Patent Application
20190203009
The present invention relates to a process for producing foam particles composed of thermoplastic elastomers having polyamide segments by blowing agent impregnation in suspension, and also foam particles obtainable by the process.
WO 2011/134996 describes expandable polyamide pellets and the production thereof by extrusion of a blowing agent-comprising polymer melt and palletization under water. The blowing agent-comprising pellets can be foamed in a prefoamer to give foam particles and fused together in an automatic molding machine to give expanded polymer foams having a high long-term use temperature and solvent resistance.
WO 2006/045513 describes closed-cell, crosslink foam sheets or plates composed of polyether-polyamide block copolymers, which are obtainable by foaming a crosslinked polymer film or plate loaded with blowing agent in an automatic molding machine or autoclave.
WO 2016/030026 and WO 2016/030333 describe processes for producing expanded polymer particles based on polyamides, e.g. polyether block amides, by impregnation of the polymer melt with a blowing agent and expansion through a nozzle, wherein the polymer comprises a chain extender, for example a styrene-acrylate copolymer having epoxide groups.
WO 2014/198779 describes a process for producing expanded pellets composed of thermoplastic elastomers having a high elongation at break by palletization of a polymer melt loaded with carbon dioxide or nitrogen. Thermoplastic elastomers mentioned are, inter alia, polyether copolyamides having elastic polyether units and crystalline polyamide units. The foam particles obtained by this process frequently have excessively high bulk densities.
JP-A 60-042432 describes foam particles composed of crosslinked block copolymers made up of crystalline polyamide segments and polyether segments for producing elastic foam moldings. The foam particles obtained by this process likewise have excessively high bulk densities.
Processes for producing expanded foam particles composed of polypropylene (EPP) or biodegradable polyesters by blowing agent impregnation in suspension are, for example, known from EP 2 336 225 A1 or WO 2015/052019.
WO 2015/052265 describes a process for producing expanded, closed-cell thermoplastic elastomer particles having a closed outer skin, a low density and a homogeneous cell distribution by impregnation with gaseous CO2 or N2 in an autoclave reactor. This process requires very high pressures, long impregnation times and is not economically feasible on a large scale.
It was an object of the present invention to provide a process for producing foam particles which are composed of thermoplastic elastomers having polyamide segments and have a low bulk density and are able to be processed to give elastic foam moldings having a high recovery capability.
The object has been achieved by a process for producing foam particles composed of thermoplastic elastomers having polyamide segments, which comprises the following steps:
(a) production of a suspension of pellets of the thermoplastic elastomer in a suspension medium,
(b) addition of a blowing agent,
(c) impregnation of the pellets with the blowing agent by heating of the suspension in a pressure vessel to an impregnation temperature IMT at an impregnation pressure IMP,
(d) depressurization of the suspension by emptying of the pressure vessel via a depressurization device and work-up of the foam particles obtained.
As thermoplastic elastomers, preference is given to using polyamide TPEs (TPA) having soft segments having ether (TPA-ET), ester (TPA-ES) or both ether and ester linkages (TPA-EE), particularly preferably polyether block amides (PEBA).
The thermoplastic elastomer preferably has a nitrogen content in the range from 0.5 to 7.5% by weight, particularly preferably in the range from 1 to 5% by weight. The nitrogen content can be determined by means of elemental analysis. The proportion of the polyamide blocks and thus the proportion of hard segments can be calculated from the nitrogen content.
In general, the thermoplastic elastomers are used in the form of pellets in step (a). Preference is given to using cylindrical, ellipsoidal or spherical pellets having an average diameter of from 0.2 to 10 mm, in particular from 0.5 to 5 mm. In the case of cylindrical or ellipsoidal pellets, the diameter is for the present purposes the longest dimension.
The individual pellets generally have an average mass in the range from 1 to 50 mg, preferably the range from 5 to 25 mg. This average mass of the pellets (particle weight) is determined as arithmetic mean by triplicate weighing of in each case 10 pellets. These preferably cylindrical or round pellets can be produced by all compounding processes known to those skilled in the art with subsequent palletization as cold or hot cutting. For example by compounding, optionally together with further additives in a twin-screw extruder, expression from the extruder, optionally cooling and palletization. Such processes are described, for example, in the Kunststoff Taschenbuch, Hauser-Verlag, 28th edition, 2001.
The pellets can comprise not only the thermoplastic elastomer but also optionally customary additives such as antioxidants, stabilizers, flame retardants, waxes, fillers, pigments and dyes. Preference is given to using nucleating agents such as talc, paraffins, waxes, carbon black, graphite, pyrogenic silicas, natural or synthetic zeolites or bentonites in order to adjust the cell structure. These are generally used in amounts in the range from 0.01 to 5% by weight, based on the pellets.
The pellets are suspended in a suitable suspension medium, for example water, polar organic solvents such as alcohols, ketones or mixtures thereof. In general, water is used as suspension medium.
In general, the amount of the suspension medium is selected so that the phase ratio as weight ratio of pellets to suspension medium is in the range from 0.2 to 0.9.
In order to achieve uniform distribution of the pellets in the suspension medium, suspension aids are generally added. Suitable suspension aids are water-insoluble inorganic stabilizers such as tricalcium phosphate, magnesium pyrophosphate, metal carbonate such as calcium carbonate and also polyvinyl alcohol and ionic or nonionic surfactants. The suspension aids are usually employed in amounts of from 0.01 to 5% by weight.
In step (b), a blowing agent is added. Volatile substances having a boiling point at atmospheric pressure in the range from −10 to 125° C. or gases such as carbon dioxide or nitrogen are generally used. The bulk density, cell structure and crystallinity of the polymer matrix can be influenced by the choice of the type and amount of the blowing agent. Preference is given to using hydrocarbons having from 3 to 6 carbon atoms, in particular n-butane and isobutane, carbon dioxide, nitrogen or mixtures thereof as blowing agents. Particular preference is given to using butane. The blowing agents are generally used in amounts of from 1 to 50% by weight, based on the pellets.
Nitrogen can also be introduced as co-blowing agent at an onset temperature below the first melting peak in the DSC of the thermoplastic elastomer, for example in the range from 30 to 75° C., by injection and raising of the internal pressure in the impregnation reactor by from 200 to 3000 kPa.
The impregnation in step (c) is preferably carried out at an impregnation temperature IMT in the range from 80 to 180° C. For this purpose, the suspension is generally heated at a heating rate of preferably 2° C./min or higher to the impregnation temperature (IMT) and optionally maintained at this temperature or in a range from 2° C. above the IMT to 5° C. below the IMT for a period of from 2 to 100 minutes (hold time HT).
Depending on the type and amount of the blowing agent and the temperature or the treatment with a gas, a pressure (impregnation pressure IMP) is established in the closed pressure vessel. The impregnation in step (c) is preferably carried out at an impregnation pressure IMP in the range from 150 to 5500 kPa, particularly preferably in the range from 500 to 4000 kPa absolute.
In step (c), the pressure vessel is preferably supplied with nitrogen and the impregnation pressure IMP set at a temperature of the suspension in the range from 30 to 75° C.
The blowing agent-comprising pellets obtained in step (c) are foamed to give foam particles by depressurization in a subsequent step (d). The depressurization of the suspension in step (d) is generally effective by emptying the pressure vessel via an opened shut-off valve into an expansion vessel. As shut-off valve, it is possible to use a valve, a slider, a cock or a flap, with preference being given to ball valves. During emptying of the pressure vessel, the suspension can be depressurized directly to atmospheric pressure (1013 Pa) or in an intermediate vessel having a gauge pressure in the range from 100 to 1000 kPa. It can also be advantageous to keep the pressure (expression pressure) in the pressure vessel constant during depressurization by introduction of nitrogen or increase the pressure further to an expression pressure of up to 6000 kPa, preferably to a range from 3000 to 4000 kPa, by injection of nitrogen a few seconds before the depressurization. The increase in the expression pressure makes it possible to obtain foam particles having a lower bulk density and a narrower foam particle size distribution.
In step (d), the suspension is preferably brought into contact with a liquid coolant downstream of the depressurization apparatus. This step, which is also referred to as quenching, has been described, for example, for the production of expandable polypropylene (EPP) in EP-A 2 336 225. The process of the invention is preferably carried out using an amount of water which corresponds to the formula (mass of quenching water)/(mass of suspension medium)=0.5−2.0.
In an optional work-up step, the suspension aids which have been used and are still adhering to the foam particles can be removed from the foam particles obtained. The foam particles are subsequently washed and separated off from the liquid phase by filtration or centrifugation and then dried.
The foam particles composed of thermoplastic elastomers having polyamide segments which are obtainable by the process of the invention preferably have a bulk density in the range from 20 to 250 kg/m3, particularly preferably in the range from 35 to 150 kg/m3 and very particularly preferably in the range from 40 to 120 kg/m3.
The expanded foam particles are generally at least approximately spherical. The precise geometric shape or the diameter is dependent on the selected geometry and the particle weight of the starting pellets and on the bulk density produced.
The expanded foam particles produced according to the invention are predominantly closed-celled, with the determination of the proportion by volume of closed cells being carried out by a method based on DIN EN ISO 4590 of Aug. 1, 2003, and generally have a cell density (number of cells/area) of from 1 to 750 cells/mm2, preferably from 2 to 500 cells/mm2, in particular from 5 to 200 cells/mm2 and particularly preferably from 10 to 100 cells/mm2.
To characterize the crystalline structure, the expanded foam particles can be examined by differential scanning calorimetry (DSC) in accordance with ISO 11357-3 (German version of Apr. 1, 2013). For this purpose, 3-5 mg of the foam particles are heated between 20° C. and 200° C. at a heating rate of 20° C./min and the resulting heat flow is determined in the 1st run. Depending on the type of the thermoplastic elastomers used, at least two endothermic peaks can in each case be determined in the 1st DSC run.
The foam particles can be fused together by means of steam to give foam moldings having a low density of the molding. The density of the molding is preferably in the range 70-300 kg/m3, particularly preferably in the range 80-200 kg/m3.
Depending on the type and proportion of the soft phase in the thermoplastic polyamide elastomers used, surprisingly low steam pressures below 250 kPa (gauge pressure), in particular in the range from 80 to 150 kPa, can be used.
The mechanical properties of the foam moldings obtained by fusion of the foam particles obtainable by the process of the invention generally also depend on the thermoplastic polyamide elastomers used and on the type of filling process used in production of the moldings.
However, the foam moldings surprisingly display a high elasticity and recovery ability over a wide hardness range (Shore hardness A) of the thermoplastic polyamide elastomers used. They always have a ball rebound resilience measured in accordance with DIN EN ISO 8307:2007 (Determination of resilience by ball rebound DIN EN ISO 8307:2008-03) of at least 55%.
The invention will be illustrated by the following examples, without being restricted thereby:
Test Methods:
The following test methods and parameters were used, inter alia, to characterize the raw materials used and also the resulting foam particles and moldings:
Melting Point Determination by Means of DSC:
Procedure in accordance with ISO 11357-3 (German version of Apr. 1, 2013) using a DSC Q100 from TA Instruments. To determine the melting point of the thermoplastic elastomers used or of other thermoplastic elastomers according to the invention in pellet form, 3-5 mg are heated at a heating rate of 20° C./min in a 1st run between 20° C. and 200° C., subsequently cooled at 10° C./min to 20° C., followed by a further heating cycle (2nd run) at a heating rate of 10° C./min. The temperature of the peak maximum in the 2nd run was reported as melting point.
Crystalline Structure by DSC:
To characterize the crystalline structure of the compact thermoplastic elastomer or the expanded foam particles, 3-5 mg are heated at a heating rate of 20° C./min between 20° C. and 200° C. and the resulting heat flow is determined.
Bulk Density:
The determination was carried out by a method based on DIN EN ISO 60: 2000-1. Here, the foam particles were introduced into a measuring cylinder having a known volume with the aid of a funnel having a predetermined geometry (completely filled with bulk material), the excess of the bulk material was struck off from the measuring cylinder by means of a straight-edged bar and the contents of the measuring cylinder were determined by weighing.
The funnel used has a height of 40 cm, an opening angle of 35° C. and an outlet having a diameter of 50 mm. The measuring cylinder had an internal diameter of 188 mm and a volume of 10 l.
The bulk density (BD) is given by the mass of the bed [kg]/0.01 [m3].
The average of 3 measurements in kg/m3 was reported as bulk density.
The degree of compaction DC is the ratio of density of the molding (M density) to bulk density (BD). DC=M density [kg/m3]/BD [kg/m3].
The test specimens (180×60×M density mm) were placed in an oven which had been preheated to the appropriate storage temperature (110° C.) and stored at this temperature for 96 hours.
Assessment of the Surfaces/Edges as Follows:
The surface and edge of the test specimens was assessed every 24 hours during the storage time according to a scale of grades. For this purpose, the test specimens were briefly taken from the oven.
After the end of the hot storage, the test specimens were carefully taken from the oven, stored at room temperature for 24 hours under room conditions and the change in dimensions was subsequently measured by means of the sliding caliber.
The change in dimensions (length, width, height) is calculated according to the following formula:
CD=[(Lo−L1)/Lo)]×100
CD=change in dimension in %
Lo=original dimension
L1=dimension after hot storage
The heat resistance was satisfactory (OK) when surfaces and edges did not display any changes and the average change in dimensions over length, width and height was <10%. It is limited when this change in dimensions is achieved only in the case of storage at lower temperatures.
A TPA-EE, i.e. a polyether block amide (PEBA), was used as thermoplastic polyamide elastomer (TPA) in the examples according to the invention. Such products are supplied, for example, by Arkema Speciality Polyamides under the tradename PEBAX. The products listed in table 1 consist of flexible polytetrahydrofuran and crystalline polyamide units (PA-12).
Pellets having a particle weight of about 19 mg, whose composition is described in table 1, were used.
The experiments were carried out with a degree of fill of the vessel of 80% and a phase ratio of 0.41.
100 parts by weight (corresponding to 28.5% by weight, based on the total suspension without blowing agent) of the pellets, 245 parts by weight (corresponding to 69.6% by weight, based on the total suspension without blowing agent) of water, 6.7 parts by weight (corresponding to 1.9% by weight, based on the total suspension without blowing agent) of calcium carbonate, 0.13 part by weight (corresponding to 0.04% by weight, based on the total suspension without blowing agent) of a surface-active substance (Lutensol AT 25) and the appropriate amount of butane as blowing agent (based on the amount of pellets used) were heated while stirring. Nitrogen was then additionally injected at a temperature of the liquid phase of 50° C. and the internal pressure was set to a previously defined pressure (800 kPa). Depressurization is subsequently carried out via a depressurization apparatus after attainment of the impregnation temperature (IMT) and optionally after a hold time (HT) and at the impregnation pressure (IMP) set at the end. The gas space is here brought to a predetermined expression pressure and kept constant during the depressurization. The depressurization jet can optionally be cooled by means of a particular volume flow of water having a particular temperature (water quench) downstream of the depressurization apparatus. In examples 1-4 and 10, cooling was carried out using an amount of water at 25° C. which corresponds to the ratio (mass of quenching water)/(mass of suspension medium)=0.85.
After removal of the suspension aid (dispersant and soap) and drying, the bulk density (BD) of the resulting particles is measured.
As for examples 1-4, but 12% by weight of CO2 are used instead of butane as blowing agent and no additional nitrogen is injected.
The experiment was carried out with a degree of fill of the vessel of 70% and a phase ratio of 0.27.
100 parts by weight (corresponding to 21.2% by weight, based on the total suspension without blowing agent) of the pellets, 365 parts by weight (corresponding to 77.4% by weight, based on the total suspension without blowing agent) of water, 6.7 parts by weight (corresponding to 1.4% by weight, based on the total suspension without blowing agent) of calcium carbonate, 0.14 part by weight (corresponding to 0.03% by weight, based on the total suspension without blowing agent) of a surface-active substance (Lutensol AT 25) and the appropriate amount of butane as blowing agent (based on the amount of pellets used) were heated while stirring. No additional injection of nitrogen was carried out at 50° C. Depressurization is subsequently carried out via a depressurization apparatus after attainment of the impregnation temperature (IMT) and optionally after a hold time (HT) and at the impregnation pressure (IMP) set at the end. The gas space is here brought to a predetermined expression pressure (3700 kPa) and kept constant during the depressurization.
After removal of the suspension aid (dispersant and soap) and drying, the bulk density (BD) of the resulting foam particles is measured.
The experiments were carried out with a degree of fill of the vessel of 80% and a phase ratio of 0.31.
100 parts by weight (corresponding to 23.4% by weight, based on the total suspension without blowing agent) of the pellets, 320 parts by weight (corresponding to 75.0% by weight, based on the total suspension without blowing agent) of water, 6.7 parts by weight (corresponding to 1.6% by weight, based on the total suspension without blowing agent) of calcium carbonate, 0.13 part by weight (corresponding to 0.03% by weight, based on the total suspension without blowing agent) of a surface-active substance (Lutensol AT 25) and the appropriate amount of butane as blowing agent (based on the amount of pellets used) were heated while stirring.
In the case of example 15, no additional nitrogen is injected. In the case of example 16, nitrogen was additionally injected and the internal pressure set to a previously defined pressure (800 kPa) at a temperature of the liquid phase of 50° C.
The further course of the experiment is as in example 14.
The experimental parameters (blowing agent, amount of blowing agent, impregnation temperature (IMT), impregnation pressure (IMP), expression pressure) and the resulting bulk density (BD) for examples 1 to 16 according to the invention are reported in table 2.
The phase ratio is defined as the ratio of pellets, measured in kilograms, to suspension medium, which is preferably water, likewise in kilograms.
The hold time (HT) is defined as the time [min] for which the temperature of the liquid phase is in a temperature range from 5° C. below the IMT to 2° C. above the IMT.
Production of the Moldings:
The production of the moldings was carried out on a commercial automatic EPP molding machine (model K68 from Kurtz GmbH). Cuboidal test specimens having different thicknesses were produced using tools having the dimensions 315×210×25 mm and 315*210*20 mm. The moldings were produced by the pressure filling process or the crack filling process. After production of the moldings, the moldings were stored at 60° C. for 16 hours.
The results of the subsequent tests on the moldings are reported in table 3.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16175980.8 | Jun 2016 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/065275 | 6/21/2017 | WO | 00 |
