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    • 专利摘要:
    process for producing expanded foam particles made from a granule comprising at least one biodegradable polyester, such expanded foam particle, process for producing a mold part, such mold part, use of such a mold The invention relates to a process for producing expanded foam particles made from a granule comprising at least one biodegradable polyester, comprising the following steps: (i) producing a suspension containing a granule in a suspension medium, (ii) impregnating the granule in suspension from step (i) with at least one physical blowing agent, in order to obtain a granule loaded with blowing agents in suspension, while the mixture is heated under stirring to the imt relaxation temperature, (iii) relaxation of the suspension obtained in step (ii) after the retention time has expired and the relaxed suspension has been cooled with a watery liquid cooling medium in order to obtain expanded particles of foam. the process is carried out in an aqueous suspension medium, the blowing agent in step i or step ii is added during the heating phase or immediately after the cementing phase, and in step ii the suspension after heating is maintained for 3 to 100 minutes at a temperature ranging between mt and -5°c and mt and +2°c and the ratio of amount of cooling medium to suspending medium is at least 0.3.
    公开号:BR112016006949B1
    申请号:R112016006949-8
    申请日:2014-09-29
    公开日:2021-09-14
    发明作者:Uwe Keppeler
    申请人:Basf Se；
    IPC主号:
    专利说明:

    [0001] The invention relates to a process for the production of expanded foam particles from a granule comprising at least one biodegradable polyester obtained by means of polycondensation from: A1) 40 to 60% by mol, based in components A1) to A2), of a succinic acid, adipic acid or sebacic acid, brassilic acid or their respective ester-forming derivatives or mixtures thereof, A2) 40 to 60% by mol, based on components A1) to A2) , of a terephthalic acid or its ester-forming derivative, B) 98.5 to 100% by mol, based on components A1) to A2), of 1,4-butanediol or 1,3-propanediol or mixtures thereof ; and C) 0.05 to 1.5% by weight, based on components A1) to A2) and B, of a compound or several compounds selected from the group consisting of: C1) a compound with at least three groups capable of producing esters, C2) a di- or polyfunctional isocyanate, C3) a di- or polyfunctional epoxide; comprising the following steps: (i) Production of a suspension containing a granule in a suspending medium, (ii) Impregnation of the granule contained in the suspension of step (i) with at least one physical expansion agent, in order to obtain a granule loaded with expansion agents in suspension, while the mixture is heated under stirring to the relaxation temperature IMT, (iii) Relaxation of the suspension obtained in step (ii) after the end of the retention time and the cooling of the relaxed suspension with a watery liquid cooling medium, in order to obtain expanded foam particles, a process characterized by the fact that it is conducted in an aqueous medium of suspension, the blowing agent in step i or in step ii it is added during the heating phase or immediately after the heating phase and, in step ii, the suspension, after heating, is maintained for 3 to 100 minutes at a temperature ranging between IMT and -5 °C and the IMT and +2°C and the ratio of the amount of the cooling medium to the suspending medium is at least 0.3.
    [0002] In addition, the invention relates to the expanded foam particles obtained according to this process, the production of mold parts from these foam particles as well as the use of these mold parts for a layer for sports floors or stables or sports, for body protectors, for a protective padding on bicycle helmets, for covering elements in the automotive industry, for sound and vibration dampers, for packaging or for shoe soles.
    [0003] Foams made from plastics are artificially produced materials with a cellular structure in their full volume and have a lower density than the compact material from which they were produced. Through the often unique combination of its mechanical properties, despite low densities, its importance as a light substance is continually greater. Due to their often very low thermal conductivities, some foams are of considerable importance as an insulating material.
    [0004] After the use of foams made from plastic, disposal is, in part, associated with problems. In addition to energy recycling, material recycling is often also possible. However, biodegradability would be desirable, for example, in a composting facility.
    [0005] Polyester-based foams are known from various publications. Such foams are usually produced through an extrusion process. A disadvantage of this process is that, with it, generally only simple molds such as blocks, slabs and thin layers (foam sheets) can be produced. Often, with this process, the maximum thickness that blocks can be produced is limited.
    [0006] However, through the use of foam particles, mold parts of almost any geometry can be produced.
    [0007] WO 2012/020112 describes, for example, the production of expandable particles based on polyester and thus foam particles obtained from them by means of an extrusion process. However, mold parts produced from this process are not always suitable, with regard to their mechanical properties, for uses that require high tensile strength and elongation at break.
    [0008] These problems can be circumvented by the so-called autoclave process as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A11, 1988.
    [0009] The demand profile of the foam particles produced in this way or of the resulting mold parts can be quite different according to the field of application. However, common minimum requirements can be defined for the suitability of the process for different substances. These are:• producibility of foam particles over a wide range of bulk density, where in particular a low bulk density, if possible, should be achievable irrespective of particle geometry and size. A low weight of the resulting mold parts results in cost savings.• Foam particles with a predominantly closed cellular structure of foam. This results in good processability with conventional molding machines in the pressure filling process and in a low water absorption.• integral polymer particle impregnation for foam particles without compact core. (Without prejudice to the mechanical properties and feel of the parts resulting from the mold.)
    [0010] To satisfy these requirements, several parameters can be varied during the autoclave process. These include, among others, the suspending medium, the type of blowing agent and its concentration, the heating curve and the impregnation temperature (IMT). Particularly suitable parameters or a particularly suitable combination of parameters, generally in this case cannot be transferred from one substance to another.
    [0011] WO 00/68303 generally describes the production of expanded polymer particles based on biodegradable saturated polyesters in an autoclave process. Here, preferably ethylene glycol and glycerol with a density between 1.1 and 1.25 g/cm3 is used as suspension medium. This process cannot always completely satisfy with regard to the mode of operation, the process capacity and the profile property of the expanded and thereby accessible foam particles.
    [0012] From JP 2004 143269, an autoclave process is known, the microgranule foams from the above defined biodegradable polyesters, the advantageous cooling of the suspension medium by adding a cooling medium is not described in JP 2004 143269. With regard to batch homogeneity, foam particle surface composition and hence particle connected brightness cannot be satisfied from the known process of JP 2004 143269. Furthermore, particles of foams accessible from micro-granules and the mold parts thus obtained have an unsatisfactory return elasticity.
    [0013] We have now found a competent autoclave process for the production of expanded foam particles from a granule containing at least one biodegradable polyester obtained by means of polycondensation: A1) 40 to 60% by mol, based on the components A1 ) to A2), of a succinic acid, azelaic acid, adipic acid, sebacic acid, brassilic acid or their respective ester-forming derivatives or mixtures thereof, A2) 40 to 60% by mol, based on components A1) to A2) , of a terephthalic acid or its ester-forming derivative, B) 98.5 to 100% by mol, based on components A1) to A2), of 1,4-butanediol or 1,3-propanediol or mixtures thereof ; and C) 0.05 to 1.5% by weight, based on components A1) to A2) and B, of a compound or several compounds selected from the group consisting of: C1) a compound with at least three groups capable of producing esters, C2) a di- or polyfunctional isocyanate, C3) a di- or polyfunctional epoxide; comprising the following steps: D) ) Production of a suspension containing a granule in a suspending medium, E) i) Impregnation of the granule contained in the suspension of step (i) with at least one physical blowing agent, in order to obtain a granule loaded with blowing agents in suspension, while the mixture is heated under stirring to the relaxation temperature IMT, eF) ii ) Relaxation of the suspension obtained in step (ii) after the end of the retention time and the cooling of the relaxed suspension with a watery liquid cooling medium, in order to obtain expanded foam particles, a process characterized by the fact that it is conducted in a aqueous medium of suspension, the blowing agent in the step i or step ii is added during the heating phase or immediately after the heating phase and, in step ii, the suspension after heating is maintained for 3 to 100 minutes at a temperature ranging between IMT and - 5°C and IMT and +2°C and the ratio of the amount of the cooling medium to the suspending medium is at least 0.3.
    [0014] With this process, it is possible to produce the expandable foam particle capable by the process without the problems described above, wherein the expandable foam particle comprises the minimum requirements described above. Foam particles can be easily worked into mold parts, which have excellent mechanical properties with respect to tensile strength, elongation at break, return elasticity (rebound) and pressure deformation residue.
    [0015] Next, the invention will be described in detail.
    [0016] For the process according to the invention for producing expanded foam particles, granules containing the above-mentioned biodegradable polyesters are used.
    Biodegradable polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds are also referred to as partially aromatic polyesters. Together these polyesters are biodegradable in accordance with DIN EN 13432. Of course, blends of several of these polyesters are also suitable.
    [0018] According to the invention, partially aromatic polyesters (aliphatic-aromatic) are also to be understood as polyester derivatives, which comprise up to 10% by mol of other functions such as ester functions, such as ester-polyether, starch -polyester or amide-ester-polyether and polyester-urethane. Suitable partially aromatic polyesters include non-chain extended linear polyesters (WO 92/09654). Preferably, non-chain extended and/or branched partially aromatic polyesters. The latter are known from the aforementioned documents WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242 to which they are expressly referred. Blends of different partially aromatic polyesters also come into consideration. Interesting recent developments are based on renewable raw materials (see WO-A 2006/097353, WO-A 2006/097354 and WO2010/034689). Partially aromatic polyesters include products such as ecoflex® (BASF SE) and Enpol® (Ire Chemicals).
    Preferred partially aromatic polyesters include polyesters which contain, as essential components: A1) 40 to 60% by mol, preferably 52 to 58% by mol, based on components A1) to A2), of a succinic acid, acid adipic, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures or mixtures thereof, in particular preferably of a succinic acid, adipic acid or sebacic acid, A2) 40 to 60% by mol, preferably 42 to 48 % by mol, based on components A1) to A2), of a terephthalic acid or its ester-forming derivative, G) 98.5 to 100% by mol, based on components A1) to A2), from 1, 4-butanediol or 1,3-propanediol or mixtures thereof; eH) 0.05 to 1.5% by weight, based on components A1) to A2) and B, of a compound or of several compounds selected from the group consisting of: C1) a compound with at least three groups capable of producing esters, preferably glycerol or pentaerythritol; C2) a di- or polyfunctional isocyanate, preferably hexamethylene diisocyanate; C3) a di- or polyfunctional epoxide, preferably a copolymer of styrene, (meth)acrylic acid and glycidyl acid methacrylate.
    [0020] As A1 components are used succinic acid, adipic acid, azelaic acid, sebacic acid, brassilic acid or their respective ester-forming derivatives or mixtures thereof. Particularly preferably, succinic acid, adipic acid or sebacic acid or their respective derivatives or their respective ester-forming mixtures are used. Succinic acid, azelaic acid and brassylic acid also have, in addition, the advantage that they are accessible from renewable raw materials.
    Particularly preferred are the following aliphatic-aromatic polyesters: polybutylene adipate terephthalate (PBAT) polybutylene sebacate terephthalate (PBSeT) or polybutylene succinate terephthalate (PBST), and more particularly preferred are polybutylene adipate terephthalate (PBAT) and polybutylene sebacate terephthalate (PBAT) and polybutylene sebacate terephthalate (PBSeT).
    Aromatic dicarboxylic acids or their A2 ester-forming derivatives can be used singly or as a mixture of two or more of them. Preferably terephthalic acid or its ester-forming derivatives such as dimethyl terephthalate is used. As component B, 1,4-butanediol and 1,3-propanediol are used. These also have, in addition, the advantage that they are accessible from renewable raw materials. And mixtures can also be used.
    Generally 0.01 to 2% by weight, preferably 0.05 to 1.5% by weight, and particularly preferably 0.1 to 0.3% by weight, based on the total weight of the polyester, are used. of a branching agent (C1) and/or 0.1 to 1.5% by weight, based on the total weight of the polyester, of a chain extender (C2 or C3). The branching agent is preferably at least a trifunctional alcohol or a carboxylic acid at least trifunctional. Chain extenders are particularly suitable for difunctional isocyanates or epoxides.
    Particularly preferred C1 branching agents have three to six functional groups. Examples are: tartaric acid, citric acid, malic acid; trimethylolpropane, trimethylolethane; pentaerythritol; polyether triols and glycerol, trimesic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic dianhydride. Preferably polyols are, for example, trimethylolpropane, pentaerythritol, and particularly glycerol. By means of component C, biodegradable polyesters can be constructed with a structural viscosity. Biodegradable polyester can be easily worked.
    [0025] As chain extenders (C2 or C3), which can also be understood as long-chain branching agents, particularly hexamethylene diisocyanate or a copolymer of styrene, (meth)acrylic acid and glycidyl acid methacrylate are used .
    [0026] Polyesters generally have a number average molecular weight (Mn) ranging from 5,000 to 100,000, particularly from 10,000 to 75,000 g/mol, preferably from 15,000 to 38,000 g/mol, a weight average molecular weight (Mw) ranging from 30,000 to 300,000, preferably 60,000 to 200,000 g/mol and a Mw/Mn ratio from 1 to 6, preferably from 2 to 4. The viscosity index is between 50 to 450, preferably between 80 to 250 g/ ml (measured in o-dichlorobenzene/phenol (weight ratio 50/50)). The melting point ranges from 85 to 150, preferably from 95 to 140°C.
    [0027] Preferred partially aromatic polyesters are characterized by a molecular weight (Mn) ranging from 1,000 to 100,000, particularly from 9,000 to 75,000 g/mol, preferably between 10,000 and 50,000 g/mol, and a melting point that ranges from 60 to 170, preferably from 80 to 150°C.
    [0028] The MVR (melt volume ratio), according to EN ISO 1133 (190°C, 2.16 kg in weight), is generally between 0.1 and 70, preferably between 0.8 and 70 and particularly between 1 to 60cm3/10 min.
    [0029] The acidity indices, according to DIN EN 12634, are generally between 0.01 and 1.2mg of KOH/g, preferably between 0.01 and 1.0mg of KOH/g, and preferably, in in particular, between 0.01 and 0.7mg KOH/g.
    [0030] The individual steps (i) to (iii) of the process according to the invention are described in detail below.
    [0031] Step (i) of the process according to the invention comprises the production of a suspension containing a polyester granule described above in a suspension medium.
    [0032] In step (i) of the process according to the invention, the polyester is used in the form of a granule. The process allows the use of a wide range of different particle sizes and therefore also different particle weights. The average particle size (the average particle weight), however, is one of the crucial specific values, which influence the choice of the right production parameters.
    [0033] The weight of the particles determines the weight and influences the size of the expanded foam particles.
    [0034] The mean particle weight is determined as the arithmetic mean weighing 3 times 10 particles.
    [0035] The polyester bead may have an average diameter of 1 to 6 mm, particularly 2 to 5 mm, particularly preferably 3 to 4.5 mm.
    [0036] This preferably cylindrical or round granule can be produced by means of all compounding processes known to the person skilled in the art, with a subsequent granulation such as cold or hot cutting. For example, through the composition of the polyester, as the case may be, together with other additives in a twin screw extruder, extrusion from the extruder, eventually cooling and granulation. Said processes are described, for example, in Kunststoff Taschenbuch, HanserVerlag, 28. Auflage, in 2001.
    The individual particles of such granules generally have a weight of 0.5 to 100 mg/particles. Depending on the use, different particle sizes and foam particle bulk densities are preferred. It has now been found that for applications that require high elasticity of return (rebound) such as, for example, shoe soles of sports shoes or layers for sports floors, particularly foam particles with an average particle weight of 10 to 60mg/particle and particularly preferably from 21 to 50mg/particle. Mold parts produced from these foam particles generally have a return elasticity, measured according to DIN EN ISO 8307 of 01.01.2008, of 50% to 80% and preferably 60% to 75%. However, if the foam particles are produced according to the process described in JP 2004 143269, then the mold parts produced from them have a significantly lower return elasticity.
    [0038] Preferred granules to be used in step (i) of the process according to the invention may optionally include other additives.
    [0039] These can be, for example, nucleation agents, through which cellularity can be influenced. These are generally used in amounts between 0.001 and 10.0%, preferably 0.01 to 1.0%, and particularly preferably 0.02 to 0.2%, based on the granules. Suitable examples are, for example, talc, paraffins and/or waxes, as well as soot, graphite and fumed silicic acid, in addition to natural or synthetic zeolites and, optionally, modified bentonite, particularly preferably talc.
    [0040] The preferred granule used in step (i) may further comprise conventional additives such as antioxidants, stabilizers, flame retardants, waxes, fillers, pigments and dyes. Suitable additives are known to the person skilled in the art and are shown, for example, in EP 1514896 A1.
    [0041] In step (i) of the process according to the invention, the granule is suspended in a suitable suspending medium. In general, all suitable means of suspension known to the person skilled in the art can be used, in which it is ensured that the granule used does not dissolve therein. According to the invention, particularly suitable aqueous suspension media are, for example, water, or mixtures of water with 5 to 50% by weight, based on a mixture of a polar organic solvent, such as methanol, ethanol, propanol, such as iso-propanol, glycerol, ethylene glycol, or ketones such as acetone, or mixtures of organic solvents. In order to obtain, if possible, a homogeneous suspension of the granule with the least possible agitation effort, a suspension medium having a density comparable to that of the granule, i.e. a density between 1, was preferably selected in WO00/68303. 1 and 1.3 kg/m3. In WO00/68303 it is therefore recommended to use liquids such as ethylene glycol and glycerol with densities between 1.1 and 1.3 kg/m3 as suspension medium. However, substances such as ethylene glycol are harmful to health and form flammable vapor-air mixtures above the flash point. It has been found that, in step (i) of the process according to the invention, a watery mixture or, preferably, water can be used as a suspending medium, which does not have the aforementioned disadvantages.
    [0042] The amount of suspension medium of the suspension is generally selected in such a way that the proportion of phases of the granule used in step (i) in relation to the suspension medium is greater than 0.2, preferably greater than 0. 25. The proportion of phases of the granule used in step (i) to the suspending medium is generally less than 1.20, preferably less than 1.00, and particularly preferably less than 0.80.
    [0043] The proportion of phase according to the invention refers to the proportion of granule, measured in kilograms, in relation to the suspension medium, also in kilograms. It is known to the person skilled in the art how the proportion according to the invention can be adjusted, for example, in the case of 500 kg of granule in 1000 kg of water, the proportion of granule phase to water is 0.5 .
    [0044] The amount of granule, which is added to the suspension according to step (i), results from the above-described phase ratio of granule to the suspension medium.
    [0045] Preferably, the granule is suspended in a stirred reactor in water. At the same time, at least one suspension aid is preferably added in order to ensure an even distribution of the granule in the suspending medium.
    Suitable suspension adjuvants are water-insoluble inorganic stabilizers such as, for example, tricalcium phosphate, magnesium pyrophosphate, metal carbonates such as particularly calcium carbonate, and furthermore polyvinyl alcohol and surfactants. Such suspension adjuvants, particularly the water-insoluble inorganic stabilizers mentioned above, are generally used in amounts of 0.005 to 10% by weight, based on the total suspension. Ionic surfactants such as, for example, sodium dodecyl aryl sulfonate, or non-ionic surfactants such as, for example, fatty alcohol ethoxylate, as described in "Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Topic: Surfactants", are commonly used in an amount of 2 to 2000 ppm, particularly 2 to 500 ppm, based on the total suspension. Typically, a water-insoluble compound is used in combination with a surface-active substance (surfactant). In the process according to the invention, a water-insoluble inorganic stabilizer can also be dispensed with.
    [0047] Step (i) of the process according to the invention can be carried out at all suitable temperatures. These temperatures are known to the person skilled in the art, for example, step (i) of the process according to the invention is generally carried out at a temperature at which the suspending medium used is liquid, for example at a temperature of 15 to 35 °C, preferably at room temperature.
    [0048] Step (ii) of the process according to the invention comprises the impregnation of the suspended granule of step (i) with at least one expansion agent, in order to obtain a granule loaded with suspended expansion agents.
    [0049] In step (ii) of the process according to the invention is worked, for example, in an impregnation reservoir, for example, in a stirred tank reactor. In the reactor, for example, in an impregnation tank there is usually the suspension of step (i) of the process according to the invention, preferably as a mini granule, in water as a suspension medium, as well as, if necessary, an adjuvant. suspension. Then at least one blowing agent is added to this suspension.
    [0050] In general, all blowing agents known to the person skilled in the art can be used. The boiling point of the blowing agent is generally at atmospheric pressure between -25 to 150 °C, particularly between -10 and 125 °C.
    [0051] The blowing agent is preferably an aliphatic hydrocarbon, linear or cyclic, such as methane, ethane, n-propanol, iso-propane, n-butane, iso-butane, pentane, cyclopentane, hexane and heptane, halogenated hydrocarbons such as dichlorodifluoromethane, trichloromonofluoromethane, an alcohol such as methanol, ethanol, n-propanol, isopropanol and n-butanol, a ketone such as 3,3-dimethyl-2-butanone and 4-methyl-2-pentanone, an ether, ester or nitrogen, air or carbon dioxide. Mixtures of blowing agents can also be used. Preferably, butane is used as a blowing agent - in practice, often a technical mixture of n- and iso-butane - and nitrogen as a co-blowing agent.
    [0052] Due to the different solubilities of blowing agents in polyesters according to the invention, the properties of the expanded foam particle can be influenced through the choice of blowing agent and the amount of blowing agent used, particularly, the density apparent, cellularity and crystallinity. These particle properties, in turn, influence the subsequent workability and properties of mold parts resulting from processing. In particular, hydrocarbons such as butane differ significantly in their solubility in the polyesters according to the invention compared to carbon dioxide.
    Preferred as blowing agents are n-butane, iso-butane, the aforementioned technical mixture of both butanes, carbon dioxide and/or nitrogen, and particularly preferably n-butane or carbon dioxide. Carbon dioxide and/or nitrogen, preferably nitrogen, can be used as co-blowing agents as mentioned above.
    [0054] Likewise, at least one blowing agent is used, generally in an amount of 1 to 50% by weight, preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight, each one based on the bead. In this quantity of blowing agent a particularly good impregnation quality is ensured. The blowing agent can be introduced all at once or in portions. A co-expanding agent such as nitrogen is normally introduced at a (initial) temperature below the first melting point in the DSC (differential scanning calorimetry) of the polyester according to the invention, e.g. 50 °C. At the same time, the internal pressure in the impregnation reactor is increased by means of the pressure of the co-expanding agent to preferably 2 to 15 bar.
    [0055] When using butane or carbon dioxide as a blowing agent with nitrogen as a co-blowing agent, particularly, cell density can be increased and the resulting bulk density can be reduced.
    [0056] The reactor contents are heated, generally, at a high heating rate, i.e. greater than 1.5°C/min, preferably greater than 2.0°C/min to a suspension temperature of 90 to 110°C. The addition of the blowing agent can take place before, during or after heating the reactor contents, preferably before heating. The blowing agent must, however, be added before the start of the retention time.
    [0057] The actual impregnation temperature, that is, the temperature in the case of a sudden relaxation that occurs in step (iii), should be close to the softening temperature of the copolyester, for example, 30 °C at least 20°C above the melting temperature (crystalline melting point) of polyester. In the copolyesters according to the invention, impregnation temperatures are preferred between 100 and 130°C, particularly between 100 and 120°C.
    [0058] Depending on the amount and type of blowing agent, as well as after increasing the temperature, a pressure (impregnation pressure) is used in the closed reactor, which generally represents an excess pressure of 10 to 40 bar .
    [0059] By means of the present increase in temperature and excess pressure in the impregnation conditions, the blowing agents diffuse into the granule particles of the copolyesters according to the invention. Depending on the type and concentration of blowing agent, the particle weight, the selected phase ratio, as well as the degree of filling of the tank, this occurs at a different speed. However, only with a complete impregnation, in step (iii) of the process, foam particles with the desired property profile are obtained.
    [0060] Selected impregnation parameters: particle weight, suspending medium, type and concentration of blowing agent, phase ratio, degree of tank filling and IMT influence, within certain limits, the subsequent crystallinity of the particle. foam and thus on its other particle physical properties as well as on its properties during mold part processing.
    [0061] It has now been found that the essential parameter for adjusting the crystallinity of the foam particle is a slower rate of heating of 5°C before reaching the IMT. Particularly, it has an average heating rate of from 0.05 to 1.5 °C/min, preferably from 0.08 to 0.5 °C/min and particularly preferably from 0.1 to 0.24 °C/min , where 5°C proved to be advantageous before reaching the IMT.
    [0062] The average heating rate in the IMT range corresponds, in practice, to a retention time of the suspension during the impregnation process at a temperature range of 5 °C below the IMT and 2 °C above the IMT for one period from 3 to 100 minutes, preferably from 10 to 60 minutes and particularly preferably from 21 to 50 minutes.
    [0063] At high average heating rates (>1.5 °C/min) or retention times below 3 minutes, even at high blowing agent concentrations or through an increase in IMT, it is not possible to achieve densities apparent lows (<300 kg/m3) or acceptable impregnating qualities. Product homogeneity (narrow particle size distribution) worsens dramatically in some cases. Lower average heating rates or even longer retention times, above 100 minutes, do not show any significant improvement, nor are they economically viable.
    [0064] The aim of the process according to the invention is a narrow particle size distribution within a batch and a complete expansion of the output granules to foam particles. However, generally, the batch of unfoamed or partially foamed material should be separated with a sieve with a screen width MM=PD*1.25, where PD of UWG corresponds to the mean particle diameter and in the case of pellets, corresponds to the length of diameter of the circular or ellipsoidal cutting surface. In case of insufficient impregnation, the sieve residue is around 15%, that is, the product fraction (yield) is less than 95%. In the case of an acceptable homogeneity, the sieve residue is between 5% and 15% and in a good homogeneity, the sieve residue is less than 5%, that is, a yield greater than 95%. The particles must be expanded to a uniform cell structure. In case of insufficient cell structure, a compact material is located in the center but also partially on the periphery of the foam particle, or the cells are located (although only a few) along the entire volume of the foam particle with ends cells or cell walls with a thickness greater than 500μm.
    [0065] An acceptable cell structure means a complete impregnation of the polymer particle (cell structure over the entire volume of the foam particle without a compact core or the cell ends or cell walls have a thickness between 150μm and 500μm in the center). The outer covering of the foam particle is from thin to compact cells in a layer thickness of less than 500μm.
    [0066] In case of good cell structure, the thickness of cell ends or cell walls in the center is less than 150μm. The outer layer of the foam particle is from thin to compact cells at a layer thickness less than 500μm.
    [0067] Depending on the choice of impregnation parameters (for example, the improper combination of blowing agent concentration, impregnation temperature and retention time), the particles may indeed have a good cell structure, but even so, at the end of the step according to the invention, they can have a fully cracked particle surface. This happens particularly if the use of a temper is dispensed with. The goal is to produce firm foam particles with smooth, shiny particle surfaces.
    [0068] At the end of step (ii) according to the invention a granule loaded with expansion agents in suspension is obtained.
    [0069] Step (iii) of the process according to the invention comprises the relaxation and cooling of the suspension obtained in step (ii) by means of contact with a suitable cooling medium (quenching process).
    [0070] Generally, in step (iii) of the process according to the invention, the suspension is relaxed by means of a suitable device. Preferably, the suspension first leaves the impregnation tank via a valve. Then, in order to soften the relaxation jet and form a laminar flow, it can preferably be guided by means of a short piece of a relaxation tube, which supports a shield with an orifice at the end. By means of the length and diameter of the relaxation tube, as well as the diameter of the orifice shield, the relaxation time can be controlled.
    [0071] It is possible to relax the suspension directly at atmospheric pressure, eg 1013 mbar. Preferably, however, it is relaxed in an intermediate reservoir, where its pressure for foaming the particle loaded with granule blowing agent is sufficient, however it may be greater than atmospheric pressure. For example, it is relaxed to a pressure of, for example, 0.5 to 5, particularly 1 to 3 bar overpressure. During relaxation, the resulting impregnation pressure (pressure that results from selected impregnation parameters before the relaxation step) can be maintained in the impregnation reservoir, while the expansion agent or inert gas such as nitrogen is pressed. But it is also possible and often advantageous, a few seconds before relaxation, to increase the pressure resulting from impregnation by means of nitrogen pressure (extrusion pressure), generally up to 40bar, and then keep this extrusion pressure also constant. Increasing extrusion pressure, in particular, results in lower bulk densities and a more homogeneous product (narrower particle size distribution).
    [0072] During relaxation, the blowing agent contained in the granule expands so that expanded foam particles are obtained. Thus, after relaxation, a suspension of expanded foam particles is obtained.
    [0073] During the relaxation step, the suspension may be brought into contact with a suitable liquid medium for cooling (quenching). The addition of the cooling medium generally takes place by means of one or more annular nozzles arranged immediately after the corresponding relaxation device. This results in foam particles with a thicker skin and therefore a smoother and shinier particle surface compared to an untempered relaxation step. Such products result in advantages during subsequent processing for mold parts and in the resulting mold parts (smoother and brighter surface of mold parts). A corresponding process is described, for example, for foams made of polypropylene particles in EP 2336225. As a cooling medium, water with a temperature of between 5°C and 50°C is preferably used. The ratio of the amount of cooling medium to the amount of suspension medium used is at least 0.3 and 20, and preferably 0.6 and 10.
    [0074] The expanded foam particles can be separated in a conventional way from the suspension, for example, by means of filtrations, for example, with a screen sieve or a curved sieve or by a continuously operating centrifuge.
    [0075] Furthermore, it can be removed, if necessary, before or after separation, adjuvants still adherent to suspension and/or suspension adjuvants. The expanded foam particles can then be washed and dried.
    [0076] In another step, at least the non-foamed particles are separated with appropriate sieves.
    [0077] The expanded foam particles obtained after step (iii) generally have a bulk density of 5 to 300 kg/m3, preferably 30 to 200 kg/m3 and particularly preferably 60 to 120 kg/m3.
    [0078] In another modality of the process according to the invention, the expanded foam particles (expanded foam particles S) obtained in step (iii) are again foamed in order to obtain expanded foam particles N with a bulk density bottom. This step is also called "post-foaming". This additional step is particularly used to take advantage of transport and storage of foam particles with high bulk densities. Thus, a necessarily low bulk density can then be produced only when needed.
    [0079] The processes, in order to continue forming foams in the expanded foam particles obtained in step (iii) of the process according to the invention, are known to the person skilled in the art and are described, for example, in EP 1 533 335.
    [0080] The foam particles S can optionally be supplied before post-foaming with an anti-sticking medium. This happens in a preferred modality, by means of coatings. Typical anti-sticking means are also described in EP 1 533 335.
    [0081] The ratio of the bulk density of the expanded foam particle S to the bulk density of the expanded foam particle by the post-foam formation N, the so-called expansion factor, is particularly preferably 1.2 to 3.
    [0082] The foam particles produced according to the invention S or N are predominantly closed cell, in which the determination of the volume share of closed cells occurs based on DIN EN ISO 4590 of 01.08.2003 and generally have a cell density (number of cells/area) from 1 to 750 cells/mm2, preferably from 2 to 500 cells/mm2, particularly from 5 to 200 cells/mm2 and particularly preferably from 10 to 100 cells/mm2.
    [0083] The expanded foam particles S or N are generally at least approximately spherical. The diameter is dependent on the selected output granule particle weight and the apparent produced density. But the foam particles usually have a diameter of from 1 to 30 mm, preferably from 3.5 to 25 mm, and particularly from 4.5 to 25 mm. In the case of non-spherical foam particles such as elongated, cylindrical or ellipsoidal foam particles, diameter is understood to be the longest dimension.
    [0084] For the characterization of the crystal structure, the expanded foam particles can be analyzed with Differential Scanning Calorimetry (DSC) according to ISO 11357-3 (German version of 01/04/2013). With this, 3 to 5mg of foam particles are heated between 20 °C and 200 °C with a heating rate of 20 °C/min and determine the resulting heat flux in the first cycle.
    [0085] In the initial run of DSC, respectively at least two and often up to four endothermic peaks can be detected respectively (see Fig. 1 for explanation). Thus the maximum peak of the peak appearing at higher temperatures is always above the melting point temperature of the polyester used or above the melting point when polyester blends are used. Furthermore, the peak maximum of at least one peak is at least two endothermic peaks existing below the temperature of the melting point of the polyester used (the melting point of the used polymer blend).
    [0086] It is revealed that the foam particles obtained by the process according to the invention always have this double or multiple peak structure in the DSC. Furthermore, it is demonstrated that there is good processability, particularly soldering, of the foam particle when the sum of the endothermic peaks (i.e., in Figure 1, the sum of the amounts of heat corresponding to areas A, B and C) results in a amount of heat at least 5 J/g. Through improved welding, mold parts with improved mechanical properties are accessible, for example, in a tensile test.
    [0087] The present application also refers to expanded foam particles, which can be obtained by the process according to the invention. These differ from the known foam particles from WO00/068303 in that they have a double or multiple peak structure in the DSC as per ISO 11357-3 (German version of 01/04/2013). The greater crystallinity of the foam particles according to the invention is evident in the measured endothermic amount of heat (greater than/equal to 5J/g) in the DSC according to ISO 11357-3 (German version of 01/04/2013). Exclusively endothermic heat fluxes occur.
    [0088] The S or N foam particles can be supplied with an antistatic agent. This takes place in a preferred modality by means of coatings.
    [0089] From the expanded foam particles produced according to the invention S or N, foamed mold bodies (foams) can be produced according to processes known to the person skilled in the art.
    [0090] For example, the expanded foam particles S or N can be bonded together in a continuous or batch process with the aid of an adhesive, for example, with polyurethane adhesives known in the literature.
    [0091] Preferably, the expanded foam particles made of polyester are, however, heat-welded together in a closed mold. For this purpose, the foam particles are filled in the mold and after the mold is closed, steam or hot air is introduced, whereby the foam particles continue to expand and are welded together into a foam, preferably , with a density ranging from 8 to 300 kg/m3. Foams can be semi-finished products such as plates, structural profiles or raceways, or finished mold parts with a simple or complex geometry. Therefore, the term encompasses foam, semi-finished foam products and foam mold parts.
    [0092] The present invention, therefore, also relates to a foam comprising expanded particles of foam S or N, which can be produced, preferably produced by means of the process according to the invention.
    [0093] Furthermore, the present invention relates to a mold part that can be produced, preferably produced from expanded particles of foam S or N produced according to the invention.
    [0094] The present invention also relates to a mold part comprising expanded foam particles that can be produced by means of the process according to the invention.
    [0095] The present invention thus also relates to a process for the production of a mold part that involves at least the steps:
    [0096] 1. Production of foam particles S or N expanded according to the process according to the invention mentioned above and
    [0097] 2. Foaming of expanded particles of foam S or N in a corresponding mold in order to obtain a mold part.
    [0098] In this process, the expanded foam particles S or N, in accordance with steps (i) to (iii), are first produced as described above. Optionally, foam particles N can be produced from the foam particles S expanded via post-foaming.
    [0099] Step (2) involves foaming the expanded foam particles S or N into a corresponding mold in order to obtain a mold part.
    [00100] In a preferred embodiment, step (2) is performed while the expanded foam particles S or N are heat-welded together in a closed mold. For this purpose, the foam particles are preferably filled in the mold and after the mold is closed, steam or hot air is introduced, whereby the foam particles are expanded again and are welded together to one another. mold piece, preferably, with a density ranging from 8 to 350 kg/m3. The ratio of the density of the mold part to the bulk density of the expanded foam particles is generally less than 1.1.
    [00101] In a particularly preferred embodiment, the mold parts are obtained according to processes known to the person skilled in the art, such as the pressure filling process or the compression process, sinking process, or symmetry formation process or after pre-pressure loading. Such processes are disclosed in DE-A 25 42 453 and EP-A-0 072 499.
    [00102] The present invention also relates to the use of the expanded foam particle produced according to the invention with an average particle weight of 10 to 60 mg/particle for the production of mold parts.
    [00103] It has now been found that mold parts made from expanded foam particles with an average particle weight of 10 to 60 mg/particle have a high return elasticity in accordance with DIN EN ISO 1856 (50%, 22h, 23°C), of 01.01.2008 (repercussion). Rebound is significantly greater than the expanded foam particles of mold parts that were produced from expanded foam particles (JP 2004 143269) known in the literature.
    [00104] Furthermore, these mold parts have good tensile and compressive strength, a sufficiently low pressure deformation residue, as well as acceptable thermal resistance, so that they can be used for corresponding applications in the sports and leisure sector , in the packaging and automotive industries, as well as for technical applications. In particular, due to their high impact, these moldings are suitable for coverings for stable floors such as cow mattresses or sports floors or, for example, shoe soles for sports shoes.
    [00105] The invention is explained on the basis of the following examples, without being limited by them. EXAMPLES POLYESTERS USED AS GRANULES
    [00106] In the examples according to the invention aliphatic-aromatic polyesters listed in Table 1 were used. MATERIALS USED POLYESTER A
    [00107] For the production of polyester, 87.3 kg of dimethyl terephthalate, 80.3 kg of adipic acid, 117 kg of 1,4-butanediol and 0.2 kg of glycerol were mixed together with 0.028 kg of tetrabutyl-orthotitanate ( TBOT), in which the mole ratio between the alcohol components and the acid components was 1.30. The reaction mixture was heated to a temperature of 180°C and reacted at this temperature for 6 hours. Thereafter, the temperature was raised to 240°C and the excess of dihydroxy compound was vacuum distilled over a period of 3h. Then, 0.9 kg of hexamethylene diisocyanate was slowly metered in within 1h at 240°C.
    [00108] Polyester A thus obtained has a melting temperature of 119 °C and a molecular weight (Mn) of 23000 g/mol and an MVR (at 190 °C; 2.16 kg) of 3.3 g/10 min .
    [00109] This polyester A was granulated by an extruder with underwater granulation (UWG) into particles with a weight (arithmetic mean) of 40mg (A1) and 10mg (A2). POLYESTER B
    [00110] Polyester A was mixed with 0.1% by weight, referring to polyester, with talc (Micro Talc IT extra) from the company Mondo Minerals BV and was compounded in an extruder and produced in an underwater granulation (UWG) with an average particle weight (arithmetic mean) of 10mg. POLYESTER C
    [00111] Polyester C was produced like polyester A, but with only 0.5 kg of hexamethylene diisocyanate.
    The polyester C thus obtained had an MVR (at 190°C; 2.16 kg) of 8.8 g/10 min.
    II. EXPERIMENTAL OVERVIEW OF STEPS (I) TO (III) OF THE AGREEMENT PROCESS WITH THE INVENTION
    [00113] The experiments were carried out with a tank filling degree of 80%. EXAMPLES 1-13, AND V1-V2 WITH A PHASE RATIO OF 0.34
    [00114] 100 parts by weight (corresponding to 26.9% by weight, based on the total suspension without blowing agent) of the polyester granule, 265 parts by weight (corresponding to 71.3% by weight, based on the suspension total without blowing agent) water, 6.7 parts by weight of calcium carbonate, 0.13 parts by weight of a surface-active substance and the corresponding amount of blowing agent (based on the amount of granule used) were heated under stirring up to the impregnation temperature (IMT). At a temperature of 50°C in the liquid phase, nitrogen was pressed partially and additionally as a co-expanding agent and the internal pressure was adjusted to the previously defined pressure (eg 8bar or 14bar). The exact final adjusted pressure with nitrogen in the gas phase corresponds to Table 2. No pressure data means that, in this experiment, no additional nitrogen was pressed.
    [00115] Then, upon reaching the IMT and the corresponding IMP (impregnation pressure) after the retention time has been met, it is relaxed by a relaxation device and, during that time, it is cooled by quenching, with a total 350 parts by weight with cold water as a cooling medium by three arranged annular nozzles. EXAMPLE 14 WITH PHASE RATIO 0.74:
    [00116] 100 parts by weight (corresponding to 41.2% by weight, based on the total suspension without blowing agent) of the polyester granule, 136 parts by weight (corresponding to 56.0% by weight, based on the suspension total without blowing agent) water, 6.7 parts by weight of calcium carbonate, 0.13 parts by weight of a surface-active substance and the corresponding amount of blowing agent (based on the amount of granule used) were heated under stirring up to the impregnation temperature (IMT). At 50°C of the liquid phase, additional nitrogen is pressed and the internal pressure is adjusted to a pre-set pressure of 8 bar.
    [00117] Then, upon reaching the IMT and the corresponding IMP (impregnation pressure) after the retention time has been met, it is relaxed by a relaxation device and, during that time, it is cooled by quenching, with a total 350 parts by weight with cold water as a cooling medium by three arranged annular nozzles. COMPARATIVE EXAMPLE 3
    [00118] Comparative example 3 was carried out as in example 1 to 13 and V1-V2, however, it was worked without cooling by means of added cold water (quenching).
    [00119] The exact production parameters of examples 1 to 14 according to the invention, as well as comparative examples V1-V3, as well as the properties of the resulting S-foam particles are specified in Table 2. 111. PRODUCTION OF MOLD PARTS
    [00120] The production of the mold parts takes place on a conventional EPP molding machine (type K68 from the company Kurtz GmbH). It was produced with tools with dimensions 315x210x25 mm and rectangular test bodies 300*200*60 mm of different thickness. The 60mm thick molded parts were produced according to the pressure filling process, the 25mm thick molded parts were produced by the crack filling process.
    [00121] After production, the mold parts were stored at 60°C for 16h.
    [00122] The results of testing the mold parts are specified in Table 3. APPARENT TEST METHODS
    [00123] The determination takes place in accordance with DIN EN ISO 60: 2000-1. The foam particles are introduced with the aid of a funnel with fixed geometry (completely filled with bulk material) into a measuring cylinder with a known volume, the excess of the bulk material was removed with a rod with square edges of the measuring cylinder and the contents of the measuring cylinder was checked by weighing.
    [00124] The funnel used is 40 cm high, had an opening angle of 35° and an outlet with 50 mm in diameter. The measuring cylinder had an internal diameter of 188 mm and a volume of 10 I.
    [00125] The bulk density (SD) calculated from the bulk mass [kg]/0.01 [m3].
    [00126] The arithmetic mean was indicated from three measurements in km/m3 as apparent density.
    [00127] Execution in accordance with ISO 11357-3 (German version dated 01/04/2013) with DSC Q100 from TA Instruments.
    [00128] To determine the melting point of the polyester used in granular form, 3 to 5mg were heated in a first cycle between 20 °C and 200 °C with a heating rate of 20 °C/min, then they were cooled by 10°C/min to 20°C, followed by another heating cycle (second cycle) with a heating rate of 10°C/min.
    [00129] The peak maximum temperature was specified in the second cycle as the melting point.
    [00130] For the characterization of the crystal structure of the expanded foam particles, 3 to 5mg were heated between 20 °C and 200 °C with a heating rate of 20 °C/min and the resulting heat flux was determined. IMPREGNATION QUALITY
    [00131] The impregnation quality was determined according to a grading scale:- Insufficient Acceptable+ Good
    [00132] The impregnation quality was evaluated according to three criteria:- Homogeneity of a batch (PGV - particle size distribution),- Particle surface quality,- Particle cell structure.
    [00133] Each criterion is ranked according to the scale above. The overall impregnation quality score was the worst individual score. BATCH HOMOGENEITY CRITERIA
    [00134] The batch of foam particles was separated from the non-foamed or partially foamed materials with a sieve with a screen width MM=PD*1.25, where PD of UWG corresponds to the mean particle diameter and in the case of pellets, corresponds to the length of diameter of the circular or ellipsoidal cutting surface. In case of insufficient homogeneity, the sieve residue is around 15%, that is, the product fraction (yield) is less than 85%. In the case of an acceptable homogeneity, the sieve residue is between 5% and 15% and in a good homogeneity, the sieve residue is less than 5%, that is, a yield greater than 95%. PARTICULATE SURFACE QUALITY CRITERIA
    [00135] In the case of an insufficient particle surface, the particle has been completely cracked. In the case of an acceptable particle surface, the particle surface was rough and matte. In the case of a good particle surface, the particle was firm and the surface smooth and shiny. CRITERIA OF THE PARTICLE'S CELL STRUCTURE
    [00136] In the case of insufficient cell structure, a compact material is located in the center but also on the periphery of the foam particle, or the cells are located (although only a few) along the entire volume of the foam particle with cell ends or cell walls with a thickness greater than 500μm.
    [00137] An acceptable cell structure means a complete impregnation of the polymer particle (cell structure over the entire volume of the foam particle without compact core or the cell ends or cell walls have a thickness between 150μm and 500μm in the center). The outer covering of the foam particle is from thin to compact cells in a layer thickness of less than 500μm.
    [00138] In case of good cell structure, the thickness of cell ends or cell walls in the center is less than 150μm. The outer layer of the foam particle is from thin to compact cells at a layer thickness less than 500μm. CLOSED CELLULARITY
    [00139] The determination of the volume portion of the closed cells took place in accordance with DIN EN ISO 4590 of 01.08.2003. AVERAGE CELL DENSITY
    [00140] The evaluation of the foam structure occurred through optical image analysis using a PORE!SCANAdvanced Plus from the company Goldlücke Ingenieurleistungen. For this purpose, each 10 foam particles were divided in half and the respective cut surfaces were measured. In the case of non-spherical foam particles such as elongated, cylindrical or ellipsoidal foam particles, splitting towards the longer dimension has occurred.
    [00141] Mean cell density is the ratio of the number of cells on the cut surface to the cut surface and is expressed in 1/mm2.
    [00142] The value is associated with a classification: mean cell density [1/mm2]>10010-100<10GRADE OF COMPACTION (VG)
    [00143] The degree of compaction VG is the proportion of the density of the mold part (FT - Density) in relation to the apparent thickness (SD).
    [00144] VG = FT-Density [kg/m3]/SD [kg/m3]. PRESSURE DEFORMATION RESIDUE (DVR)
    [00145] Pressure deformation residue was determined in accordance with DIN EN ISO 1856, Method C. After removal of the test body from the test device, the thickness was measured first 24 hours after the recovery of the test body. TEMPERATURE STORAGE
    The test bodies (180x60x40 mm) were placed in the oven preheated to a corresponding storage temperature (100°C) and were stored at this temperature for 240 hours. Then, the evaluation of surfaces/corners.
    [00147] The surface and corner of the test bodies were evaluated during the storage period every 24 hours according to a grading scale. For this, the test bodies were briefly removed from the greenhouse.


    [00148] The test bodies were carefully removed from the oven after completion of temperature storage, were stored at room temperature for 24 hours under ambient conditions, and then the size change was measured with the slide gauge.
    [00149] The dimension change (length, width, height) is calculated using the following formula: DÃ = [(Lo-L1)/Lo)] x 100DÃ = dimension change in %Lo = initial measurement L1 = measurement after storage of heat
    [00150] The temperature resistance was good (OK), when the surfaces and corners had no changes and the average dimension change was less than 10% in length, width and height.

    - no or almost no expansion of the granule particles, the check was not applicable or not significant.
    权利要求:
    Claims (9)
    [0001]
    1. PROCESS FOR THE PRODUCTION OF EXPANDED FOAM PARTICLES MADE FROM A GRANULE, comprising a biodegradable polyester, which is composed of: A1) 40 to 60% by mol, based on components A1) to A2), of a succinic acid, adipic acid or sebacic acid, or mixtures thereof, A2) 40 to 60% by mol, based on components A1) to A2), of a terephthalic acid, (i) 98.5 to 100% by mol, based on components A1) to A2), of 1,4-butanediol or 1,3-propanediol or mixtures thereof; and (ii) 0.05 to 1.5% by weight, based on components A1) to A2) and B, of a compound or of several compounds selected from the group consisting of: C1) a compound of three to six groups capable of producing esters, C2) a di- or polyfunctional isocyanate, C3) a di- or polyfunctional epoxide; comprising the following steps: (iii) Production of a suspension containing a granule, having an arithmetic mean weight of particle from 10 to 60 mg/particle in a suspension medium, (iv) Impregnation of the granule obtained in the suspension of step (i) with a physical expansion agent, in order to obtain a granule loaded with expansion agents in suspension, while the mixture is heated under stirring to the relaxation temperature IMT, (v) i) Relaxation of the suspension obtained in step (ii) after the end of the retention time and cooling of the relaxed suspension with an aqueous cooling fluid medium, in order to obtain expanded foam particles, the process characterized by being conducted in a aqueous medium of suspension, the blowing agent in step (i) or step (ii) is added during the heating phase or immediately after the heating phase and, in step (ii), the suspension after heating is maintained, for 3 to 100 minutes, at a temperature ranging between IMT and -5 °C and IMT and +2 °C and the ratio of the amount of the cooling medium to the suspending medium is 0.3 to 20.0.
    [0002]
    2. PROCESS, according to claim 1, characterized in that the suspension is maintained, after heating, for 21 to 50 minutes at a temperature ranging between IMT and -5°C and IMT and +2°C and the IMT between 100 and 120°C.
    [0003]
    3. PROCESS, according to any one of claims 1 to 2, characterized in that a physical expansion agent selected from the group: n-butane, iso-butane, or CO2 is used.
    [0004]
    Process according to any one of claims 1 to 3, characterized in that a talc is used as nucleating agent 0.02% - 0.2% by weight, based on the biodegradable polyester.
    [0005]
    5. PROCESS, according to any one of claims 1 to 4, characterized in that in step (ii), with an initial temperature below the melting point of the polyester and measured with a Differential Scanning Calorimetry according to ISO 11357-3, of 01 /04/2013, the gas pressure along the suspension is raised by means of nitrogen pressure by 2 to 5 bar.
    [0006]
    6. EXPANDED FOAM PARTICLE, comprising a biodegradable polyester, which is composed of: A1) 40 to 60% by mol, based on components A1) to A2), of a succinic acid, adipic acid or sebacic acid, or mixtures thereof , A2) 40 to 60% by mol, based on components A1) to A2), of a terephthalic acid, B) 98.5 to 100% by mol, based on components A1) to A2), from 1.4 -butanediol or 1,3-propanediol or mixtures thereof; and C) 0.05 to 1.5% by weight, based on components A1) to A2) and B, of a compound or several compounds selected from the group consisting of: C1) a compound with three to six groups capable of producing esters, C2) a di- or polyfunctional isocyanate, C3) a di- or polyfunctional epoxide; With an arithmetic mean particle weight of 10 to 60 mg/particle and a bulk density of 5 to 150 kg/m3, characterized because it can be obtained through a process as defined in claim 2.
    [0007]
    7. PROCESS FOR THE PRODUCTION OF A DEMOLD PART, characterized in that the expanded foam particles, as defined in claim 6, are foamed in a mold.
    [0008]
    8. MOLD PART, characterized in that it is obtained through the process, as defined in claim 7, in which the mold part has a return elasticity, measured according to DIN EN ISO 8307 of 03/01/2008, greater than 50 %.
    [0009]
    9. USE OF THE CAST PART, as defined in claim 8, characterized in that it is for a layer for sports or stable floors, for body protectors, for a protective padding on bicycle helmets, for coating elements in the automotive industry, for sound and vibration dampers, for packaging or for shoe soles.
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    同族专利:
    公开号 | 公开日
    US20160244583A1|2016-08-25|
    EP3055352A1|2016-08-17|
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    JP6422957B2|2018-11-14|
    EP3055351A1|2016-08-17|
    US10138345B2|2018-11-27|
    EP3055351B1|2017-09-13|
    WO2015052019A1|2015-04-16|
    EP3055352B1|2017-09-13|
    CN105814126B|2019-05-07|
    ES2652344T3|2018-02-01|
    US9938389B2|2018-04-10|
    WO2015052020A1|2015-04-16|
    JP2016537450A|2016-12-01|
    US20160244584A1|2016-08-25|
    CN105793337A|2016-07-20|
    BR112016006949A2|2017-08-01|
    CN105814126A|2016-07-27|
    CN105793337B|2018-12-14|
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    法律状态:
    2020-01-28| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-07-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/09/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13187895|2013-10-09|
    EP13187895.1|2013-10-09|
    PCT/EP2014/070728|WO2015052020A1|2013-10-09|2014-09-29|Method for producing expanded polyester foam particles|
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