<??>The invention also relates to the use of the elastomer compositions thus produced as hot-melt sealing and hot-melt adhesive material and as binders of base stocks in the plastics and rubber industry and as additives for modifying one or more polymer(s).

Description

The present invention relates to a process for the preparation of thermoplastic elastomer and elastomer compositions.

Five types of thermoplastic elastomers are distinguished: polyurethanes, styrene / butadiene-based block copolymers, ethylene / propylene-based block copolymers or polyolefin blends, polyesters and syndiotactic polybutadiene. These thermoplastic elastomers are not necessarily cross-linked, and in most cases are not, although they may be cross-linked at the final stage of manufacture. The appearance of their rubber-like properties is due to their special morphological structure. Chemically, these thermoplastic elastomers are so-called. They consist of "hard" and "soft" segments, molecular chain segments, blocks, and respectively "hard" and "soft" phases. The "soft" segment and an amorphous phase is always less,-ambient glass transition temperature _(Tg), the "hard" and T _g above room -jű polymer. The "hard" and "soft" segments form a microheterogeneous structure through phase separation, whose spheres, domains provide nodes of a pseudo or physical network structure. The latter can also be understood as analogs of reinforcing filler particles [P. Dreyfuss,

LJ Fetters: Rubb. Chem. Technol., 53 (3), 728 (1980)]. Generally, these "hard" lumps, phases, are formed because they are frozen at room temperature due to molecular motions or high T _g of the polymer forming the phase (e.g., in polystyrene inclusions in styrene / butadiene block copolymers), or molecular movement is inhibited by the formation of crystalline areas (polyester, polyurethane-polyolefin-based thermoplastic elastomers and 1,2-polybutadiene). Such non-covalent intermolecular attachment of chain molecules of block copolymers leads to the formation of a physical network structure. In principle, there are three ways in which the physical cross-linking structure resulting in the appearance of rubber elastic properties can be formed [D. Braun, JH Wendorff: Kautschuk, Gummi, Kunststoffe, 33 (10), 821 (1980)]:

- the corresponding segments of the molecular chains are involved in the formation of crystallites (this is the case for the thermoplastic elastomer containing all blocks, segments which tend to crystallize)

- mutual translational movement of chain molecules by formation of glassy regions or frozen (examples of amorphous thermoplastic elastomers are butadiene / styrene or isoprene / styrene-based block copolymers)

- Chain looping occurs at the molecular level.

Although chain-linking necessarily occurs over certain molecular chain lengths (but its effect on physical-mechanical properties is small), there is no known thermoplastic elastomer whose properties are determined by molecular chain or phase looping.

The term "thermoplastic elastomer" is derived from the fact that, above a certain temperature, the "hard" segment polymer or "blend" polymer softens, flows, and can be processed in the same way as thermoplastic materials. Upon cooling, the physical cross-linking structure or mixture will re-form the biphasic structure, imparting a rubbery appearance to the material. These thermoplastic elastomers, which are thus block copolymers or blends, can only be prepared by extremely complex polymerization techniques, except of course blends [P. Dreyfuss, L. J. Fetters: Rubb. Chem. Technol., 53 (3), 728 (1980) and H. L. Hsieh, R. H. Burr, Mod. Plast. Intern., 12 (6), 46 (1982)]. Thus, it is understood that the production of thermoplastic elastomers by melt mixing is encouraged. In these mixtures, the "hard" and "soft" constituents form a separate phase, but they must have sufficient interaction to ensure proper properties. This is to be achieved by mixing the "hard" phase crystalline polyolefins primarily with rubbers having good interfacial adhesion to the crystalline polyolefins. Amorphous or partially crystalline ethylene (propylene) diene terpolymer rubbers (EPDM) have been used for this purpose (U.S. Patents 3,758,643, 3,835,201, 3,862,106, 4,031,169, 4,036,912, 4,046,840). . However, thermoplastic elastomers have also been produced in the dynamic vulcanization of isotactic polypropylene and EPDM [A. Y. Coran, R. Patel: Rubb. Chem. Technol., 53 (1), 141 (1980)].

A thermoplastic composition containing dynamically vulcanized rubber was first described by Gessler (U.S. Patent No. 3,037,954). Dynamic vulcanization means that the rubber is cured by mixing the plastic melt. In mixtures produced by dynamic vulcanization, these mixtures are also referred to as thermoplastic vulcanizates [A. Y. Coran, R. P. Patel, D. Williams: Rubb. Chem. Technol., 54 (1), 116 (1982)], is present in the form of a fine dispersion of vulcanized rubber. It has also been stated in the aforementioned work that such a thermoplastic elastomer can be prepared only if the constituents have nearly the same surface energy and the crystalline polymer forming the non-caustic is also a condition for the production of the thermoplastic elastomers by blending. Crystalline polyolefins are also (dynamically) vulcanized with rubbers other than EPDM to produce thermoplastic elastomers (German Patent Application Nos. 2,657,109, 2,736,003, 2,757,430 and French Patent No. 2,364,946). .

In summary, it is not known that a thermoplastic elastomer in which the formation of the physical crosslinking would be the consequence of the looping of the molecular chain and the various phases. Further, there is no known thermoplastic elastomer in which amorphous polyolefin is the main constituent, not crystalline polyolefin.

In many cases, the purpose of producing partially cured polyolefin blends is to increase the cold and impact resistance of polypropylene.

The preparation of 189,266 additives (U.S. Patent Nos. 3,806,558 and Japanese Patent Nos. 80,804,450 and 80,106,250). Both crosslinked and slightly crosslinked rubber additives are used to increase the impact resistance of polypropylene. According to some, the use of the latter is more favorable due to the increased impact resistance and lower sensitivity to processing conditions [K. C. Dao: J. Appl. Polytn. Sci., 27 (12), 4799 (1982)], according to other authors, it has the opposite effect, since the melt viscosity of the additive increases, leading to a coarser distribution within the isotactic polypropylene matrix, which results in a decrease in impact resistance [J . Karger-Kocsis, V.N. Kuleznev: Polymer 23 (5), 699 (1982) and J. Karger-Kocsis, A. Kalló,

V. N. Kuleznev: ibid. (Press)]. To date, no thermoplastic elastomer having a melt viscosity close to or less than the isotactic polypropylene to be modified has been prepared by blending. Diluted oil extended dilution types have been marketed to reduce the melt viscosity of the thermoplastic elastomer used as the impact-enhancing additive but have not been used as such additive [J. Karger-Kocsis, Z. Balajthy, L. Kollár: Kuhststoffe (in press)]. The occasional cross-linking of the additive used to increase the impact resistance of polypropylene is supposed to influence its modulus of elasticity (E modulus), which plays an important role in triggering energy absorption processes. The dynamic modulus of elasticity of the rubber additive can reach 30% of its matrix and is advantageous if its numerical value is elongation-dependent, i.e. its starting value is low, since it increases the efficiency of stress collection and reduces [G. H. Michler, Plaste und Kautschuk 26 (12), 680 (1979). To date, such an additive for impact resistance has not yet been produced.

Impact-enhancing additives are material-specific, meaning that there is little known additive that can be used to modify polymers other than polypropylene. The polystyrene impact enhancement is mainly based on butadiene / styrene-based thermoplastic elastomers, while in the case of PVC ethylene / vinyl acetate, methacrylate / butadiene / styrene-based rubbers and chlorinated polyethylene are used.

They are not used to form the thermoplastic atactic polypropylene elastomer, as this material can only play a role as a "soft" phase is set and that only a limited extent, since _Tg is in the vicinity of 0 ° C, i.e. already behaved "hard" phase below that temperature. It is also known that rubber mixtures containing more than 33.3% by weight of atactic polypropylene cannot be vulcanised (Italian Patent No. 770,084).

However, the use of atactic polypropylene with various thermoplastic elastomers is known (e.g., butadiene / styrene-based block copolymers, Japanese Patent Publication No. 82,59,745). The use of atactic polypropylene in combination with a thermoplastic amorphous elastomer is sometimes intended to produce a melt sealant (French Patent No. 2,464,138), although for this purpose atactic polypropylene bulk compositions (French Patent No. 2,262,081) are also prepared. Hot sealants containing atactic polypropylene have acceptable physical-mechanical properties, since atactic polypropylene has a strength of 0.3 MPa and an elongation at break of less than 20% only when the rubber or elastomer content is high, generally above 50% by weight. Their design has been complicated by the use of specially designed mixing devices with a discharge screw, due to the high stickiness of the melt of atactic polypropylene.

The source of many difficulties with thermoplastic polymers is that the carrier material of the masterbatch used for their addition is not sufficiently compatible with the material to be modified, or has low filler capacity, possibly aging resistance, etc. For polyolefins, polyethylenes, polypropylene, ethylene / vinyl acetate copolymers are mainly used for this purpose. Although atactic polypropylene is used in some applications to replace it (eg as a binder for a pigment masterbatch, German Patent Publication No. 2,713,708), its presence in the matrix is not desirable because it causes deterioration of the physical-mechanical properties and enhances sensitivity. Anyway, due to its chemical composition due to the chemical structure of atactic polypropylene, it can only be a binder for polyolefin masterbatches. There is no known master blend which has other technical requirements than high filler [e.g. shock resistance enhancement, filler or reinforcement distribution, filler or reinforcing material compatibility ("olefilization", etc.), which is compatible with and can be made with a variety of chemically structured polymers.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a new type of thermoplastic elastomer which is inexpensive in the dynamic vulcanization of an atactic polypropylene based mixture by overcoming the above disadvantages and the disadvantages of the prior art.

It is a further object of the present invention to provide a thermoplastic elastomer which can be formulated in the form of granules to modify one or more polymers (polypropylene, polystyrene, PVC, styrene copolymers, poly (phenylene oxide), etc.) as an impact additive. , which can be used to fill fillers, reinforcing agents, pigments, dyes, lubricants, stabilizers, other processing and auxiliary materials, etc. for a wide variety of user needs. or a mixture of plastics and / or rubber masterbatches or mixtures thereof.

Finally, it is an object of the present invention to provide a hot-melt adhesive and sealant composition of increased strength and tensile strength, particularly for construction applications.

The invention is based on the discovery that it has a tensile strength of greater than 0.4 MPa and 50%. greater elongation at break and greater than 50% by weight3

189,266 more gélhányadú thermoplastic elastomer, and elastomeric material can be prepared, where 35 to 85 parts by weight of atactic polypropylene, of which at least half amount of 5xl0 larger x KP at more than ^three numerical (M _n) and 8 parts by weight of (M _m) of average molecular weight, 65 to 15 parts by weight of rubber - occasionally free-radical monomers polymerized, thermal decomposing peroxides, fillers, reinforcing agents, plasticizers, pigments, polymers, thermoplastic elastomers, stabilizers, lubricants, and other plastics and / or rubber additives known in the art using a known vulcanisation additive, it is dynamically vulcanized and then granulated, extruded into endless strips of various cross sections or otherwise packaged.

The present invention is further based on the discovery that the aforesaid thermoplastic elastomer can be made compatible with a variety of thermoplastic polymers by a suitable choice of the rubber (s) to be vulcanized and the monomer which may be used for grafting and thus be used as an impact additive.

The present invention is further based on the discovery that the dynamically vulcanized thermoplastic elastomer has a high filler capacity, which makes it suitable for use as a carrier and binder for plastics and / or rubber masterbatches.

Finally, the present invention is based on the discovery that the thermoplastic elastomer so produced can be made of high strength, tensile elastic sealants and adhesives, possibly in different cross-sections and endless forms.

These findings are surprising to the person skilled in the art, as it is not expected in the prior art to produce a thermoplastic elastomer blend that does not contain a "hard" phase polymer, and it is also surprising that a rubber blend containing more than 35 parts by weight of atactic polypropylene it can be vulcanized at all.

It is also surprising that the thermoplastic elastomeric polymers thus produced can be used to increase the impact resistance of certain thermoplastic polymers, and moreover, certain types of polymers can be used. Because of the cross-linking nature of the rubber-forming agent and the high melt viscosity of the thermoplastic elastomer thus obtained, mixing and distribution difficulties would be expected which would impair the physical-mechanical and impact properties. It is also not expected that the produced thermoplastic elastomer will simultaneously serve to increase the toughness of several polymers with very different chemical structures. Speaks against the use of impact-resistant additive is that the atactic pofipropilén T _g is high, and the way that the shear modulus of the additive requirements seem to be insatiable. It is also surprising that due to the sticky nature of the obtained thermoplastic elastomer, the content of granular atactic polypropylene is not expected.

It is also surprising that high filler content does not affect dynamic vulcanization.

In the case of a highly charged system, it would be expected that the vulcanizer would be ineffective and that the uptake of the finished thermoplastic elastomer would be limited due to the crosslinking of the rubber.

It is also surprising that the thermoplastic elastomer produced by dynamic vulcanization retains its melt-stick adhesion, and can be influenced in any direction, since it would be expected that this adhesion would be lost after vulcanization.

According to the above method of the present invention therefore thermosetting elastomer and elastomeric material thereof, which consists in 35-85, preferably 50-80, preferably 60-80 parts by weight, preferably in an amount of at least half of the Mn _of> 10 5χ ³ and M _m> 8x10 * average molecular weight atactic polypropylene

65 to 15, preferably 20 to 50, preferably 20 to 40 parts by weight of rubber, optionally

0-20 parts by weight of monomer polymerizable by free radical mechanism,

0-5 parts by weight of peroxide decomposed by heat,

0-300 parts by weight of filler, reinforcement, plasticizer, pigment, crystal, nucleating additive, other polymer, thermoplastic elastomer, liquid elastomer, light, heat stabilizer, lubricant and other known plastic and / or rubber auxiliaries or mixtures thereof using vulcanisation additives known per se, under dynamic conditions, and then granulated, extruded into an endless strip of various cross-sections or otherwise packaged.

According to the invention, the rubber constituents are preferably ethylene / propylene based (EPM) and ethylene / propylene / diene based (EPDM), butadiene / styrene based (SBR) rubber, butyl rubber (IIR), acrylonitrile / butadiene based rubber (NBR), polycarbonate (CR).

Styrene and its derivatives, vinyl chloride, vipsilanes and silane compounds are preferably used as the grafting monomer.

Peroxide constituents include dicumyl peroxide, 1,3-bis (tert-butyl peroxyisopropyl) benzene, tert-butyl rubber peroxide, butyl 4,4-bis (tert-butyl peroxide) valerate, 2,5-dimethyl -2.5 (di-tert-butyl peroxy) hexane, di-tert-butyl peroxide is preferred.

Preferred fillers are carbon black, chalk, limestone flour, aerosil, dolomite flour, wood flour, zeolite, quartz sand, barite, talc, rubber flour.

Preferred reinforcing materials for the present invention are glass fibers, beads, spheres, carbon fibers, leather fibers, man-made fibers, asbestos.

Other polymers which may be used are crystalline polyolefins, polystyrene, ABS, styrene copolymers, polymer waxes, ethylene / vinyl acetate, resins, PVC, homogenous or mixed waste of thermoplastic materials, but also raw materials of the cross-linking composition according to the invention.

The main advantages of the process according to the invention are as follows:

189,266

- allows for the preparation of a thermoplastic elastomer other than those previously known,

The thermoplastic elastomer according to the invention is inexpensive to form because, on the one hand, it is made by mixing, and, on the other hand, it is a by-product of production (atactic polypropylene). The thermoplastic elastomer may include other plastics and rubber waste, scrap,

- the thermoplastic elastomeric granules of the present invention can be formulated and used as impact-enhancing additives for the thermoplastic polymers,

- the process according to the invention can also produce impact-enhancing additives which can be used simultaneously to modify several polymers with very different chemical structures (eg polypropylene and polystyrene),

- the melt viscosity of the thermoplastic elastomer according to the invention does not differ significantly from that of the polymer to be modified, i.e. it has better processability, finer distribution in the given system and, consequently, a greater impact resistance enhancement than previously known,

- the compatibility of the thermoplastic elastomer produced by the process of the invention with the thermoplastic polymers can be adjusted, designed by grafting with a suitable monomer during mixing,

- due to its high filler uptake and controllable compatibility with the thermoplastic elastomer produced by the process, it can be a binder, carrier for plastics and rubber masterbatches,

- the process according to the invention provides the possibility to form reinforced filled systems with greater compatibility with the polymer matrix by suitable surface treatment, "finishing", "oleophilization" of the reinforcing material or filler,

- melt sealing strips of various cross-sections can be extruded from the thermoplastic elastomer produced according to the invention,

- the thermoplastic elastomer produced by the process of the invention can also be used as a hot sealant and adhesive in the latter case for a wide variety of substrates,

- the thermoplastic elastomer produced by the process according to the invention can be adjusted within a wide range of physico-mechanical and rheological properties according to the requirements of the particular application and processing,

- the thermoplastic elastomer of the present invention extends the range of thermoplastic elastomers,

- the environmental problems caused by depositing atactic polypropylene in landfills can be eliminated using the process of the invention.

The main advantages of the process according to the invention are illustrated by the following examples:

Example 1

In a Werner-Pfleiderer GK 4SU type 1 dm ³ internal mixer, the following composition was homogenized and vulcanized at 160 ° C at min ^-1 kneading speed for 15 minutes:

250 g of butyl rubber (Essobutyl 268, Exxon

Chemicals Co.), ⁵ g ZnO 15 g polychloroprene (Neoprene WRT, Du Pont Co.), g PVC waste, g alkylphenol / formaldehyde resin (Rousse ¹⁰ 75 Lot 00, Neville Co.),

165 g of liquid pilisobutylene (Oppanol B-3 from BASF),

165 g of bitumen bit-90,

420 g of atactic polypropylene (product K 501 of Tisza Chemical Kom ¹⁵ bininate, M _n = 5.1 x 10 ³ ;

M _m = 8.4 x 10 ⁴ ).

The resulting thermoplastic elastomer has tensile strength and elongation at break according to DIN 53 455. determined according to Standard ₂₀ (test piece 4, speed VI ^υ ), respectively, 0.5 MPa and 50%. The thermoplastic elastomer is compressed to 200 ° C for pre-degreased aluminum foils are then cut to 25 mm wide strips of the value of 90 ° tear strength was determined at 200 mm / min from ⁵ ° nor deformation velocity. Composition tear strength of example 1 to 20 N / 25 mm, and measured in a similar mixture conditions without vulcanization auxiliaries between 5, whereas only a liquid rubber, bitumen and atactic polymer ³⁰ Propylene is 6 N / 25 mm had one comprising.

Example 2 35

Apparatus mentioned in Example 1 'inch 300 g of SBR rubbers (SZKSZ ARKP-30 / N. Soviet product) was mixed with addition gyúrókar rpm 25 min 5 min at 150'C was added ⁰ 900 g of atactic polypropylene (a TVK In the manufacture of Tipplen's K 823, the by-product is K 801, Mn = 6.5 x 10 ³ , Mm = 1.7 x 10 ⁵ ) and stirred for 5 minutes. Was then treated with N-cyclohexyl-2-benzothiazole-sulfonamide 4.5 g of ⁵ fenamidone (Santocure, Monsanto Co.),

6.6 g of sulfur and 15 g of ZnO were added and the mixture was vulcanized under dynamic conditions for 12 minutes. The obtained thermoplastic elastomer had a tensile strength and a tensile elongation of 0.58 MPa ⁵⁰ and 125%, respectively, and the elongation after elastic recovery at 100% was 5.2%. The thermoplastic elastomer 50 and 100 The stress measured at% elongations was the same as the tensile strength. A 45 Shore A ^b s outcome a product with a glass transition temperature of - 33'C has a complex dynamic elastic -20'C for 9.1 x 10 ^7, and 10 had a 4.5 χ ⁶ PANA Du Pont made at 0 ° C 981 Measured on a Dynamic Mechanical Analyzer. Initial characteristics of atactic polypropylene were as follows: - 15 'C, 1.9 χ 10 ® Pa, and not measurable at' C '.

The granulated thermoplastic elastomer of Example 2 was 10% by weight of impact-resistant polystyrene (Soviet product UPM 612 L) and polypropylene 5.

189,266 homopolymers (Tipplen H 523 from Tisza Chemical Plant) were stirred at 190 ° C for 10 minutes with stirring in the above apparatus. The impact resistance of the modified mixtures as well as of the starting polymers on the grooved specimens is determined according to DIN 53 453. standard. The initial impact-resistant polystyrene - measured at 20.0 and 23 ° C - 6.6, 6.6 and 7.2 µg, respectively, contains 10% by weight of the exemplary thermoplastic elastomer, 7.9, 7.7 and 8.5 kJ / m ² . These results are the same as those obtained by incorporating 10% by weight of a thermoplastic butadiene / styrene block copolymer (Solprene 416 from Phillips Petroleum) into the same matrix. The impact resistance of Tipple H 523 at 20 and 23 ° C is 5.0 and 12.8 kJ / m ² , respectively, when added with the thermoplastic elastomer of Example 2 to 6.8 and 19.5 kJ / m ^{2, respectively} . grow. This increase in impact resistance corresponds to that obtained by blending 10% by weight of EPDM or thermoplastic polyolefin elastomer (Buna AP 447 or Vestopren TP 2047; manufactured by Hüls).

Example 3

Equipment referred to in Example 1. 300 g of natural rubber (Smoked 1) 's for 5 minutes under _these 30min'- speed C was added subsequently mixed with 150,900 g of atactic polypropylene (of the same characteristics as in Example I 2), and the mixture was homogenized for 5 minutes . Subsequently, 0.9 g of sulfur, 15 g of ZnO, 3 g of tetramethylthiuram disulfide and 6 g of N-cyclohexyl-2-benzothiazole sulfenamide (product of Santocure, Monsanto) were added and stirred for another 12 minutes. The thermoplastic elastomer produced in this dynamic vulcanization has a tensile strength of 0.69 MPa, a tensile elongation of over 250%, a tensile strength of 50 and 100%, a glass transition temperature of -45 ° C, and a 100% elongation after recovery. Permanent deformation measured during 6.9%. Dynamic elastic modulus of thermoplastic elastomeric complex

5.2 x ^{10 8} at 40 ° C and 7 x ^{10 7} Pa at -20 ° C.

The thermoplastic elastomer of Example 3 was also tested to increase the impact resistance of impact-resistant polystyrene (same as Example 2) and polypropylene copolymer by 10% by weight. DIN 53 453 grooved impact strength at 20 and 23 'C - 8.0 and 9.3 kJ / m ² for impact-resistant polystyrene and 11.6 kJ / m ² for polypropylene copolymer, respectively . The starting polypropylene copolymer (Tipplen K 523, product of the Tisza Chemical Plant) had a value of 7.5 kJ / m ² at -20 ° C and 29 kJ / 23 ° C. In the case of the polypropylene copolymer, the increase in the application of the thermoplastic elastomer of Example 3 at 10 wt.

Example 4

In the mixing apparatus mentioned in Example 1, 645 g of a mixture of non-liberated crosslinking agents were also added, which was ca. 30% by weight of rubber, polychloroprene, polybutadiene and SBR in a ratio of 1: 1: 2, ca. 35% by weight of carbon black, 10% by weight of kaolin, ca. 10% by weight of plasticizer and ca. It was mixed with 15% cross-linking and other additives in the presence of 6.5 g of N-cyclohexylthiophthalimide (Santograd PVI, product of Monsanto) at 150 ° C for 5 minutes, followed by the addition of 300 g of atactic polypropylene (same characteristics as in Example 1). in Example I) and 55 g of less ömledékviszkozitású atactic polypropylene (H 701, product of TVK, m '= ³ 3,8xl0, m _m = 4.1 x 10 ⁴⁾ and stirred for another 3 minutes. Thereafter, 400 g of hot melt adhesive containing 10: 10: 5: 75 polyisobutylene (same as Example 1), bitumen Β-200, pine resin and atactic polypropylene (same as Example 1) was added. Stir for 10 minutes. The resulting thermoplastic elastomer can be used as a melt sealant. Tensile strength 0.64 MPa, elongation at break 50%, glass transition temperature - 32 'C. It has an adhesive tear strength of 7.9 N / 25 mm between aluminum / aluminum foils. The thermoplastic elastomer strip of Example 4 was extruded into a strip of 20 x 4 mm ² , which was used to seal joints in asphalt pavements. After a winter, the application test was positive.

Example 5

100-100 g of plant rubber (identical to Example 3) and SBR (identical to Example 2) were kneaded at 150 ° C for 6 minutes in the mixer mentioned in Example 1 and then mixed with 500 g of K 801 and 250 g. K 501 atactic polypropylene and stirred for another 5 minutes. Thereafter, 50 g of tar, 50 g of butadiene / styrene block copolymer (Solprene 415 from Phillips Petroleum), 50 g of low-density polyethylene waste, 25 g of dolomite flour and 25 g of mordenite were added and homogenized for an additional 5 minutes. After adding 3 g of t-Santocure, as 5.5 g and 10 g of ZnO, and 60 min ^-1 5 rpm, and was then mixed for another 5 min 30 min w ^_l speed. The resulting melt adhesive and sealant composition can be used as a thermoplastic elastomer having a tensile strength of 0.42 MPa, a tensile elongation of 50%, a tear strength of 17 N / 25 mm between aluminum / aluminum foils, and a glass transition temperature of -40 ° C.

Example 6

In the mixing apparatus mentioned in Example 1, 480 g of EPDM (product of Buna AP451, Hüls) was kneaded at 160 ° C for 6 minutes and then added.

189,266

600 g Κ 501 and 120 g Η 701 of atactic polypropylene and stirred for another 6 min. Subsequently, 15.8 g of Devulk EG 28, 2.4 g of 2-mercaptobenzothiazole, 4.3 g of sulfur and 24 g of ZnO were added and stirred for another 10 minutes. The obtained thermoplastic elastomer had a tensile strength of 1.36 MPa, a tensile elongation of 210%, and a tensile strength values of 50, 100 and 200% of 0.95 and 1.04 respectively.

1.29 MPa. The thermoplastic elastomer of Example 6, when mixed with 10% by weight of the polypropylene homopolymer described in Example ^2, was measured at -20 ° C to 7.6 and at 23 ° C to 25 kJ / m ² .

Example 7

Each was prepared as in Example 6, but after 10 minutes of dynamic vulcanization, 15 cm ^{3 of} methyl vinyl dichlorosilane oligomer and 0.1 g of dicumyl peroxide were added. The resulting thermoplastic elastomer had a glass transition temperature of -40 ° C. The product obtained was tested as a master blend of hard PVC granules for impact resistance. The thermoplastic elastomer granulate of Example 7 was mixed with 15% by weight of the hard PVC granulate (Selfgrovil KE 109, product of Borsodi Chemical Plant) just prior to extrusion. The impact resistance of the extruded articles produced was the same as that obtained by using 30% by weight of a PVC / chlorinated polyethylene-based masterbatch (Self-Grovil Hl 50/64, product of Borsodi Chemical Plant) as an impact additive.

Example 8

300 g of atactic polypropylene (identical to Example 1) was added to 300 g of SBR (USSR 30 ARKP / N, Soviet production), which was stirred for 6 minutes at 160 ° C in the apparatus mentioned in Example 1, and stirred for another 4 minutes. . Then 800 g of TiO ₂ were added and stirred for 5 minutes, followed by 6.6 g of sulfur, 4.5 g of N-cyclohexyl-2-benzothiazole sulfenamide (product of Santocure, Monsanto) and 15 g of ZnO and more. After stirring for 10 minutes, 20 g of calcium stearate, 5 g of phenolic antioxidant (Ongrostab 2246, product of Borsodi Chemical Plant) and 5 g of light stabilizer (Ongrostab HOB, product of Borsodi Chemical Plant) were added and homogenized for 5 minutes. The resulting thermoplastic elastomer was used as a master coloring compound in the manufacture of polyethylene and polypropylene products. Using the thermoplastic elastomer described in Example 8 at 4% by weight, achieved the same opacity as with conventional masterbatches. A further advantage of its use was that its incorporation reduced the tendency of high density polyethylene to stress corrosion (increased by about 10% the time required for fracture of the specimens) and significantly improved the impact resistance of the polypropylene homo- and copolymers.

Example 9

In the apparatus described in Example 1, 200 g of SBR (identical to Example 8) was stirred at 140 ° C for 5 minutes, then 200 g of K 501 atactic polypropylene and 600 g of K 801 atactic polypropylene were added and homogenized for another 6 minutes. Thereafter, 150 g of 3 mm glass fiber (Silone 400 P 3, product of Potters-Ballotini) and 150 g of glass sphere (CP01 3000, product of Potters-Ballotini) were added, and after stirring for 2 minutes, 20 cm ^{3 of} styrene, 0.5 g 3-bis (tert-butyl peroxyisopropyl) benzene (Perkadox 14/40, product of Noury) and 5 g of 3- (trimethoxysilyl) -1-propanamine (A-1100, product of Union Carbide) and stir for minutes. Subsequently, 4.4 g of sulfur, 15 g of ZnO and 3 g of Santocure were mixed and the mixture was vulcanized at 140 ° C for 15 minutes at 40 min 'kneading speed.

The resulting thermoplastic elastomer was added to the impact-resistant polystyrene mentioned in Example 2 at 10% by weight. The resultant polymer blend had a score of 8.7, 9.0 and 11.0 kJ / m ² , respectively, on the grooved specimens at -20, 0 and 23 ° C.

Example 10

340 g of EPDM (product of Dutral Square 038 EP, Montedison) was stirred for 6 minutes at 140 ° C, then 860 g of atactic polypropylene (identical to Example 1) was added and stirred for another 4 minutes on the equipment of Example 1. Then added to 15 g of hydrogen peroxide (same as in Example I 9), 15 g of ZnO, 5 g of NaA molecular sieves (Baylith T Pulver, Bayer Co.) and 5 g of perlite and this mixture for 12 min 30min '' - _inch gyúrókar rpm We cured. The resulting thermoplastic elastomer has a tensile strength of 0.87 MPa, a tensile elongation of 400%, and a tensile strength of 100, 200 and 300% of 0.45, 0.47 and 0.62 MPa. The resulting thermoplastic elastomer was used to modify the impact resistant polystyrene and polypropylene homopolymer of Example 2 at 10% by weight. The impact resistance at -20 ° C was 10.5 kJ / m ² for polystyrene.

Example 77

650 g of polychloroprene (Baypren 610, product of Bayer) and 350 g of atactic polypropylene of Example 1 were homogenized for 10 minutes at 160 ° C in the apparatus of Example 1, and then 37.5 g of ZnO, 30 g of MgO were added. and 8 g of ZnA molecular sieve, and cured for another 15 min. The resulting joint sealing tape made of a thermoplastic elastomer complied with the relevant German Federal Government Regulations [U. Hansen, P. Weyer, Strasse und Autobahn 33 (1), 20 (1982)].

189,266

Example 12

300 g of polypropylene copolymer (Tripplen K 523, manufactured by Tisza Chemical Plant), 100 g of high density and 100 g of low density polyethylene waste were kneaded at 180 ° C for 5 minutes, followed by the addition of 300 g of SBR. (identical to Example 8) and stirred for 4 minutes, then 700 g of atactic polypropylene (identical to Example 2) were added and stirred for another 5 minutes. Subsequently, 7 g of sulfur, 17 g of ZnO, 5 g of Santocure were added and the ^mixture was cured at 50 rpm for 10 minutes. Then bring it. 20 g of microcrystalline polyethylene wax and 20 cm ^{3 of} silicone oil (NM-1-1000, product of Nünchritzer) were obtained. The resulting thermoplastic elastomer was tested as an impact additive for polypropylene, polystyrene and poly (phenylene oxide) and found to be as effective as the copolymers of the currently available butadiene / styrene block.

Claims (1)

A patent claim A process for a thermoplastic elastomer, and the elastomeric material thereof, characterized in that 35 to 85 parts by weight, preferably 50-80 parts by weight, preferably 60-80 parts by weight, in part, preferably half the amount of at least M _n> 5 x 10 ³ M and _m> 8x10 * average molecular weight atactic polypropylene, 65 to 15 parts, preferably 20 to 50 parts, preferably 20 to 40 parts by weight of rubber, optionally 0 to 20 parts by monomer and / or oligomer to be polymerized or grafted according to the free radical mechanism; 0-5 parts by weight of heat when decomposing peroxide pouch _15; 0-300 parts by weight of a filler, reinforcing agent, plasticizer, pigment, crystal nucleating additive, other polymer, thermoplastic elastomer, liquid elastomer, light, heat stabilizer, lubricant or other known plastic and / or 2q or rubber auxiliary, or mixtures thereof , with vulcanisation additives known per se, are dynamically vulcanized and subsequently granulated, ext2θ, or otherwise packaged into an endless strip of various cross-sections.