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    公开号:BE1020318A5
    申请号:E2008/0277
    申请日:2008-05-19
    公开日:2013-08-06
    发明作者:Alessandro Casalini；Riccardo Felisari
    申请人:Polimeri Europ S P A；
    IPC主号:
    专利说明:

    PROCESS FOR PREPARING PELLETS BASED ON EXPANDABLE THERMOPLASTIC POLYMERS AND RELATED PRODUCTS
    The present invention relates to a process for the continuous production of expandable granules based on thermoplastic polymers, and the associated product.
    The term "expandable granules based on thermoplastic polymers" as used in the specification and claims of the present invention means thermoplastic polymers, for example vinyl aromatic polymers, in the form of granules, containing a expansion system and possibly other additives, the shape of the granules being essentially ellipsoidal (nut-shaped or lenticular for example), whose particle size ranges from 0.02 to 3.5 mm3.
    These expandable thermoplastic polymers in the form of granules, after expansion and molding, are particularly used in the production of household equipment or industrial equipment, in the building (packaging and thermal insulation) because of their thermo-insulating properties.
    The method and equipment described herein, object of the present invention, allow the large scale production of said expandable thermoplastic polymers at moderate costs and with better quality regularity.
    Thermoplastic polymers, for example aromatic vinyl polymers such as polystyrene, can be made expandable by incorporating a blowing agent into the polymer die. Typical blowing agents used with the aromatic vinyl polymers include at least one liquid hydrocarbon containing from 3 to 7 carbon atoms, halogenated hydrocarbon, carbon dioxide or water. The amount of blowing agent is from 2 to 15% by weight.
    Expansible polymers are generally produced in the form of beads or granules which, under the action of heat provided by steam, for example, are first dilated to the desired density and, after a certain period of maturation , are agglomerated in close molds so as to produce desired blocks or final products.
    The expandable beads can be obtained by a discontinuous suspension polymerization process. This process, well known to those skilled in the art, is described in US Pat. Nos. 2,673,194 and 4,500,692 and includes the following steps: dispersing the liquid vinyl aromatic monomer in an aqueous medium using stabilizing agents; adding polymerization catalysts and polymerizing the aromatic vinyl monomer in a heated and stirred reactor; adding the blowing agent to a certain degree of monomer conversion; - terminate the polymerization; - evacuate, wash, dry and sieve the resulting beads. The diameter of the balls generally ranges from 0.1 to 3 mm.
    This suspension process makes it possible to obtain a product of good quality but has several drawbacks, in particular: a very wide distribution of the diameter of the balls, then the need to separate the various fractions by sieving and to eliminate the rejects; significant limits in the production of special products, such as colored beads and / or beads containing heterogeneous fillers or additives, for example nucleating agents and / or flameproofing agents, because they are difficult to remove. incorporate into the beads, or they can inhibit the polymerization. See, for example, U.S. Patent No. 4,360,611 or International Patent Applications WO 98/51734 and WO 00/29471; other limitations in the use of blowing agents, which must be dispersible and / or soluble in the polymer die or in the use of the monomers, which must be capable of polymerizing in aqueous solution; the difficulty in reducing the residual monomer, for example styrene, in the polymer to below 1000 ppm and in reducing the total internal water content; - environmental problems due to the considerable consumption of water that can not be eliminated simply by the sewage systems unless subjected to a prior purification treatment, and the impossibility to recycle the expanded polymer after use.
    These and other disadvantages can be overcome by a continuous bulk process in which a melt polymer composition is mixed with solid additives and blowing agents. These methods are described, for example, in GB-A-1,062,307 and EP-A-668,139. These patents disclose a process for producing expandable polystyrene (EPS) granules in which the polymer melted and the blowing agent are mixed via static mixing elements. After cooling, the mixture is granulated through a die.
    The product thus obtained generally has the disadvantage of having a cellular structure, after expansion, in which the cells are irregular and normally too large. The number of cells and the structure of the foam obtained during the expansion play a very important role in obtaining ideal thermal insulation properties and a good surface area on the foams. For this reason, the use of a nucleating agent is often necessary. European Patent EP-A-126 459 describes a method for overcoming these problems by means of heat treatment of the granules carried out under pressure and at a temperature above the glass transition temperature of the expandable polymer.
    In addition, the expandable resin leaving the die is difficult to cut because of its natural tendency to swell. In US patent application 2006/167123, a method is described which exploits this feature to obtain low density foamed granules by direct cutting of the expansible molten polymer exiting the die.
    In other processes, described for example in US Pat. Nos. 5,108,673 and 5,573,790, the expandable polymer is extruded into continuous filaments, which are immediately cooled with cold water at the outlet of the die and granules in a subsequent step. However, it is not possible to obtain substantially spherical balls because the cutting of the filaments produces cylindrical pellets whose diameter normally exceeds 1 mm and the equipment must be kept under pressure in order to avoid the prior swelling of the pellets.
    Incorporation of organic fillers can be problematic. International Patent Application WO 00/43422 claims that the atherman materials have a large nucleation effect and that, therefore, in order to avoid pre-swelling, it is necessary to work with a granulation system under water and under pressure. This method involves the use of a specific die in which the polymer is extruded through a series of small orifices. The person skilled in the art knows that this process produces an extremely strong fixation because the temperature of the surface of the die is close to that of water, which leads to a polymer stream close to its solidification temperature. Due to this swelling during extrusion and the need to produce extruded granules with very small dimensions, very small orifices are required, with diameters ranging from 0.3 to 1.2 mm. Extrusion through these orifices therefore requires very high shear deformation speeds, which implies that with this technology it is impossible to obtain extruded particles with dimensions smaller than 1 mm.
    US patent application 2005/156344 describes the influence of the geometry of the orifices of the die (diameter of the orifices, length / diameter ratio, angles of the inlet and outlet cones), the temperature of the melted product and the plasticizers on the expansion of the polymer at the exit of the orifices of the die and, consequently, on the diameter of the final ball. The patent describes that the expandable resin may contain various additives, such as organic and inorganic, soluble or insoluble nucleating agents, plasticizers, flame retardants, colorants and pigments, such as carbon black, graphite or aluminum, up to 30%.
    One of the problems known in the literature, relating to the production of expandable vinyl aromatic polymer beads obtained in a continuous bulk process, is the need to cool the blowing agent-containing polymer prior to extrusion thereof. the sector. This cooling can be achieved, for example, by means of cooling elements housed inside the extrusion devices, by means of heat exchangers or by a static mixing equipment with integrated cooling devices.
    According to the known art, cooling the polymer before granulation is essential to prevent its swelling in the mill and to obtain products whose shape is regular.
    European Patent EP No. 668,139 discloses a process for preparing expandable plastic granules having a diameter of at least less than 1 mm. According to this method, the temperature of the expansible molten polymer must be reduced to a few degrees above the solidification temperature of the polymer itself, in order to obtain these granules.
    It is well known that the viscosity of thermoplastic polymers increases considerably as the temperature of the molten polymer approaches the solidification point. It appears that when the high viscosity is associated with a high shear deformation rate, corresponding to the passage of the polymer through the die orifices, a considerable pressure drop occurs as the polymer stream passes through the die. This phenomenon requires the use of specific dies, appropriate to mechanically support these pressure gradients.
    Moreover, the rapid cooling of the polymer, following the immersion of the surface of the die under water ("underwater" configuration) increases the probability of closing the orifices of the die and making the current unstable. .
    US patent applications 2005/140039 and 2005/123638 describe a method (first) and equipment for hot granulation (second) for preparing granules of expandable thermoplastic polymers. According to these patent applications, the problems of obstruction and current irregularity mentioned above can be prevented by a new granulation device in which the molten polymer is extruded and is immediately cooled by means of a minced spray. water, and not by immersion. By doing so, it prevents the swelling of the reduced product granules and, at the same time, avoids clogging of the orifices of the die. In these patent applications, no data is provided on the procedure or the process for producing expandable beads containing a large amount of additives.
    European Patent Application No. 1,702,738 describes a method and equipment for continuously producing expansible polymer granules. According to this application, clogging of the die orifices can be avoided by building a dedicated electronic control system that controls the process conditions and maintains the pressure and temperature of the molten polymer within a pre-set range of values. But systems based on active electronic stability control are generally not considered intrinsically reliable. They therefore do not allow to guarantee a high reliability of the equipment, their use is therefore generally not recommended for large-scale production.
    International patent application WO 2006/88392 discloses a process which allows the continuous production of polystyrene and impact polystyrene in the form of expandable granules, within a wide range of molecular weights. The innovation lies in the mixing system between the molten polystyrene and the blowing agent. The expandable beads are prepared by extruding and cooling the molten polymer preceding the granulation process. In this patent application, no data is provided on the quality of the expandable granule obtained and more specifically on the expandable granulate with a high content of inorganic additive.
    EP Patent Application No. 1,693,413 discloses a method for continuously producing expandable polystyrene particles containing silicates and inorganic zeolites to improve the insulating properties of the corresponding foams. The polymer is introduced into an extruder and is mixed with a blowing agent and with additives. It is then extradited, cooled and cut into particles. In this patent application, no indication is given on the configuration of the mill, the process conditions, the size and shape of the particles obtained.
    Expanding vinyl aromatic polymer particles obtained in a continuous bulk process can be altered by the orientation and mechanical stresses generated by the extremely rapid cooling to which the particles are exposed when reduced to granules. When these granules swell and are molded, this constraint causes a heterogeneity of the honeycomb structure which, in turn, alters the mechanical and aesthetic properties of the final products manufactured. The patent application US 2005/140039 explains that, to solve these problems, it is possible to relax this constraint by annealing the granules at a temperature close to the glass transition temperature (Tg) or by adding nucleating additives. In any case, the effect of inorganic additives on nucleation has not been studied.
    The object of the present invention is to propose a method for producing expandable particles or granules based on thermoplastic polymers, said process making it possible to obtain an optimal dispersion of the expansion system possibly containing additives, in particular appropriate concentrations. inorganic pigments, insoluble in the polymer matrix.
    Another object of the present invention is to provide a process for producing expandable particles comprising a polymer die made of polymers and copolymers with an aromatic vinyl base, for example polystyrene, impact polystyrene (HIPS), polymer styrene-acrylonitrile (SAN); non-vinyl aromatic polymers, such as polyethylene, polybutylene terephthalate (PBT), polyethylene terephthalate; and their mixtures.
    Another object of the present invention is to provide a process for producing expandable particles having a polymer base suitable for large scale production, said process being characterized in that it is compatible and easy to introduce into a petrochemical site. , with good product quality consistency and easy operation of the equipment.
    It is another object of the present invention to provide a process for producing expandable particles having a polymer base, said process being capable of producing expanded articles with a high closed cell content (> 90%), with high sintering capacity. and having a uniform alveolar size, ranging from 70 to 200 microns.
    Another object of the present invention is to provide a method for producing expandable particles having a polymer base, said expandable particles obtained having a reduced residual stress, so as to eliminate or strongly reduce the annealing phase of said particles.
    It is also an object of the present invention to provide a process for producing expandable particles having a polymer base which, after swelling and molding, can yield articles meeting fire resistance specifications according to B2 test, DIN 4102 regulation, part 2.
    The above-mentioned advantages as well as other advantages of the present invention will become apparent as the following description is read, the contents of the present invention being described in detail and illustrated in the accompanying drawings. Variations in the procedures, structural features and arrangement of the parts may be identified by those skilled in the art and should be considered to be within the scope of the present invention as well as the advantages of use which they generate.
    The Applicant has discovered that the objects and scope of the present invention are achieved through the use of a novel method described in the claims.
    According to the present invention, the method comprises incorporating into a first polymer stream (hereinafter referred to as a "main stream") a second polymer stream (hereinafter referred to as a "side stream") containing the polymer system. expansion and additive.
    Alternatively, the expansion system can be directly incorporated into the main stream.
    The resulting melt composition is then homogenized and finely sieved by one or more sieving steps which removes or dissociates the polymeric aggregates and the undispersed inorganic fillers.
    The polymer composite product is then extruded through a die and granulated, preferably by the water chopped spray technology described in US Patent Application 2005/140039.
    According to a preferred embodiment, the polymer forming the main stream is taken, in the molten state, from a continuous polymerization process. The polymer, resulting from one or more polymerization steps, is typically extracted from the possible dilution solvent, the unreacted monomer and the oligomers, in a section called "devolatilization".
    The polymer thus purified is used directly, in the molten state, as the main polymer stream of the process of the present invention. For this purpose, the polymer from the devolatilizer preferably contains an amount of monomers not exceeding 2000 ppm and a quantity of dimers, trimers and oligomers not exceeding 8000 ppm, so as to avoid damaging the structure foam obtained after expansion of the resulting expandable particle polymers.
    In another embodiment, the polymer used as the main stream is in the form of granules. Said granules are melted in a suitable device (extruder single screw or extruder double screw, for example).
    In both embodiments, the molten polymer material is pressurized and propelled to the next section of the process by a suitable device, typically a gear pump.
    Advantageously, the additives are incorporated in a secondary polymer stream joining the main polymer stream in the molten state.
    In a preferred embodiment, the additives are metered in a twin-screw extruder together with the polymer pellets. Suitably, the extruder, after the melting section, contains mixed elements which allow a better distribution of the additives in the polymer phase. The mass fraction of the polymer phase should be at least 20%, preferably at least 40%, based on the polymer content in the side fraction, to treat the resulting melt successfully.
    Advantageously, the extruder contains a degassing phase to remove any solvents contained in the additive mixture.
    The temperature of the molten stream must be maintained within a predefined range. Typically, the minimum temperature equals the maximum temperature selected from the solidification temperatures of the molten components, to which 20 ° C is added, while the maximum temperature is the same as 150 ° C.
    Optionally, before entering the extruder, the additives and the granulated polymer can be premixed in a suitable mixer for the solids, to promote a homogeneous distribution of the components. The preferred device for this operation is a screw mixer.
    When using liquid or gaseous additives, an effective way of incorporating them is to inject them into a lateral introduction point of said extruder, downstream of the melting and degassing section.
    Said additives consist of any material capable of improving the performance of the polymer and suitable for processing in a single-screw or twin-screw extruder. These additives generally include lubricants, plasticizers, hydrophobic agents, antioxidants, nucleating agents, flame retardants, bromine stabilizers, smoke suppressors. The following examples are non-limiting examples: elemental carbon: graphite materials, carbon blacks, cokes, carbon nanofibers, vitreous carbon; self-extinguishing agents: halogen-based compounds or compounds lacking halogens such as hexabromocyclododecane, pentabromomonochlorohexane, tetrabromobisphenol A bis (allyl ether) and pentabromo phenyl allyl ether; of these, hexabromocyclododecane and tetrabromobisphenol A bis (allyl ether) are preferred; nucleating agents such as polyethylene waxes having a molecular weight of less than 10,000 Daltons; synergistic self-extinguishing agents, that is to say the molecules having a weak bond of the CC, NN or 0-0 type such as didumyl peroxide, cumene hydroperoxide, 3,4-dimethyl- 3,4-diphenylhexane, 3,4-dimethyl-3,4-diphenylbutane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynomane; inorganic derivatives of silicon, magnesium and aluminum, such as talc, pyrophilite, silica, hydrotalcite, mica, montmorillonite and similar products; - oxides and dichalcogenides of metals and semi-metals.
    The degree of graphitization and the crystalline parameters are calculated as follows:
    A concentrate of the graphite material, as described below, is diluted in chloroform and mixed with a magnetic paddle stirrer for 24 hours. The solution is then washed, filtered and dried in an oven for 10 hours at 500 ° C to remove water and other chloroform-insoluble substances.
    Then, the material is placed in an X-ray diffractometer. The diffraction spectrum is read between 10 ° and 70 °.
    The distance doo2 between the graphene planes is measured by the angle Θ002 according to Bragg's law:
    where λ is the length for the Cu K al line, i.e. 0.154 nm.
    The highly oriented pyrolitic graphite has an interplanar distance of 0.3354 nm. However, both artificial and natural graphite are of greater value because of defects between planes. As a result, doo2 is always higher than 0.3354 nm. The difference between the observed interplanar spacing and the 0.3354 nm reference value is the measure of crystallinity and degree of graphitization.
    In the present invention, the degree of graphitization "g" is calculated according to the formula of Maire and Mering:
    where doo2 is calculated from the peak value of the diffractogram curve, after removing the noise and performing the smoothing.
    Solid additives that do not melt at the melt extrusion temperature should be in the form of fine particles. In particular, considering the population of particles unable to melt, the "d90" value, ie the size below which 90% of the population figure, should not typically exceed half the diameter of the orifices. of the sector. Preferably, the value d90 should not exceed one quarter of the diameter of the orifices of the die. Dimension means the diameter calculated by laser diffraction of materials that can not melt.
    Non-limiting examples of suitable granular polymers for the preparation of the side stream according to the present invention include: homopolymers, random copolymers and block copolymers having an aromatic vinyl base; in particular polystyrene, styrene-butadiene-styrene rubber, styrene-isoprene-styrene rubber, styrene-ethylene-butylene-styrene rubber (SEBS), styrene-ethylene-propylene rubber (SEP), styrene-butylacrylate copolymer , impact polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN); ethylene-based polymers, such as ethylene-vinyl acetate (EVA), polyethylene (PE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET); condensation (co) polymers such as polycarbonates and polyesters, (meth) acrylic polymers, polyphenylene oxide (PPO), polymers, techniques, polyamides, polylactates.
    The fragments of the aforementioned polymers, as well as the ground materials from the products after their use and the unwanted expandable polystyrene beads (unwanted fractions resulting from the slurry production process) can be introduced into the equipment for recycling.
    The term "expansion system" as used in the specification and claims of the present invention means an expanding agent, when used as such in the expandable polymer composition, or a mixture expandable agents when more than one is used.
    The "critical temperature" of the expansion system means the critical temperature of the blowing agent, when the expansion system consists of only one blowing agent; or the critical temperature of the blowing agent which is the majority by weight, when the blowing system consists of a blowing agent mixture, one of said blowing agents being greater than 50% by weight of the blend; or in other cases, the critical temperature of the blowing agent mixture.
    The "critical pressure" of the expansion system means the critical pressure of the blowing agent, when the expansion system consists of only one blowing agent; or the critical temperature of the blowing agent which is the majority by weight, when the blowing system consists of a blowing agent mixture, one of said blowing agents being greater than 50% by weight of the blend; or in other cases, the critical temperature of the blowing agent mixture.
    Non-limiting examples of the blowing agents that can be used include hydrocarbon compounds having 3 to 7 carbon atoms, carbon dioxide, carbon monoxide, water, ethyl alcohol and ether. Among these compounds, it is preferable to use hydrocarbon compounds having from 4 to 6 carbon atoms. Data has shown that a mixture or system of blowing agents having different boiling points promotes swelling of the foam. The expansion system is preferably used in a content of from 2 to 10% by weight, based on 100 parts by weight of the expandable polymer composition.
    In a first embodiment, the expandable system is injected into the side polymer stream which is in the molten state. The injection can be performed by any procedure known in the art. For example, in the single-screw extruder, through a side port, or downstream of the extruder, into the stream of molten extrudates.
    The expansion system can be dispensed and dispersed in the additive stream. Any useful device for this purpose can be used, for example static or dynamic mixers. Complete mixing of the expansion system in the additive stream is not required.
    In a second embodiment, the expansion system and the side polymer stream are added to the main stream separately.
    In a third embodiment, the expansion system is divided into two streams, the largest being injected directly into the main polymer stream, while the other is injected into the side stream.
    Advantageously, the expansion system may initially be pressurized (for example by a membrane metering pump) and then heated prior to injection into the polymer stream. According to this scheme, the temperature of the expansion system, after heating, is at least 60 ° C, it preferably exceeds the glass transition temperature of the majority polymer by weight.
    To obtain a constant flow of the expansion system and a constant ratio between the flow rate of the system and that of the expansive composition of the resulting polymer, any technique known in the art can be used. For example, it is possible to adjust the speed of the metering pump of the expansion system in return with respect to its mass flow rate (measured by a flowmeter according to the Coriolis principle). Pulsation dampers can be inserted downstream of the metering pump to stabilize the current. It is effective to use restraining devices, located very close to the injection point, to prevent dangerous polymer backflows into the expansion system stream that are likely to occur during accidental pressure changes. sudden in the polymer itself.
    According to the present invention, it is preferable that the additive stream be less viscous than the main stream of the vinyl aromatic polymer at shear deformation rate and temperature conditions existing at the injection point and in the mixing device. subsequent.
    One or more devices are used to disperse and dispense the expansion system and the side stream into the main stream. It is possible to use static and dynamic mixers.
    Typically, the minimum residence time for this mixing phase is 100 seconds. If static mixers are used, the overall pressure reduction in the mixers is greater than 20 bar, and the rate of pressure reduction of the polymer, calculated on the basis of polymer flow and cross section, is maintained beyond 0.2 bar per second, for at least 5 seconds.
    According to the present invention, the polymer stream must be brought to a reference temperature before mixing with the expansion system. This reference temperature is calculated as the critical temperature of the expansion system, increased or decreased by 25 ° C; preferably as the critical temperature of the expansion system, increased or decreased by 15 ° C.
    The pressure of the polymer stream must be greater than the critical pressure of the expansion system, i.e. a value which exceeds the value of said critical pressure.
    Preferably, these pressure and temperature reference conditions must be maintained from the injection point of the expansion system until substantially mixed with the polymer. Alternatively, these conditions can be maintained until the granulation of the composition.
    Optionally, moderate cooling of the final expandable polymer stream may be effected prior to granulation. In this embodiment, the temperature of the compound without the optional cooling step should preferably be at least 50 ° C higher than the glass transition temperature of the majority polymer by weight. A tube bundle of heat exchangers or static mixing reactors (RMS) may be used.
    On the contrary, according to the state of the art techniques (see for example international patent applications WO 98/51735 and WO 04/3442 or US 2005/0156344), the cooling of the polymer before granulation is essential, or at least preferable . For example, in EP 668,138, the melt is cooled to a few degrees above the solidification temperature, i.e., under conditions very different from those specified herein.
    Advantageously, the expandable polymer compound passes through a filtration device before passing through the die and being granulated. Said filtration device consists of one or more grids through which the composition in the molten state passes.
    Surprisingly, it has been found that the filtration grids cause a micro-mixing of the additives and the expansion system in the polymer die. This micromixing phenomenon is favored by the extremely high shear deformation rates produced as the polymer passes through the mesh of the grids, and it can be controlled by varying the cross-section of the filtration surface (and hence the speed of the polymer) and mesh size.
    The second, and no less important, filtration action is the sieving of particles and aggregates of polymer and excessively bulky additives, which may contribute to clogging the die orifices.
    The filter not only removes the fraction of additives which, from the beginning, has a very large dimension, but also possible aggregates that can occur in the polymer stream during the previous operations because of chemical reactions and physicochemical effects. -chemicals between the components of the polymer mixture (for example crosslinking reactions between molecules having unsaturated bonds).
    Severe mesh size control is necessary: too large mesh filters are inefficient in the above filtration actions; on the contrary, an extremely fine mesh prevents the passage of the additive particles and considerably increases the reduction of the pressure, which forces to change frequently the filter.
    In order to obtain the expandable polymer particle composition of the present invention, the mesh size of the grid must be smaller than half the diameter of the orifices of the die, and is preferably one-third to one-tenth of said diameter.
    The pressure reduction of the polymer composition through the filtration grids is preferably less than 200 bar, and is preferably 10 to 100 bar.
    To enable continuous operation of the process, it is preferable to use a system to clean the filter grids regularly, or to replace them without affecting the production of the equipment. For this purpose, systems (so-called filter exchangers) can be used which make it possible to replace a filter clogged with a new filter in a few seconds, or continuous filters, the filtration filter being moved slowly, but continuously, in one direction. transverse to the polymer stream.
    The filtering device may be a grid in the form of a disc, which completely covers the cross-section of the polymer composition, or it may have a more complex shape, it may be for example a series cartridges arranged in the direction of the fluid. In this case, advantageously, a redistribution of the polymer stream is obtained, which improves its homogeneity.
    The use of several filter grids, arranged in series, can also improve the dispersion of the additives and the expansion system. In this case, it is useful to use a succession of fine mesh grids alternating with grids with wide mesh, arranged in the direction of the current.
    The expandable composition is then introduced into a cutting head which distributes the polymer homogeneously in the die, wherein the expandable composition is extruded and granulated.
    The die is preferably heated to at least the temperature of the expandable composition entering said die, preferably 10 to 60 ° C above this temperature. The heating may be carried out by any method known in the art, for example by electrical resistors or by circulation of heated fluid in channels within the die body.
    The cutting device used to produce the expandable particle composites of the present invention is described in detail in US Patent Application 2005/123638. For the characteristics of the die and the granulation chamber, refer to the above mentioned publication.
    Typically, the swelling of the expandable compositions ranges from about 1.2 to 3.0, depending on the composition, the shear rate, and the melt temperature. By controlling the diameter of the orifices and the swelling, it is possible to obtain expandable particles of the desired size, in particular in the range of 0.6 to 2.2 mm.
    The granulation chamber must be pressurized to prevent swelling of the expandable granules. The pressure necessary to prevent this undesirable phenomenon depends, in particular, on the content and typology of the expansion system and the additives used. Typically, the required pressure is from 1.5 to 12 barg, preferably from 2 to 8 barg.
    Preferably, the pressure of the water injectors (spraying) is greater than the pressure of the cutting chamber by at least 2 bar. Thus, the jets of water have a correct and uniform flow, which is essential to prevent clogging of the orifices of the die.
    It is important to evaluate the fraction of time (relative to the total time) that the water coming from the injectors to reach the surface of the die, instead of being interrupted by the movement of the blades and the relative support.
    It is necessary to avoid this fraction of time is zero because in this case, the blades completely block the passage of water towards the surface of the die, preventing proper cooling. The factors influencing this fraction of time are, among others, the speed of rotation of the blades and the pressure of the water.
    According to the present invention, said time fraction is preferably 5 to 80%, preferably 10 to 60%.
    The temperature of the water should preferably exceed the glass transition temperature of the expandable granule by 10 ° C to not more than 20 ° C, preferably from 10 ° C to no more than 15 ° C of the glass transition temperature of the expandable granulate.
    The granulation of the expandable polymer can furthermore be facilitated by using separating additives which must be dosed in water, before the formation of the jet.
    The preferred release agents are polysiloxanes such as polydimethylsiloxane, used as such or in emulsion. The amount of polysiloxanes to be added to the water is greater than 10 ppm, and is preferably 10 to 400 ppm.
    Between the mixing devices and the die, it is possible to insert, possibly, a three-way valve for the polymers. Under normal operating conditions, the valve is aligned with the die. On the contrary, at startup, the valve is aligned with an evacuation system or other suitable device for receiving the molten polymer. By passing the polymer stream from the start position to the operating position, the polymer stream can begin to flow almost immediately from the die orifices, thereby reducing the risk of clogging of said orifices.
    The expandable particles thus obtained may optionally, but not necessarily, be subjected to heat treatment in an annealing step, to relax any residual stress and improve the cellular structure resulting from the transformation of the expandable product. The annealing process comprises maintaining the expandable product for a period of time preferably greater than one minute at a predetermined temperature. Said temperature generally ranges from the glass transition temperature of the expandable particle increased or minus 15 ° C.
    The annealing is preferably carried out by maintaining the expandable particle at a pressure greater than 0.5 barg and cooling it to a temperature below 45 ° C before depressurization.
    The vinyl aromatic polymers treated according to the processes proposed in the present invention, show a reduced residual stress in the product reduced in granules: the alveolar structure resulting from the transformation of said granules can therefore be done without annealing or without incorporation of nucleating agents .
    The process for producing granules of expandable thermoplastic polymers, object of the present invention, is explained in more detail with reference to the diagrammatic representations in FIGS. 1 and 2, which represent illustrative and nonlimiting embodiments.
    In the schematic representation illustrated in Figure 1, vinyl aromatic monomers, comonomers, ethylbenzene and other additives 11 are introduced into the reactor 31 and polymerized. The stream is heated by the heat exchanger 32a, passes through a perforated distributor and enters a vacuum container 32b to remove monomers, oligomers, ethylbenzene and other volatile materials. The resulting molten polymer is introduced through a pump 32c into a second heat exchanger 33 where it is brought to the reference temperature (for example 190 ° C). The pumps 32c and 35 are controlled to ensure a pressure in the polymer stream 21 greater than the reference pressure.
    A polymer stream 15 and a stream of additives 16 are introduced, by metering devices, into a continuous screw mixer 44 and then into a twin screw extruder 45 in which the polymer is melted and the additives incorporated.
    The expansion system 12 is dosed by a diaphragm pump 41 and is fed to a heat exchanger 43 where it is heated. The pressure variations produced by the pump 41 are regulated by a pulsation damper 42. The expansion system is heated and is injected into the additive load 46a by a non-return valve located inside the conduit carrying the additives. A small static mixer 46b produces an initial mixture between the additive feed and the expansion system. The resulting composition 22 is added to the main stream of the aromatic vinyl polymer 21, and is then mixed by means of a static mixer 34. The resulting stream, whose pressure increases with the pump 35, is first introduced into a device. filtration 40, and is then fed to the dispenser 36 and then to the die 37, the expandable polymer composition being subdivided into small channels and extruded through a plurality of orifices.
    In the granulation chamber 38, water 13 is sprayed against the die by a set of injectors. To avoid clogging, a controlled amount of nitrogen 14 is metered before being introduced into the granulation chamber. The expandable composition is cut by a set of blades joined by a rotor 39, and the resulting mixture of water + granules is recovered.
    The schematic representation in Figure 2 shows a different arrangement of the side polymer stream and the expansion system. According to this scheme, the side stream 16, after incorporation of the additives into the polymer through the extruder 45, passes through a mixing device 51 which completes the dispersion of the additives in the polymer stream. The expansion system 12 is sucked 41 and heated 43 as in the previous scheme. However, instead of being injected into the side stream, it is directly added to the main stream of the polymer and mixed therein.
    Under the aforementioned conditions, the particles or granules of expandable composites obtained have a substantially ellipsoidal shape, for example the shape of a nut or a lenticular shape (see Figure 3a, 3b and 3c). It is possible to characterize this form quantitatively thanks to a form factor. Numerous definitions of the latter appear in the literature (see, for example, Sukumaran, B. and Ashmawy, AK (2001) Quantitative characterization of the Geometry of Discrete Particles, Geotechnique, Vol 51, No. 7, September, pages 619 to 627). In the present invention, the following nondimensional definition of the form factor is used:
    wherein V is the volume of the expandable composite particle and the area of the corresponding surface. The form factor SF is equal to 1 for a perfect sphere and it decreases with an increase in anisotropy, close to zero for cylinders with a ratio length / diameter that tends to infinity.
    According to the present invention, the expandable composite granules are obtained with a form factor SF, defined as above, ranging from 0.60 to 0.99, said form factor preferably ranging from 0.70 to 0.98. .
    Higher form factors can be achieved by increasing the temperature of the polymer and decreasing the cooling with the water (for example by reducing the flow). Under these conditions, however, pre-expansion is more likely and the polymer emerging from the orifices of the die may spread over the surface of said orifices.
    Typically, the polymer extrusion granules and subsequent underwater granulation are non-nut shaped and smaller form factor values are obtained.
    These smaller form factors frequently cause difficulties during the subsequent charging of these expandable granules in molding machines, and should therefore be avoided.
    Surprisingly, the composite granules produced according to the present invention generally exhibit excellent expandability and moldability when processed according to current standard methods.
    The examples proposed below are a few illustrative and non-limiting examples to better understand the present invention and its embodiments.
    Example 1
    A liquid mixture consisting of 8.0% by weight of ethylbenzene, 84.98% by weight of styrene, 7.0% by weight of [alpha] -methylstyrolene, 0.02% by weight of divinylbenzene is introduced. in the reactor 31. The mixture is gradually brought to a temperature of 135 ° C. After a residence time of about 4 hours, the reactive polymer composition, having a conversion ratio of 70%, is heated to 240 ° C. by a diathermic oil heat exchanger 32a and is then introduced into a devolatilizer 32b. to remove residual monomer and solvent. The resulting composition has a beginning of glass transition temperature ("Tv start") at 104 ° C, a melt index (IF at 200 ° C, 5 kg) of 9, a molecular weight Mw of 190,000 g / mol and a Mw / Mn ratio of 2.8, where Mw is the weight average molecular weight and Mn is the number average molecular weight. An amount of 830 parts of said composition is introduced into the heat exchanger 35 which reduces the temperature to 180 ° C.
    A quantity of 151.6 parts of N2982 (polystyrene whose mass Mw is 130,000 g / mol, the Mw / Mn ratio is equal to 2.3, the IF value (200 ° C., 5 kg) is 25 g / 10 ' , produced by Polimeri Europa) is introduced into a twin screw extruder 45.
    A mixture consisting of 8.0 parts of styrene-isoprene-styrene block copolymer SOL T 190, produced by Polimeri Europa, 8.4 parts of BR-E5300 (stabilized hexachlorocyclododecane marketed by Chemtura) and 2.0 parts of Perkadox (2,3-dimethyl-2,3-diphenyl butane, marketed by Akzo Noble) 16 is introduced into the same device. A gear pump increases the load pressure of the molten additives to 270 barg.
    A quantity of 55 parts of a mixture of n-pentane and isopentane, in which the ratio n-pentane / isopentane is 70/30 by weight, is metered, by means of a pump 41, is fed to the exchanger 43, where the temperature of the expansion system is raised to 110 ° C. The heated expansion system is injected into the additive stream 46a and is incorporated therein through a set of mixing elements 46b. The resulting side stream 22 has a temperature of 180 ° C and a pressure of 240'bar. A quantity of 150 parts of the stream 22 is added to 850 parts of the main stream 21 and mixed therein by a second mixing device 34.
    A second gear pump 35 charges the resulting polymer stream to a filter exchanger device 40 in which a filter grid is inserted, of a mesh of 200 microns, doubled by a second grid of a mesh of 1000 microns .
    The filtered composition is first fed to the distributor 36 and then to the die 37, where it is extruded by a series of orifices having a diameter of 0.5 mm 37, and reduced to granules 38. The jet of water 13 has a temperature of 45 ° C and a pressure upstream of 20 bar. A stream of nitrogen 14 prevents the granulation chamber from clogging. The mass current ratio between the nitrogen stream 14 and the water stream 13 is 1: 3. The pressure in the granulation chamber is set to 3.5 bar.
    The granulated expandable resin is collected from the slurry 15, dried by a centrifuge and coated with a coating of 0.2% diglyceryl monostearate stearate and 0.1% zinc stearate based on the weight of the expandable particle. . The expansion is carried out under atmospheric current at 100.3 ° C for 3 minutes, the swollen beads are then allowed to air dry for 24 hrs.
    Part of the expanded beads are then molded into a press having a cylindrical mold chamber (90 mm high, 250 mm in diameter), while the remainder of the beads is inflated a second time in an atmospheric stream for 2 minutes.
    The expandable granules have a typical nut shape, as shown in Figure 3b.
    Example 2
    The mixture used in Example 1 is reproduced and processed in the units arranged as in FIG. 2.
    Example 3
    The procedure of Example 1 is repeated, but the side stream 16 consists of 33.1 parts of BR-E 5300, 47 parts of Minstron 002 talc produced by Luzenac, 10 parts of ethylene-di-stearamide and 6.5 parts of Perkadox30, and the polymer charge consisted of 73.4 parts of N2982. The pressure in the granulation chamber is set to 4.8 bar.
    The expandable granules have the typical shape of a nut, as shown in Figure 3c.
    Example 4
    The procedure of Example 1 is repeated, but the side stream 16 consists of 24.3 parts of BR-E 5300, 52 parts of Graphite MetalPure 5595 produced by Superior Graphite, 10 parts of ethylene-di-stearamide and , 1 part Perkadox 30, while the polymer charge 15 consists of 78.6 parts N2982. The pressure in the granulation chamber is set at 5.2 bar.
    The expandable granules have the typical shape of a nut, as shown in Figure 3a.
    Example 5
    The process of Example 4 is repeated, but a third heat exchanger is placed between the mixer 34 and the pump 35. The expandable polymer composition is cooled to 170 ° C. by the said heat exchanger and is then granulated under the same conditions than those indicated in Example 1.
    Example 6
    The procedure of Example 1 is repeated, but the side stream 16 consists of 35 parts of magnetite produced by Palabora Mining Company and 10 parts of ethylene-di-stearamide, while the polymer load consists of 125, 0 parts of N2982. The pressure in the granulation chamber is set at 5.5 bar.
    Example 7
    The procedure of Example 1 is repeated, but a charge of 750 parts of polymer is fed to the heat exchanger 35. The side stream 16 is composed of 10 parts of ethylene-di-stearamide, while the polymer load 15 consists of 140.0 parts of Polveri Europa produced polyethylene FG-20 and 100 parts of styrene-isoprene-styrene block copolymer SOL T 190 produced by Polimeri Europa.
    Example 8
    The procedure of Example 1 is repeated, but the liquid mixture fed to the reactor 31 consists of 8.0% by weight of ethylbenzene, 84.5% by weight of styrene, 7.0% by weight of weight of [α] -methylstyrolene, 0.5% by weight of styrene-butadiene-styrene rubber (SBS) sequenced.
    Comparative Example 1
    The process of Example 1 is repeated, but the temperature of the polymer at 21 and 22 is increased and raised to 230 ° C.
    Comparative Example 2
    The process of Example 1 is repeated, but the mass flow ratio between water 13 and nitrogen 14 introduced into mill 38 is brought to 10: 1, causing the granulation chamber to become clogged.
    Comparative Example 3
    The process of Example 1 is repeated, but a third heat exchanger is placed between the mixer 34 and the pump 35. The expandable composition is cooled to 150 ° C. by means of the said exchanger, and is then granulated according to the same conditions as in FIG. Example 1
    Table 1 and Table 2 show, for each example and each comparative example, the form factor, the average size of the granules, the average cell size, the quality of these cells, the density after 3 minutes of expansion, the density obtained after a second expansion of 2 minutes, the result obtained in fire test B2 according to DIN 4102, part 2, and the sintering percentage of the molded product.
    From the results, the expandable granules made according to the present invention, and the associated foamed and molded products, exhibit good processability during expansion and molding. Surprisingly, the data have shown that it is possible to obtain foamed products containing large amounts of different additives, using the same methods as those used with expandable vinyl aromatic polymers not containing said additives, without the performance is impaired.
    The comparative examples, which show products obtained by modifying the parameters of the processes so as to leave the ranges described in the present invention, or by modifying the processes proposed in the present invention, show a difficulty to manufacture low density products or to obtain quality products: the honeycomb structure in particular is not appropriate.
    Throughout this document, and in the absence of any other guidance, the term "part" implicitly refers to "part by weight". Same for the percentages values.
    The present invention is described in detail, with reference to its preferred embodiments, but it is clear that variations or modifications can be made to them without departing from the spirit and purpose of the present invention. . While the embodiments presented herein as examples of the invention clearly meet the objectives specified above, many modifications and other embodiments may of course be devised by those skilled in the art.
    It should be clear that the appended claims cover all of these modifications and embodiments, which represent a part of the scope and object of the present invention.
    Table 1
    Table 2
    Of course, the invention is not limited to the embodiments described above and shown, from which we can provide other modes and other embodiments, without departing from the scope of the invention. .
    权利要求:
    Claims (18)
    [1]
    A process for the continuous preparation of expandable granules based on thermoplastic polymers, by a granulation die, which comprises the following steps: i) bringing a stream of molten vinyl aromatic polymer to a reference temperature, said temperature of reference ranging from the critical temperature of the expansion system minus 25 ° C to the critical temperature of the expansion system plus 25 ° C; ii) incorporating in a second stream of molten polymer material, 0 to 60% by weight, based on the weight of the resulting stream, of inorganic and organic additives characterized in that they contain less than 10 percent by weight of particles having a size greater than half the diameter of the orifices of the die; iii) incorporating an expansion system in the melt polymer composition (ii) at a reference pressure, said reference pressure being greater than the critical pressure of the expansion system; iv) incorporating the polymer composition (iii) into the vinyl aromatic polymer stream (i); vii) granulating the thus obtained expansible polymer composition in the cutting chamber of a device for thermally granulating thermoplastic polymers, said device comprising: a) a die consisting of a cylindrical body comprising a series of orifices; extrusion on the outer surface and polymer adduction channels, placed inside the cylindrical body, in correspondence with the orifices and connected thereto; b) a set of blades, placed in correspondence with the orifices of the die, rigidly connected to a rotating rod; c) a set of injectors, located behind the set of blades, which generates a jet of liquid towards the die; d) an intake port through which a gas stream is introduced; and wherein the flow of gas from said inlet port (d) prevents clogging of the granulation chamber.
    [2]
    The method of claim 1, wherein said expansion system is an expansion agent or a mixture of blowing agents.
    [3]
    The method of claim 1 or claim 2, wherein the expansion system is heated to a temperature equal to or greater than the glass transition temperature of the majority polymer by weight, prior to incorporation into the polymer stream.
    [4]
    4. A process according to any one of the preceding claims, wherein the following step is inserted before granulation (vii): vi) passing the expandable composition through a filter, characterized in that the spacing of the mesh of the grid is not more than half the diameter of the orifices of the die, maintaining the pressure of the molten product at a value higher than the critical pressure of the expansion system.
    [5]
    5. Method according to claim 4, wherein the filter is characterized by a mesh size ranging from one tenth to one third of the diameter of the orifices of the die.
    [6]
    6. A process according to any one of the preceding claims, wherein the expansion system is directly incorporated into the vinyl aromatic stream (i).
    [7]
    The process according to claim 6, wherein the incorporation (iv) of the polymer composition and the expansion system is carried out by means of static or dynamic mixing devices, for a minimum residence time of 100 seconds and, at the same time, maintaining the pressure of the melted product at a value higher than the critical pressure of the expansion system.
    [8]
    A process according to any one of the preceding claims, wherein the following step is inserted before granulation (vii): v) cooling the expandable polymer composition (iv) to a temperature which is at least 50 ° C higher that the vitreous transition temperature of the majority polymer, relative to the weight, by maintaining the pressure of the molten product to a value greater than the critical pressure of the expansion system.
    [9]
    A process according to any one of the preceding claims comprising the following steps, after granulation of the expandable polymer composition (vii): viii) heating the reduced expandable granule composition to a temperature ranging from the glass transition temperature of the expandable composition minus 15 ° C at the glass transition temperature of the expansive composition increased by 15 ° C, for a duration greater than 60 seconds; (ix) cool the annealed granules to a temperature not exceeding 45 ° C.
    [10]
    The method of claim 9, wherein the annealing step is performed for a time greater than 180 seconds, and wherein the annealing step (viii) and the cooling step (ix) are performed at a pressure greater than 0.5 barg.
    [11]
    11. A process according to any one of the preceding claims, wherein said vinyl aromatic polymer stream of step (i) is in a molten state and comes directly from a polymerization equipment.
    [12]
    The method of claim 11, wherein said vinyl aromatic polymer stream, which originates from the venting port of a devolatilizer, is directly introduced in the molten state.
    [13]
    The process of any one of claims 1 to 10, wherein said aromatic vinyl polymer stream of step (i) is obtained by melting solid polymer particles in an extruder.
    [14]
    A process according to any one of the preceding claims, wherein the vinyl aromatic polymer material (i) is produced by polymerizing styrene with 0 to 50% by weight [alpha] -methylstyrolene; alkyl (meth) acrylate wherein the alkyl group is a C1-C4 alkyl group; vinyl acetate; acrylonitrile; conjugated dienes and their mixtures.
    [15]
    A process according to any one of the preceding claims, wherein the polymer material of step (ii) is selected from one or more of the following materials: a) homopolymers, random copolymers and block copolymers having a base aromatic vinyl, selected from polystyrene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene (SEP), styrene-butyl acrylate copolymers , impact polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN); b) polymers based on olefins, chosen from ethylene-vinyl acetate (EYA), polyethylene (PE), polybutylene terephthalate (PBT), polyethylene terephthalate (PET); c) condensation (co) polymers chosen from polycarbonates and polyesters, (meth) acrylic polymers, polyphenylene ether (PPO / PPE), technical polymers, polyamides, polylactates.
    [16]
    A process according to any one of the preceding claims, wherein a part or all of the polymer of step (ii) is obtained by melting the products already used based on aromatic vinyl products.
    [17]
    The process of any one of the preceding claims, wherein the additives in step (ii) are selected from: a) elemental carbon selected from carbon black, coke, carbon nanofibers, glassy carbon and graphite materials having a degree of graphitization, calculated by means of the Marie and Mering formula of at least 0.2; b) self-extinguishing agents selected from halogenated aromatic or aliphatic compounds or halogen-free compounds; c) Synergistic self-extinguishing agents selected from compounds having a C-C, N-N or O-type labile linkage; d) inorganic silicon, magnesium, aluminum derivatives selected from talc, hydrotalcite, and mica;
    [18]
    The method of any one of the preceding claims, wherein step (ii) is replaced by the following step of: (ii) bringing at least a second stream of molten vinyl aromatic polymer to a reference temperature , said reference temperature ranging from the critical temperature of the expansion system minus 25 ° C to the critical temperature of the expansion system plus 25 ° C.
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    同族专利:
    公开号 | 公开日
    JP5466637B2|2014-04-09|
    US8535585B2|2013-09-17|
    GB201220244D0|2012-12-26|
    HK1179571A1|2013-10-04|
    BRPI0811182A2|2014-10-29|
    BRPI0811182B1|2018-09-18|
    WO2008141766A1|2008-11-27|
    ES2323119A1|2009-07-06|
    US20100130627A1|2010-05-27|
    FR2919612A1|2009-02-06|
    PL385208A1|2008-11-24|
    CN101678565A|2010-03-24|
    GB2450961A|2009-01-14|
    US9447273B2|2016-09-20|
    HU0800317D0|2008-07-28|
    RU2518862C1|2014-06-10|
    US20130345328A1|2013-12-26|
    ES2323119B1|2010-03-17|
    PL209861B1|2011-10-31|
    RU2012146341A|2014-05-10|
    GB0808912D0|2008-06-25|
    DE102008064798B3|2019-12-24|
    GB2493310A|2013-01-30|
    RU2474494C2|2013-02-10|
    MX2009012013A|2010-02-17|
    CA2687393A1|2008-11-27|
    HU230913B1|2019-02-28|
    HK1127320A1|2009-09-25|
    HU0800317A2|2011-01-28|
    CA2687393C|2016-07-19|
    DE102008023702A1|2008-11-20|
    GB2493310B|2013-04-24|
    CN101678565B|2014-09-24|
    FR2919612B1|2012-07-27|
    DE102008023702B4|2016-05-12|
    GB2450961B|2013-01-02|
    JP2010527390A|2010-08-12|
    ITMI20071005A1|2008-11-19|
    RU2009147013A|2011-06-27|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI20071005|2007-05-18|
    IT001005A|ITMI20071005A1|2007-05-18|2007-05-18|PROCEDURE FOR THE PREPARATION OF EXPANDABLE THERMOPLASTIC POLYMER GRANULES AND ITS PRODUCT|
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