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    • 专利摘要:
    PRODUCTION OF EXPANDED PELLETS The invention relates to a process for the production of expanded pellets from a thermoplastic elastomer having an elongation at break greater than 100% measured according to DIN EN 150 527-2, said process comprising the steps of : (a) pressing a melted polymer comprising a blowing agent through a perforated disc (18) controlled at a temperature between 150 ° C and 280 ° C and in a pelletizing chamber (26), (b) using a cutting device (20) to fragment the melted polymer pressed through the perforated disc (18) into individual expanding pellets, (c) unload the pellets from the pelletizing chamber (26) using a liquid stream (36), in which the blowing agent comprises CO2 or N2 or a combination of CO2 and N2 and the amount of blowing agent in the melted polymer comprising a blowing agent is in the range of 0.5% to 2.5% by weight and where the pelletizing chamber (26) is crossed by a liquid stream that is controlled at a temperature between 5 ° C and 90 ° C and whose pressure is from 0.1 bar to 20 bar above ambient pressure, the pressure and temperature for the liquid in the pelletizing chamber (26) and also the temperature for the disc (...).
    公开号:BR112015031074B1
    申请号:R112015031074-5
    申请日:2014-06-11
    公开日:2020-12-29
    发明作者:Christian DAESCHLEIN；Peter Gutmann；Frank Prissok；Uwe Keppeler；Jürgen Ahlers
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [0001] This invention relates to a process for producing expanded pellets from a thermoplastic elastomer having an elongation at break greater than 100% measured according to DIN EN ISO 527-2. Expanded pellets of thermoplastic elastomers, having an elongation at break greater than 100% measured according to DIN EN ISO 527-2, have elastic and tribological properties and are thus useful in a wide variety of applications. Examples of uses for corresponding expanded pellets include reusable gymnastics mats, body protectors, trim elements in automobile construction, sound and vibration absorbers, packaging or shoe soles. High elasticity and good homogeneity on the part of the pellets are of decisive importance for all these sectors.
    [0002] Foamed materials, including granule foams, in particular, have long been known and have been widely described in the literature, for example, in Ullmann's "Enzyklopadie der technischem Chemie", 4th edition, volume 20, p. 416 ff.
    [0003] WO 2007/082838 discloses a process for the production of expanded thermoplastic polyurethane comprising a blowing agent. A first step in the process comprises extruding a thermoplastic polyurethane into pellets. The pellets are impregnated with a blowing agent in an aqueous suspension under pressure in a second stage and expanded in a third stage. In an additional mode of the process, the thermoplastic polyurethane is melted in an extruder together with a blowing agent and the melted material is pelletized without a device to prevent foaming. Volatile organic compounds are used as expansion agents in production through extrusion.
    [0004] EP-A 0 664 197 discloses the production of expanded thermoplastic elastomers using water as a blowing agent in an effort to avoid organic blowing agents. An alternative process for producing thermoplastic elastomer foams by using carbon dioxide and nitrogen as blowing agents is known, for example, from WO 2004/018551. An additional process for producing expanded thermoplastic elastomers that is repeated for the foam production process described in WO 2004/018551 is also disclosed in WO 2007/044123.
    [0005] None of the documents known in the prior art, however, discloses that the described process can also be used to produce expanded pellets having an uninterrupted film.
    [0006] The use of an extrusion process to produce expanded TPU pellets allows continuous production and, consequently, rapid processing of a variety of hardnesses and also the rapid change between additional properties, for example, the color of the expanded granules produced.
    [0007] There is still a problem with the direct production of expanded pellets by means of extrusion, in which the granules expand without an uninterrupted film formation in the process and the expanded granules collapse, making it impossible to produce apparent low-density granules. It is similarly disadvantageous that the blowing agents used are flammable and thus difficult to process due to an ever-present risk of explosion. In addition, the expanded pellets produced must be stored until the flammable blowing agent used has volatilized before they can be shipped out.
    [0008] It is an objective of the present invention to provide a process for the production of expanded pellets from a thermoplastic elastomer having an elongation at break greater than 100% measured according to DIN EN ISO 527-2 which has an uninterrupted film, without the disadvantages known from the prior art. The pellets produced using the process will have a homogeneous shape, a homogeneous cell structure and very low apparent densities. At the same time, a wide range of various densities will be possible with the process used. In addition, the use of organic blowing agents should be avoided.
    [0009] This objective is achieved by a process for the production of expanded pellets from a thermoplastic elastomer having an elongation at break greater than 100% measured according to DIN EN ISO 527-2, said process comprising the steps of: (a ) pressing a melted polymer comprising a blowing agent through a perforated disc controlled at a temperature between 150 ° C and 280 ° C and in a pelletizing chamber, (b) using a cutting device to break up the melted polymer pressed through the temperature-controlled perforated disc on individual expanding pellets, (c) unloading pellets from the pelletizing chamber using a liquid stream, where the blowing agent comprises CO2 or N2 or a combination of CO2 and N2 and the amount of blowing agent expansion in the melted polymer comprising a blowing agent is in the range of 0.5% to 2.5% by weight and in which the pelletizing chamber is traversed by a stream of liquid which is controlled at a temperature between 5 ° C and 90 ° C and whose pressure is 0.1 bar to 20 bar above ambient pressure, the pressure and temperature for the liquid in the pelletizing chamber and also the temperature for the perforated disc being chosen in such a way that the pellets are expanded in the liquid pressurized by the blowing agent they contain, in order to produce expanded pellets having an uninterrupted film.
    [0010] It was revealed that the lowest apparent densities are not obtained, as would be expected, in amounts of very high blowing agent, but that a blowing agent quantity of not more than 2.5% by weight, preferably not greater than 2% by weight and especially not more than 1.5% by weight lead to a particularly low bulk density. When the amount of blowing agent is less than 0.5% by weight, the bulk density also increases again. The respective mass fractions here are based on the total mass of melted polymer including blowing agent present therein.
    [0011] The ideal amount of blowing agent to be used depends on the thermoplastic elastomer used and the blowing agent composition, but it is always in the range between 0.5% and 2.5% by weight.
    [0012] The melted polymer mixed with a blowing agent and, optionally, additional mixing agents, is forced through the perforated disc in step (a) of the process. The production of the melted polymer comprising the blowing agent, and optionally additional mixing agents, is generally carried out using an extruder and / or a fusion pump. These devices are also used to generate the pressure required to press the melted polymer through the perforated disc. When an extruder, for example, a twin screw extruder, is used, the polymer is first plasticized and, optionally, mixed with auxiliary agents. During mixing, the material in the extruder is transported towards the temperature-controlled perforated disc. If the blowing agent was not introduced into the extruder from the beginning together with the polymer, it can be added to the polymer after the polymer has traveled part of the distance in the extruder. The blowing agent and the polymer mix as they travel the remaining distance in the extruder. In the process, the melted material is brought to the temperature required for subsequent pelletizing. The pressure required to press the melted material through the perforated disc can be applied by a fusion pump, for example. Alternatively, the required pressure is generated by the appropriate geometry of the extruder and in particular, the screw of the extruder. The pressure required for pelletizing and the temperature required for the melted material are dependent on the polymer used and also the auxiliary agents used and the blowing agent used and are additionally dependent on the mixing ratio between the components. It is through the temperature-controlled perforated disc that the melted polymer passes through the pelletizing chamber. The pelletizing chamber is passed through a stream of a temperature-controlled liquid, whose pressure is 0.1 bar to 20 bar above ambient pressure. The pressure of the liquid flowing through the pelletizing chamber is preferably 0.1 to 5 bar above ambient pressure.
    [0013] In the pelletizing chamber, the polymer forced through the temperature-controlled perforated disc is molded into filaments that a cutting device fragments into individual expanding pellets. The cutting device can be incorporated as a fast turning blade, for example. The shape of the resulting pellets is dependent on the shape and size of the openings in the perforated disc and also on the pressure under which the molten material is forced through the holes in the perforated disc and the speed of the cutting device. It is preferred for the pressure exerting force, the speed of the cutting device and the size of the holes in the perforated disc to be chosen, such that the shape of the pellets is substantially spherical or elliptical.
    [0014] In the last stage of the process, pellets are discharged from the pelletizing chamber by the temperature-controlled liquid that flows through the pelleting chamber. The choice of pressure and temperature for the temperature controlled liquid is such that the polymer filaments / pellets are expanded by the blowing agent they contain in a controlled manner and an uninterrupted film is produced on the surface of the pellets.
    [0015] The pellets flow together with the temperature-controlled liquid in a dryer where the pellets are separated from the liquid. The final expanded pellets are collected in a container, while the liquid is filtered and returned to the pelletizing chamber by means of a pump.
    [0016] Pelletization in a pressurized liquid, where the temperature of the liquid is under control, prevents the melted polymer comprising a blowing agent from undergoing an uncontrolled expansion in which no formation of an uninterrupted film can occur. Such granules would initially have a low bulk density, but would quickly quickly collapse again. The result would be non-homogeneous granules of high apparent density and lower elasticity. The process of the present invention slows the expansion of the pellets in a controlled manner to produce structured particles that have an uninterrupted film and a cell structure inside, where the cell size is low on the surface and increases towards the center. The size of the cells in the center is preferably less than 250 μm. The apparent density of the expanded pellets is not more than 250 g / l. Maximum expansion for the individual expanded pellets is preferably in the range of 2 to 15 mm, in particular in the range of 5 to 12 mm, while the mass of an individual pellet is between 2 and 40 mg, in particular between 5 and 35 mg.
    [0017] Pellet expansion is policed by controlling the pressure and temperature of the temperature-controlled liquid in the pelletizing chamber and also by controlling the temperature of the perforated disc. When the pellets expand very quickly and / or in an uncontrolled manner, meaning that no uninterrupted film is formed, the pressure of the liquid in the pelletizing chamber is high and the temperature of the temperature-controlled liquid in the pelleting chamber is lowered. The increase in pressure of the temperature-controlled liquid surrounding the pellets neutralizes the expansion effect of the blowing agent and breaks the expansion of the pellets. Reducing the temperature of the temperature-controlled liquid in the pelletizing chamber causes a thicker film on the granules and thus offers greater resistance to expansion. When the temperature-controlled liquid is too high a pressure or too low a temperature compared to the blowing agent used, expansion of the pellets can be excessively prevented or even completely stopped, producing pellets where the bulk density is too high. In this case, the pressure of the temperature-controlled liquid in the pelletizing chamber is reduced and / or the temperature of the temperature-controlled liquid is high.
    [0018] As an addition or alternative to adjust the pressure and / or temperature of the temperature controlled liquid in the pelletizing chamber, the expansion of the pellets can also be influenced by the temperature of the temperature controlled perforated disc. Lowering the temperature of the temperature-controlled perforated disc has the effect of releasing heat from the melted polymer more quickly into the environment. This promotes the formation of an uninterrupted film, which is a prerequisite for a stable foamed pellet. If the temperature of the temperature-controlled perforated disc and / or the liquid in the pelletizing chamber is too low, the melted polymer will cool very quickly and solidify before proper expansion can begin. Expansion of the pellet by the blowing agent it contains is thus severely prevented in order to form pellets having an excessively high bulk density. Therefore, the temperature of the temperature controlled liquid in the pelletizing chamber and / or the temperature of the temperature controlled perforated disc is high in such a case.
    [0019] In accordance with the invention, the temperature of the liquid in the pelletizing chamber is preferably between 5 ° C and 90 ° C so that the pellets can undergo a controlled expansion in which an uninterrupted foam film is formed. The temperature of the liquid is preferably between 10 ° C and 60 ° C and more preferably between 25 ° C and 45 ° C. According to the invention, the temperature of the temperature-controlled perforated disk is preferably between 150 ° C to 280 ° C, more preferably between 220 ° C and 260 ° C.
    [0020] Excessive temperature on the part of the perforated disc leads to a thin film on the surface of the granules and a subsequent collapse of the surface. Excessively low temperatures on the perforated disc reduce the degree of expansion and lead to thick, non-foam surfaces on the granules.
    [0021] Thermoplastic elastomers used for the production of expanded pellets in the form of the present invention include, for example, thermoplastic polyesterelastomers, for example, polyetheresters or polyesteresters, thermoplastic polyether copolamides, for example, polyether copolamides, or block copolymers styrene, for example, styrene-butadiene block copolymers.
    [0022] It has been found that for thermoplastic polyesterelastomers, for example, polyether and polyester, and for styrene block copolymers, for example, styrene-butadiene block copolymers, lower densities can be achieved when the amount of blowing agent is greater than 0.5% by weight and less than 1.5% by weight and the pressure of the temperature controlled liquid flowing through the pelletizing chamber is in the range of 0.1 to 2 bar above ambient pressure. For thermoplastic copolyamides, for example, polyether copolyamides, the amount of blowing agent is preferably greater than 1.5% by weight and less than 2.5% by weight and the pressure in the pelletizing chamber is preferably 5 to 20 bar above ambient pressure.
    [0023] The thermoplastic polyesters and polyesters in question are obtainable according to any method of common literature by esterification or transesterification of aromatic and aliphatic dicarboxylic acids of 4 to 20 carbon atoms and, respectively, esters of these with aliphatic and aromatic polyols and diols appropriate. Corresponding manufacturing methods are described, for example, in "Polymer Chemistry", Interscience Publ., New York, 1961, p. 111-127; Kunststoffhandbuch, volume VIII, C. Hanser Verlag, Munich 1973 and Journal of Polymer Science, part A1, 4, pages 1851-1859 (1966).
    [0024] Useful aromatic dicarboxylic acids include, for example, phthalic acid, isophthalic acid and terafthalic acid, respectively, esters thereof. Useful aliphatic dicarboxylic acids include, for example, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids as well as maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydrochloric acid and tetrahydrochloric acid. as unsaturated dicarboxylic acids.
    Useful diol components include, for example, diols of the general formula HO- (CH2) n-OH, where n is an integer from 2 to 20. Useful diols include, for example, ethylene glycol, 1,3-propanediol , 1,4-butanediol or 1,6-hexanediol.
    [0026] Transesterifiable polyetherols for the thermoplastic polyetherester are preferably those of the general formula HO- (CH2) nO- (CH2) m-OH, where neither are each, independently an integer between 2 and 20 enem can be the same or different .
    [0027] Unsaturated diols and polyetherols useful for producing the polyetherester include, for example, 1,4-butenediol and also polyetherols and diols comprising aromatic units.
    [0028] In addition to the recited carboxylic acids and esters thereof and also the recited alcohols, any additional common representatives of these classes of compounds can be used to provide the polyether and polyester esters used in the process of the present invention. The rigid phases of the block copolymers are usually formed of aromatic dicarboxylic acids and short chain diols, while the soft phases are formed from readily formed aliphatic bifunctional polyesters having a MW molecular weight between 500 and 3000 g / mol. The rigid and soft phases can be additionally coupled by means of reactive connectors, such as diisocyanates that react with terminal alcohol groups, for example.
    [0029] Thermoplastic polyetheramides useful for the process of the present invention are also obtained according to any known literature method by reaction of amines and carboxylic acids or esters thereof. Amines and / or carboxylic acids, in this case, additionally comprise ether units of the type R-O-R, where R is an aliphatic or aromatic organic radical. Monomers selected from the following classes of compounds are used, in general: - HOOC-R'-NH2, where R 'can be aromatic or aliphatic and preferably comprises ether units of the R-O-R type. R in it is an aliphatic or aromatic organic radical, - aromatic dicarboxylic acids, for example, phthalic acid, isophthalic acid and terephthalic acid or esters thereof and also aromatic dicarboxylic acids comprising ROR-type ether units, where R is an aliphatic or organic radical aromatic, - aliphatic dicarboxylic acids, for example, 1,4-cyclohexane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids and also maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids and also aliphatic dicarboxylic acids comprising any ROR-type ether units, where R is an aliphatic and / or aromatic organic radical, - diamines of the general formula H2N-R "-NH2, where R" can be aromatic and aliphatic and preferably comprises ether units of the type ROR and R is an organic radical al ifactic or aromatic, - lactams, for example, D-caprolactam, pyrrolidone or laurolactam and also - amino acids.
    [0030] In addition to the carboxylic acids and esters of these recites and also the recited amines, lactams and amino acids, any additional common representatives of these classes of compounds can be used to provide the polyetheramine used in the process of the present invention. Mixed products of polytetrahydrofuran and amide syntones are also known, which can be used in the same way.
    [0031] The thermoplastic elastomers of block copolymer structure which are used according to the present invention, preferably comprise vinilaromatics, butadiene and isoprene and also polyolefin and vinyl units, for example, ethylene, propylene and vinyl acetate units. Styrene-butadiene copolymers are preferred.
    [0032] Thermoplastic elastomers, used in accordance with the present invention, preferably have a Shore hardness in the range of A40 to D80. Particular preference is given to Shore hardness in the range A44 to D60, in particular in the range A65 to A99. Particular preference is given to Shore hardness in the range of A65 to A96. Shore hardnesses are determined according to DIN 53505. The melting point of the thermoplastic elastomers used in accordance with the present invention is preferably below 300 ° C, more preferably not more than 250 ° C and especially not more than 220 ° C. The elongation at break of the thermoplastic elastomers of the present invention is greater than 100% measured according to DIN EN ISO 527-2, preferably greater than 200%, additionally, preferably greater than 300% and particularly greater than 400%. In addition, the elongation at break is preferably at most 1000%, particularly at most 800%.
    [0033] The thermoplastic elastomers used in accordance with the present invention can be amorphous or partially crystalline.
    [0034] Expanded pellets obtained using the process of the present invention may include additional mixing agents, such as dyes, pigments, fillers, flame retardants, synergistic agents for flame retardants, antistatic agents, stabilizers, surfactants, plasticizers and infrared opacifiers in effective amounts.
    [0035] Infrared opacifiers suitable for reducing the radiative contribution to thermal conductivity include, for example, metallic oxides, non-metallic oxides, metallic powders, for example aluminum powders, carbon, for example carbon black, graphite or diamond, or organic dyes and pigment dyes. The use of infrared opacifiers is advantageous for high temperature applications, in particular. Carbon black, titanium dioxide, iron oxides or zirconium dioxide are particularly preferred for use as infrared opacifiers. The materials mentioned above can be used not only each on its own, but also in combination, that is, in the form of a mixture of two or more materials. Any fillers can be organic and / or inorganic.
    [0036] When fillers are understood, these are, for example, organic and inorganic powders of fibrous materials and also mixtures of these. Useful organic fillers include, for example, wood powder, starch, linen fibers, hemp fibers, ramie fibers, jute fibers, sisal fibers, cotton fibers, cellulose fibers or aramid fibers. Useful inorganic fillers include, for example, silicates, barite, glass spheres, zeolites, metals or metal oxides. Particular preference is given to the use of powdery inorganics, such as chalk, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder , Aerosil, clayey, mica or wollastonite or inorganic spherical or fibrous, for example, iron powder, glass spheres, glass fibers or carbon fibers. The average particle diameter or, in the case of fibrous fillers, the length of the fibers should be in the region of cell size or less. Preference is given to an average particle diameter or average fiber length in the range of 0.1 to 100 μm and, in particular, in the range of 1 to 50 μm. Preference is given to expandable thermoplastic elastomers that comprise a blowing agent and also between 5% and 80% by weight of organic and / or inorganic fillers, based on the total weight of the system comprising a blowing agent.
    [0037] Surfactant substances useful for inclusion in the thermoplastic molding composition include, for example, compounds that are used to increase homogenization of starting materials and may also be able to regulate cell structure. Suitable surfactant substances include, for example, emulsifiers, for example, sodium salts of castor oil sulfates or fatty acids, and also fatty acid salts with amines, for example, dimethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate , salts of sulfonic acids, for example, alkali metals or ammonium salts of dodecylbenzene or dinaftylmethanedisulfonic acid and ricinoleic acid; foam stabilizers, such as siloxane-oxalkylene interpolymers and other organosiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil esters or ricinoleic esters, sulphonated castor oil and peanut oil, and cell regulators, for example , paraffins, fatty alcohols and dimethylpolysiloxanes. Oligomeric polyacrylates having polyoxyalkylene and flouroalkane fractions as side groups are additionally useful for improving the emulsifying effect, cell structure and / or stabilization thereof. Surfactant substances are normally used in amounts of 0.01% to 5% by weight, based on the total weight of the system comprising blowing agent.
    Suitable flame retardants include, for example, tricresil phosphate, tris phosphate (2-chloro-ethyl), tris phosphate (2-chloropropyl), tris phosphate (1,3-dichloropropyl), tris phosphate (2,3-dibromopropyl) and tetrakis (2-chloroethyl) ethylene diphosphate. In addition to the halogen-substituted phosphates already mentioned, inorganic flame retardants comprising red phosphorus, hydrated aluminum oxide, antimony trioxide, arsenic trioxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives, for example, melamine or hair mixtures at least two flame retardants, for example, ammonium phosphate and melamine and also, optionally, expandable graphite and / or starch can also be used to impart flame retardancy to the foamed thermoplastic elastomers produced. In general, it will prove advantageous to use from 0% to 50% by weight and preferably from 5% to 25% by weight of flame retardant or flame retardant mixtures based on the total weight of the system comprising blowing agent.
    [0039] Before the melted polymer is pressed into the pelletizing chamber, it is mixed with the blowing agent CO2 or a mixture of CO2 and N2. A coexpansion agent can additionally be added to the melted polymer. Useful coexpansion agents include alkanes, such as ethane, propane, butane, pentane, alcohols, such as ethanol, isopropanol, halogenated hydrocarbons or CFCs or a mixture thereof. The only use of CO2 or a mixture of CO2 and N2 as a blowing agent is particularly advantageous, since they are inert gases, which are non-flammable, so that no potentially explosive atmosphere can arise in the manufacture. This makes costly safety precautions unnecessary and greatly reduces the potential risk in production. It is also advantageous that products do not have to be stored to allow flammable volatiles to evaporate before products are shipped out.
    [0040] Additional advantages arise from additionally adding one or more nucleating agents to the melted polymer comprising a blowing agent. Useful nucleating agents include, in particular, talc, calcium fluoride, sodium phenylphosfinate, aluminum oxide, carbon black, graphite, pigments and polytetrafluoroethylene, each, individually or even in any mixtures. Talc is particularly preferred for use as a nucleating agent. The proportion of the total mass of the thermoplastic molding composition or melted polymer that is attributable to the nucleating agent is preferably in the range of 0% to 4% by weight and especially in the range of 0.1% to 2% by weight.
    [0041] The invention will now be more particularly described with reference to the drawings. The only figure shows a schematic representation of an apparatus for pelletizing molten polymers.
    [0042] Figure 1 shows a schematic representation of an apparatus for producing expanded pellets of a molten polymer comprising a blowing agent. The starting polymer is introduced into an extruder 10 via a feed funnel 14. Extruder 10 is configured, for example, as a twin screw extruder and is fed via a motor 12. The feed funnel 14 can additionally be used to add auxiliaries, such as, for example, dyes or nucleating agents. The raw material introduced is melted and plasticized in the extruder. In the process, the material is transported in the direction of a perforated disc 18.
    [0043] In the embodiment shown in figure 1, a fusion pump 16 is arranged upstream of the perforated disc 18 to apply pressure to the molten material. Pressure is chosen as a function of the type and amount of blowing agent used. The blowing agent is introduced into the melted polymer through an addition point 40 in the extruder 10 between the feed hopper 14 and the melting pump 16. In the embodiment shown, the addition point 40 for the blowing agent is arranged in such that the blowing agent is only added after all the polymer has melted. The blowing agent introduced becomes incorporated in the melted material for the remaining distance in the extruder. A mixture of carbon dioxide and nitrogen is an example of the suitable blowing agent.
    [0044] The fusion pump 16 helps to force the melted material through the perforated disc 18 and into the pelletizing chamber 26. The pelleting chamber is traversed by a stream of liquid, the pressure of which is above ambient pressure. The direction of flow is indicated by the arrows 36. Inside the pelletizing chamber 26 a rotating blade 24 is disposed in a pelletizing medium 20. The rotating blade 24 is driven by a motor 22. The molten polymer leaves the perforated disk 18 as a plurality of expanding polymeric filaments that are cut by the rotating blade 24. Individual expanding pellets are produced in the process. The pressure exerting force and also the speed of the cutting device are chosen, in such a way that the shape of the pellets is substantially spherical.
    [0045] The pellets in the temperature-controlled liquid are expanded by the blowing agent they contain, while the temperature of the temperature-controlled liquid and the temperature-controlled perforated disc and also the pressure of the temperature-controlled liquid were chosen in such a way that the expanded pellets have an uninterrupted foam film. The temperature-controlled liquid stream discharges the expanding / expanded pellets resulting from the pelletizing chamber 26 and feeds them through circuit line 38 into a dryer 30. In dryer 30, the expanded pellets are separated from the temperature-controlled liquid and dried and sent, via product discharge 32, into a collection container 34. The temperature-controlled liquid from which the pellets were removed continues to flow through circuit line 38 in a circuit pump 28, where the temperature-controlled liquid is filtered, temperature-controlled and pressurized. From the circuit pump 28, the temperature-controlled liquid flows back to the pelletizing chamber 26. EXAMPLES
    [0046] A twin screw extruder having a screw diameter of 18 mm and a length to diameter ratio of 40 is loaded with 99.5 parts by weight of a thermoplastic elastomer (TPE) and 0.5 parts by weight of talc . The thermoplastic elastomer was melted in the melting zone of the twin screw extruder and mixed with the talc. After melting the thermoplastic elastomer and mixing the talc, CO2 or, in example 6, a mixture of CO2 and N2 was added as a blowing agent. The amounts of blowing agent added are each tabulated in the examples. In the course of traveling the remaining distance in the extruder, the blowing agent and the melted polymer became mixed together to form a homogeneous mixture. The total productivity through the extruder containing TPE, talc and the blowing agent was 3.5 kg / h.
    [0047] In examples 1 to 5, the following process parameters were fixed: The temperature in the extruder in the melting zone and during the mixing of talc in the TPU was, depending on the TPE used, between 230 ° C and 220 ° C. The temperature in the extruder housing at the injection site was reduced to between 205 ° C and 220 ° C and the subsequent housing between 200 ° C and 220 ° C. All additional housing parts up to the end of the extruder and also the fusion pump were maintained at 200 ° C to 220 ° C. The fusion pump produced a pressure of 90 bar at the extruder end. The temperature of the initialization valve was set at 210 ° C or 220 ° C and the perforated disc was heated to a target temperature of 250 ° C by electric heating.
    [0048] In example 6, the following process parameters were fixed: The temperature in the extruder was uniformly set at 180 ° C until the start-up valve and the perforated disc were heated to a target temperature of 250 ° C by electric heating. The fusion pump produced a pressure of 90 bar at the end of the extruder.
    [0049] In all the examples, the mixture of TPE, talc and blowing agent was pressed through the perforated disc having a hole with a diameter of 1 mm and cut in the pelletizing chamber crossed with water downstream by 10 rotating blades connected to a ring of blades. In examples 1 to 5, the pressure in the pelletizing chamber was 1 bar and in example 6 the pressure in the pelleting chamber was established from 10 to 15 bar. The temperature-controlled medium was maintained at a constant 30 ° C. During its presence in the pelletizing chamber, the mixture expands. Granules having an average size of about 2 mm and a weight of about 2 mg were produced in the process. To determine the apparent density, a 100 ml container was filled with the expanded and weighed granules with an accuracy of ± 5 g / l. In all examples, the pellets produced have an uninterrupted film.
    [0050] The examples below report the results. EXAMPLE 1
    [0051] The TPE used was a polyetherester based on polytetrahydrofuran (poly-THF) and polybutylene terephthalate (PBT) and having an elongation at break greater than 500%, a Shore hardness of 90A and a melting range of 175 ° C at 190 ° C. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent densities corresponding to the particular proportions of blowing agent added are listed in Table 1.
    EXAMPLE 2
    [0052] The TPE used was a polyesterester based on 1,4-benzdicarboxylic acid, dimethyl ester, 1,4-butanediol and -hydro-hydroxypoly (oxy-1,4-butanediyl) and having an elongation at break greater than 700%, a Shore hardness of 96A and a melting range of 200 ° C to 220 ° C, obtainable as Pelprene® P-70B from Toyobo Co, Ltd., for example. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent densities corresponding to the particular proportions of blowing agent added are listed in table 2.

    EXAMPLE 3
    [0053] The TPE used was a styrene-butadiene block copolymer (SBC) having the properties of a thermoplastic elastomer (S-TPE, elongation at break greater than 300%, Shore hardness of 84A, an MVR (melted volume rate) ) (200 ° C / 5 kg) = 14 cm3 / 10 min), available as Styroflex® 2G66 from Styrolution, for example. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent densities corresponding to the particular proportions of blowing agent added are listed in Table 3.
    EXAMPLE 4
    [0054] The TPE used was a polyetherester having a soft polyether segment having an elongation at break greater than 450%, a Shore hardness of 38D and an MVR (190 ° C / 2.16 kg), of 28 cm3 / 10 min , obtainable as Arnitel® PL380 from DSM, for example. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent densities corresponding to the particular proportions of blowing agent added are listed in table 4.
    EXAMPLE 5
    [0055] The TPE used was a polyetherester based on segments of rigid (crystalline) polybutylene terephthalate and soft (amorphous) units derived from long chain polyether glycols having an elongation at break greater than 700%, a Shore hardness of 30D and a mass flow rate MFR (190 ° C / 2.16 kg) of 5 g / 10 min, obtainable as Hytrel® 3078 from DuPont, for example. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent densities corresponding to the particular proportions of blowing agent added are listed in table 5.
    EXAMPLE 6
    [0056] The TPE used was a polyether copolyamide based on units of elastic polyether and crystalline polyamide having an elongation at break greater than 750%, a Shore hardness of 27D and a melting point of 134 ° C according to ISO 11357 , obtained as Pebax® 2533 SD 02 from Arkema. This TPE was processed by the method described above and the bulk density was determined as described above. The apparent density corresponding to the particular proportions of blowing agent and the different pressures of the temperature controlled liquid flowing through the pelletizing chamber are listed in table 6.
    LIST OF REFERENCE NUMBERS 10 Extruder 12 Motor 14 Feed hopper 16 Fusion pump 18 Perforated disk 20 Pelletizing device 22 Motor 24 Blade 26 Pelletizing chamber 28 Circuit pump 30 Dryer 32 Product discharge 34 Collection container 36 Flow direction 38 Circuit line 40 Adding point for blowing agent
    权利要求:
    Claims (8)
    [0001]
    1. PROCESS TO PRODUCE EXPANDED PELLETS, from a thermoplastic elastomer having an elongation at break greater than 100%, measured according to DIN EN ISO 527-2, said process characterized by comprising the steps of: (a) pressing a polymer melted comprising a blowing agent through a perforated disc (18) controlled at a temperature between 150 ° C and 280 ° C and in a pelletizing chamber (26), (b) use a cutting device (20) to fragment the melted polymer pressed through the perforated disc (18) into individual expanding pellets, (c) unloading the pellets from the pelletizing chamber (26) using a liquid stream (36), wherein the blowing agent comprises CO2 or N2 or a combination of CO2 and N2 and the amount of blowing agent in the melted polymer comprising a blowing agent is in the range of 0.5% to 2.5% by weight and in which the pelletizing chamber (26) is traversed by a liquid stream that is controlled at a time temperature between 5 ° C and 90 ° C and whose pressure is 0.1 bar to 20 bar above ambient pressure, the pressure and temperature for the liquid in the pelletizing chamber (26) and also the temperature for the perforated disc (18 ) being chosen in such a way that the pellets are expanded in the pressurized liquid by the blowing agent they contain, in order to produce expanded pellets having an uninterrupted film, and in which the melted polymer comprises a thermoplastic elastomer based on polyether polyester, polyesteresters or copolymers in styrene-butadiene block.
    [0002]
    2. PROCESS, according to claim 1, characterized in that the thermoplastic elastomer has an elongation at break greater than 200%, measured according to DIN EN ISO 527-2.
    [0003]
    PROCESS according to any one of claims 1 to 2, characterized in that the temperature of the liquid in the pelletizing chamber (26) is decreased when the pellets undergo an uncontrolled expansion that does not produce an uninterrupted film, and is elevated when not there is no expansion or insufficient expansion of the pellets.
    [0004]
    PROCESS according to any one of claims 1 to 3, characterized in that the temperature of the perforated disc (18) is decreased when the pellets undergo an uncontrolled expansion that does not produce an uninterrupted film and is elevated when there is no expansion or insufficient pellets.
    [0005]
    PROCESS according to any one of claims 1 to 4, characterized in that the melted polymer comprises a blowing agent which comprises a nucleating agent.
    [0006]
    6. PROCESS, according to claim 5, characterized in that the nucleating agent has a size between 0.01 μm and 100 μm and is selected from talc, calcium fluoride, sodium phenylphosfinate, aluminum oxide, carbon black , graphite, pigments, finely divided polytetrafluoroethylene or a mixture thereof.
    [0007]
    PROCESS according to any one of claims 1 to 6, characterized in that the blowing agent comprises a co-expanding agent and in which the co-expanding agent is selected from an alkane, an alcohol, a halogenated hydrocarbon or a mixture of these.
    [0008]
    PROCESS according to any one of claims 1 to 7, characterized in that the pressure and temperature inside the pelletizing chamber are chosen in such a way that the apparent density of the expanded pellets does not exceed 250 g / l.
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    同族专利:
    公开号 | 公开日
    WO2014198779A1|2014-12-18|
    EP3008122B1|2017-08-09|
    ES2646539T3|2017-12-14|
    TW201509625A|2015-03-16|
    US20160121524A1|2016-05-05|
    BR112015031074B8|2021-02-23|
    EP3008122A1|2016-04-20|
    BR112015031074A2|2017-07-25|
    CN105452355B|2019-02-01|
    CN105452355A|2016-03-30|
    PL3008122T3|2018-01-31|
    TWI624344B|2018-05-21|
    US10279516B2|2019-05-07|
    JP6386543B2|2018-09-05|
    KR102217486B1|2021-02-22|
    KR20160021228A|2016-02-24|
    JP2016521796A|2016-07-25|
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    法律状态:
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-11-03| B09A| Decision: intention to grant|
    2020-12-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-02-23| B16C| Correction of notification of the grant|Free format text: REF. RPI 2608 DE 29/12/2020 QUANTO AO TITULO. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13171855.3|2013-06-13|
    EP13171855|2013-06-13|
    PCT/EP2014/062144|WO2014198779A1|2013-06-13|2014-06-11|Method for producing expanded granulate|
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