Patent Application
20200148851
The present invention relates to expandable, blowing agent-containing pellets based on high temperature thermoplastics having a poured density according to DIN ISO 697:1982 in the range from 400 to 700 kg/m3 and having a mass in the range from 1 to 5 mg/pellet, processes for the production thereof and expanded foam particles and particle foams obtainable therefrom and the use thereof for producing components for aviation.
WO 2013/092689 describes a process for producing foam sheets by extrusion of a blowing agent-laden polymer melt of polyphenylene ether sulfone (PPSU). It is preferable to employ a mixture of isopropanol as the blowing agent. The obtained foam sheet was subsequently subjected to forming under a vacuum and elevated temperature in a mold to afford a formed foam molding.
WO 2014/057042 describes a high temperature-resistant foam having a homogeneous cell size distribution based on a mixture of polyethersulfones.
EP 1 333 051 A2 describes a process for producing foam webs made of high temperature resistant polysulfones or polyethersulfones by foam extrusion of a mixture of a polysulfone or a polyether sulfone and a volatile blowing agent. It is preferable to employ water or a mixture of water with an alcohol or a ketone as the blowing agent.
EP 0 411 437 describes a process for producing expandable pellets based on polyaryl ether sulfones comprising 5% to 20% by weight based on the pellets of methyl ethyl ketone or acetone as a blowing agent, wherein the blowing agent and the polymers are mixed in an extruder at a barrel temperature of at least 50° C. and at most 170° C. and subsequently extruded directly into a medium having a temperature of less than 40° C. This process is limited to low through-puts. The pellets are pressed into 10 mm thick blowing agent-containing sheets in a positive mold and subsequently foamed to afford a 20 cm thick foam block. Cell diameters are in the range from 0.2 to 0.8 mm.
WO 2016/052604/EP 3 202 837 A1 describes a process for producing particle foams by sintering foam particles made of a polymer having a glass transition temperature of at least 180° C., in particular polyethersulfone (PESU), polyetherimide (PEI), polyphenylsulfone (PPSU) or polysul- fone (PSU). The foam particles preferably have a density in the range from 40 to 900 kg/m3 and average cell diameters in the range of 180-1500 μm. The particle foams obtained therefrom have a high open-cell content in the range from 33% to 64%.
The present invention has for its object to provide storage-stable, expandable pellets based on high temperature-resistant polymers, in particular polyethersulfones, which exhibit a low loss of blowing agent over several weeks' storage time and may be foamed/welded to afford foam particles or particle foams having a low density. In addition the expandable pellets shall be obtainable in high throughputs and should be simply processable into particle foams having a homogeneous, fine-celled cell structure.
The object is achieved by the expandable, blowing agent-containing pellets based on high temperature thermoplastics according to claim 1 and expanded foam particles according to claim 3.
Preferred embodiments are set out in the subsidiary claims.
The expandable pellets are preferably spherical. Spherical is to be understood as meaning that the pellets have no corners or edges, such as are a feature of cylindrical extruded pellets for example. The ratio of shortest to longest diameter of the spherical pellets is preferably in the range from 0.9 to 1.0, particularly preferably in the range from 0.95 to 0.99. Due to their sphericity the preferred expandable blowing agent-containing pellets and the foam particles obtainable by prefoaming are easy to convey and inject into foam molds via pneumatic conveying apparatuses.
The inventive expandable, blowing agent-containing pellets based on high temperature thermoplastics have a poured density according to DIN ISO 697:1982 in the range from 400 to 900 kg/m3, preferably in the range from 450 to 700 kg/m3 and particularly preferably in the range from 500 to 680 kg/m3. They have a mass in the range from 1 to 10 mg/pellet, preferably in the range from 2 to 4 mg/pellet.
Suitable high-temperature thermoplastics are thermoplastic polymers having a glass transition temperature of at least 180° C., preferably in the range from 200° C. to 240° C., determined by DSC according to ISO 11357-2-1999(E) with a heating rate of 10 K/min. The high temperature thermoplastic is preferably at least one polyethersulfone or mixtures of polyethersulfones having different weight-average molecular weights Mw or having different viscosity numbers. It is preferable to use mixtures of a polyethersulfone having a viscosity number in the range from 46 to 50 cm3/g and a polyethersulfone having a viscosity number in the range from 54 to 58 cm3/g measured according to ISO 307, 1157,1628 (in 0.01 g/ml phenol/1,2-ortho-dichlorbenzene, 1:1).
As the blowing agent the expandable pellets comprise alcohols, ketones or hydrocarbons having 1 to 4 carbon atoms, preferably acetone, methyl ethyl ketone, ethanol, isopropanol, isobutane, water or mixtures thereof in amounts of 3% to 15% by weight, preferably in amounts of 5% to 10% by weight, wherein the expandable pellets particularly preferably comprise 3% to 10% by weight of acetone.
It has now been found that, surprisingly, the poured density of the expandable pellets has an effect on blowing agent capacity/storage stability and thus also affects the achievable density reduction during prefoaming. Both the expandable pellets and the expanded foam particles preferably comprise as a nucleating agent talc, titanium dioxide, graphite, carbon black or mixtures thereof. Both the expandable pellets and the expanded foam particles comprise as a nucleating agent preferably 0.01% to 2.0%, particularly preferably 0.05% to 1.5% by weight, of talc, titanium dioxide, graphite, carbon black or mixtures thereof based on the sum of high-temperature thermoplastic and nucleating agents.
Both the expandable pellets and the expanded foam particles preferably comprise exclusively at least one polyethersulfone as the high temperature thermoplastic.
The invention also provides a process for producing expandable, blowing agent-containing pellets based on high temperature thermoplastics comprising the steps of:
The steps b) and c) may be performed simultaneously or consecutively. Step c) is preferably performed after step b). This means that the blowing agent-containing polymer melt is cooled to a temperature in the range from 180° C. to 250° C. by addition of the blowing agent and/or external cooling. In this way the blowing agent-containing polymer melt may be passed through a heated die plate and pelletized at a melt temperature in the range from 180° C. to 250° C.
As the blowing agent the process according to the invention may employ alcohols, ketones or hydrocarbons having 1 to 4 carbon atoms, preferably acetone, methyl ethyl ketone, ethanol, isopropanol, isobutane, water or mixtures thereof in amounts of 3% to 15% by weight, preferably in amounts of 5% to 10% by weight, based on the polymer melt including its additives. It is particularly preferable to add 3% to 10% by weight of acetone to the polymer melt.
Nucleating agents or flame retardants may be added to the polymer melt as additives. It is preferable to employ talc, titanium dioxide, graphite, carbon black or mixtures thereof.
The process according to the invention employs the abovementioned thermoplastics as the high temperature thermoplastics. The high temperature thermoplastic is preferably at least one polyethersulfone or mixtures of polyethersulfones having different weight-average molecular weights MW or having different viscosity numbers. It is preferable to use mixtures of a polyethersulfone having a viscosity number in the range from 46 to 50 cm3/g and a polyethersulfone having a viscosity number in the range from 54 to 58 cm3/g measured according to ISO 307, 1157,1628 (in 0.01 g/ml phenol/1,2-ortho-dichlorbenzene, 1:1).
The high poured density of the expandable pellets in the range from 400 to 900 kg/m3 was achievable through a high water pressure in the underwater pelletization and the choice of the blowing agent and the concentration thereof and the temperature profile in the extrusion apparatus with underwater pelletization.
The invention also provides expanded foam particles based on high temperature , wherein the expandable, blowing agent-containing pellets comprise at least one nucleating agent and have a poured density according to DIN ISO 697:1982 in the range from 10 to 200 kg/m3.
The mean cell diameter of the expanded foam particles according to the invention is generally in the range from 30 to 150 μm, preferably in the range from 50 to 100 μm. It is preferable when 90% of the cells, particularly preferably 99% of the cells, have a cell diameter of less than 150 pm. The average length/breadth ratio is preferably below 2.0, particularly preferably below 1.6.
These are obtainable by prefoaming of the expandable particles. Suitable therefor is a process for producing foam particles based on high temperature thermoplastics which comprises foaming the abovementioned expandable, blowing agent-containing pellets at temperatures in the range from 180° C. to 280° C., preferably in the range from 220° C. to 250° C., for 5 to 300 seconds, preferably 10 to 150 seconds, for example in a recirculating air oven.
The thus-obtainable expanded foam particles may be welded to afford particle foam moldings.
Suitable therefor are processes for producing a particle foam based on high temperature thermoplastics in which the abovementioned expandable blowing agent-containing pellets or expanded foam particles are welded in a mold using steam, hot air, IR or electromagnetic radiation or hot pressing.
The thus-obtained particle foams are generally closed-cell foams. The particle foams preferably have a density in the range from 20 to 250 kg/m3, particularly preferably in the range from 40 to 150 kg/m3.
The foam particles according to the invention are suitable in particular for use in composite sheets for aviation applications.
Due to the high poured density of the expandable blowing agent-containing pellets according to the invention and good storage stability on account of the low loss of blowing agent said pellets may be delivered at low transport costs even over relatively long transport routes to processors which can subject said pellets to prefoaming to afford expanded foam particles and subsequent processing to afford foam moldings having any desired three-dimensional shapes.
The poured density of the blowing agent-containing, expandable pellets was determined according to DIN ISO 697:1982.
The blowing agent content of the expandable pellets was determined by gravimetric means as volatile fractions. To this end about 20 g of the blowing agent-containing pellets were weighed into an aluminum dish, dried at 250° C. for at least 2 hours in a recirculating air oven and reweighed.
Compressive stresses were determined according to DIN EN ISO 844:2014.
Determination of cell size distribution and average cell diameter was carried out by imaging the cross section of the foam particles with a camera and evaluation with PORE!SCAN from Goldlücke Ingenieurleistungen. To this end, 10 foam particles were attached to a sheet of particle board (10×10 cm) with double-sided adhesive tape and cut in half. To determine the average cell areas and average cell diameters around 1500 cells were evaluated.
Melt impregnation was carried out in an apparatus consisting of a twin screw extruder divided into eight zones of equal length (Z1 . . . Z8) from Leistritz having an 18 mm screw diameter and a length to diameter ratio of 40, a melt pump (gear pump GP), diverter valve (DV), melt filter, die plate (DP) and an underwater pelletization (UWP).
Polyethersulfone (PESU) was mixed with the additives (talc, titanium dioxide, graphite) in a polyethylene bag, metered into the twin screw extruder and melted. About 2/3 along the length of the extruder the blowing agent was injected into the extruder in zone Z5 using Isco pumps (piston pumps from Axel Semrau) and an injector built into the extruder. From zone Z6 onward the polymer melt was cooled via the temperature control means of the twin-screw extruder. The temperature of the polymer melt upon passing through the die plate corresponded to the temperature established at zone 8. Using the melt pump (GP) the pressure profile in the extruder was adjusted (pressure-speed control) such that the blowing agent was completely mixed into the polymer melt. In addition to adjustment of the pressure profile in the twin-screw extruder the melt pump is also used for conveying the blowing agent-impregnated polymer melt through the downstream devices (the diverter valve, the melt sieve and the die plate). The melt strand exiting via the die plate (1 hole with 1.0 mm diameter) was cut into expandable polyethersulfone pellets having a pellet weight of about 2.3 mg under pressure in the underwater pelletizer (UWP). The total throughput of the extruder was kept constant at 5 kg/h. The strand in the water box was cut by 10 blades attached to a blade ring. In examples 1-12 the blade ring rotates at 3600 rpm. This forms expandable pellets having a pellet weight of 2.3 mg which are transported by the water circulation from the die plate into the dryer and from there are deposited into a collection vessel (presently a tin can).
The weight fractions of the employed raw materials are reported in table 1. The weight fractions relate to 100% by weight of solids (polymer and additives without blowing agent). The blowing agent fraction relates to 100% by weight of solids (polymer and additives). The process parameters are reported in table 2. The temperatures relate to the temperature values established and measured at the respective apparatus parts.
In examples 1-12, 17, 20-24 acetone was used as the blowing agent. In examples 13-16 and 18-19 mixtures of acetone with water, ethanol or isopropanol were employed in the weight ratio reported in table 1.
In examples 13-23 the knife speed was set to the value reported in table 2. Pellet weights of 2.8 mg (3000 rpm), 2.4 mg (3500 rpm) and 3,3 mg (2500 rpm) were obtained.
In comparative examples V1 and V2 the temperature of the blowing agent-containing polymer melt was kept constant and not cooled.
The expandable pellets from the examples 1-3 were foamed to afford foam particles in a recirculating air oven as follows.
The measured poured densities after foaming of the expandable pellets in week 1 are shown in table 4.
Foam particles from examples 19-22 were filled into a mold having interior dimensions of 200×300×12 mm and using steam welded to afford foam sheets in a high-pressure molding machine. Densities and compressive stresses at different compressions are reported in table 5.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17184924.3 | Aug 2017 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/070084 | 7/25/2018 | WO | 00 |
