Patent Application
20080230956
The invention relates to a process for producing foam moldings from prefoamed foam particles which have a polymer coating and also to foam moldings produced therefrom and to their use.
Expanded foams are usually obtained by sintering foam particles, for example pre-foamed expandable polystyrene particles (EPS) or expanded polypropylene particles (EPP), in closed molds by means of steam. For the foam particles to be able to undergo after-expansion and fuse together well to form the foam molding, they generally have to comprise small residual amounts of blowing agent. The foam particles must therefore not be stored for too long after prefoaming. In addition, due to the lack of after-expandability of comminuted recycled foam materials from expanded foams which are no longer usable, only small amounts of these can be mixed in for producing new foam moldings.
Filler-comprising, expandable pelletized thermoplastic materials and foam particles or foam moldings obtainable therefrom are described in WO 2005/056653. At high filler contents, processing is, relatively difficult because of the reduced foamability. The fusibility is frequently not sufficient to obtain foam moldings having very good mechanical properties.
WO 00/050500 describes flame-resistant foams produced from prefoamed polystyrene particles which are mixed with an aqueous sodium silicate solution and a latex of a high molecular weight vinyl acetate copolymer, poured into a mold and dried in air while shaking. This gives only a loose bed of polystyrene particles which are adhesively bonded together at only a few points and therefore have only unsatisfactory mechanical strengths.
WO 2005/105404 describes an energy-saving process for producing foam moldings, in which the prefoamed foam particles are coated with a resin solution which has a softening temperature lower than that of the expandable-polymer. The coated foam particles are subsequently fused together in a mold under external pressure or by after-expansion of the foam particles in a customary fashion using hot steam. Here, water-soluble constituents of the coating can be washed out. Owing to the relatively high temperatures at the entry points and the cooling of the steam when it condenses, the fusion of the foam particles and the density can fluctuate considerably over the total foam body. In addition, condensing steam can be enclosed in the interstices between the foam particles.
It was therefore an object of the invention to remedy the disadvantages mentioned and to discover a simple and energy-saving process for producing foam moldings having high filler contents and good mechanical properties, in particular a high flexural strength.
We have accordingly found a process for producing foam moldings by sintering of pre-foamed foam particles which have a polymer coating in a mold under pressure, wherein the prefoamed foam particles comprise from 10 to 70% by weight, based on the foam particles, of a filler.
As foam particles, it is possible to use expanded polyolefins such as expanded poly-ethylene (EPE) or expanded polypropylene (EPP) or prefoamed particles of expand-able styrene polymers, in particular expandable polystyrene (EPS). The foam particles generally have a mean particle diameter in the range from 2 to 10 mm. The bulk density of the foam particles is generally from 5 to 50 kg/m3, preferably from 5 to 40 kg/m3 and in particular from 8 to 16 kg/m3, determined in accordance with DIN EN ISO 60.
According to the invention, they comprise from 10 to 70% by weight, preferably from 25 to 50% by weight, based on the prefoamed foam particles, of a filler. Possible fillers are organic and inorganic powders or fibrous materials and also mixtures thereof. Organic fillers which can be used are, for example, wood flour, starch, flax cellulose, hemp cellulose, ramie cellulose, jute cellulose, sisal cellulose, cotton cellulose or aramid fibers. Inorganic fillers which can be used are, for example, carbonates, silicates, barite, glass spheres, zeolites or metal oxides. Preference is given to using pulverulent inorganic materials such as talc, chalk, kaolin (Al2(Si2O5)(OH)4), aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz flour, aerosil, alumina or wollastonite or spherical or fibrous, inorganic materials such as glass spheres, glass fibers or carbon fibers.
The mean particle diameter or in the case of fibrous fillers the length should be in the region of the cell size or smaller. Preference is given to a mean particle diameter in the range from 1 to 100 μm, preferably in the range from 2 to 50 μm.
Particular preference is given to inorganic fillers having a density in the range 1.0-4.0 g/cm3, in particular in the range 1.5-3.5 g/cm3. The whiteness/brightness (DIN/ISO) is preferably 50-100%, in particular 60-98%.
The properties of the expandable thermoplastic polymers and the expanded foam moldings obtainable therefrom can be influenced by means of the type and amount of fillers. The use of bonding agents such as styrene copolymers modified with maleic anhydride, polymers comprising epoxide groups, organosilanes or styrene copolymers having isocyanate or acid groups enables the bonding of the filler to the polymer matrix and thus the mechanical properties of the expanded foam moldings to be improved significantly.
In general, inorganic fillers reduce the combustibility. In particular, the burning behavior can be significantly improved by addition of inorganic powders such as aluminum hydroxide.
Such filler-comprising foam particles can, for example, be obtained by foaming of filler-comprising, expandable thermoplastic pellets. At high filler contents, the expandable pellets required for this purpose can be obtained by extrusion of thermoplastic melts comprising blowing agent and subsequent underwater granulation under pressure, as described, for example, in WO 2005/056653.
The foam particles based on styrene polymers can be obtained by prefoaming of EPS to the desired density by means of hot air or steam in a prefoamer. Final bulk densities below 10 g/l can be obtained here by single or multiple prefoaming in a pressure pre-foamer or continuous prefoamer.
A preferred process comprises the steps
Owing to their high thermal insulation capability, particular preference is given to using prefoamed, expandable styrene polymers which comprise athermanous solids such as carbon black, aluminum or graphite, in particular graphite having a mean particle diameter in the range from 1 to 50 μm, in amounts of from 0.1 to 10% by weight, in particular from 2 to 8% by weight, based on EPS, and are known, for example, from EP-B 981 574 and EP-B 981 575.
The polymer foam particles are, in particular, provided with flame retardants. They can for this purpose comprise, for example, from 1 to 6% by weight of an organic bromine compound such as hexabromocyclodecane (HBCD) and, if appropriate, additionally from 0.1 to 0.5% by weight of bicumyl or a peroxide.
The process of the invention can also be carried out using comminuted foam particles from recycled foam moldings. To produce the foam moldings of the invention, it is possible to use the comminuted recycled foam materials either alone or mixed with fresh material, for example in proportions of from 2 to 90% by weight, in particular from 5 to 25% by weight, without significantly impairing the strength and the mechanical proper-ties.
In general, the coating comprises a polymer film which has one or more glass transition temperatures in the range from 60° to +100° C. and in which fillers may, if appropriate, be embedded. The glass transition temperatures of the polymer film are preferably in the range from −30° to +80° C., particularly preferably in the range from −10° to +60° C. The glass transition temperature can be determined by means of differential scanning calorimetry (DSC). The molecular weight of the polymer film, determined by gel permeation chromatography (GPC), is preferably below 400 000 g/mol.
To coat the foam particles, it is possible to use customary methods such as spraying, dipping or wetting of the foam particles with a polymer solution or polymer dispersion or by drum coating with solid polymers or polymers absorbed on solids in customary mix-ers, spraying apparatuses, dipping apparatuses or drum apparatuses.
Polymers suitable for the coating are, for example, polymers based on monomers such as vinylaromatic monomers, such as α-methylstyrene, p-methylstyrene, ethylstyrene, tert-butylstyrene, vinylstyrene, vinyltoluene, 1,2-diphenylethylene, 1,1-diphenylethylene, alkenes such as ethylene or propylene, dienes such as 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, isoprene, piperylene or isoprene, α,β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, their esters, in particular alkyl esters, e.g. C1-10-alkyl esters of acrylic acid, in particular the butyl esters, preferably n-butyl acrylate, and the C1-10-alkyl esters of methacrylic acid, in particular methyl methacrylate (MMA), or carboxamides, for example acrylamide and methacrylamide.
The polymers can, if appropriate, comprise from 1 to 5% by weight of comonomers such as (meth)acrylonitrile, (meth)acrylamide, ureido(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, acrylamidopropanesulfonic acid, methylolacrylamide or the sodium salt of vinylsulfonic acid.
The polymers of the coating are preferably made up of one or more of the monomers styrene, butadiene, acrylic acid, methacrylic acid, C1-4-alkyl acrylates, C1-4-alkyl methacrylates, acrylamide, methacrylamide and methylolacrylamide.
Suitable binders for the polymer coating are, in particular, acrylate resins which are preferably applied as aqueous polymer dispersions to the foam particles, if appropriate together with hydraulic binders based on cement, lime cement or gypsum plaster. Suit-able polymer dispersions can be obtained, for example, by free-radical emulsion polymerization of ethylenically unsaturated monomers such as styrene, acrylates or methacrylates, as described in WO 00/50480.
Particular preference is given to pure acrylates or styrene-acrylates which are made up of the monomers styrene, n-butyl acrylate, methyl methacrylate (MMA), methacrylic acid, acrylamide and methylolacrylamide.
The polymer dispersion is prepared in a manner known per se, for instance by emulsion, suspension or dispersion polymerization, preferably in an aqueous phase. It is also possible to produce the polymer by solution or bulk polymerization, comminute it if appropriate and subsequently disperse the polymer particles in water in a customary way. In the polymerization, the initiators, emulsifiers or suspension aids, regulators or other auxiliaries customary for the respective polymerization process are concomitantly used, and the polymerization is carried out continuously or batchwise at the temperatures and pressures customary for the respective process in suitable reactors.
The polymer coating can also comprise additives such as inorganic fillers such as pigments or flame retardants. The proportion of additives depends on their type and the desired effect and in the case of inorganic fillers is generally from 10 to 99% by weight, preferably from 20 to 98% by weight, based on the additive-comprising polymer coating.
The coating mixture preferably comprises water-binding substances such as water glass. This leads to better and more rapid film formation from the polymer dispersion and thus more rapid curing of the foam molding.
The polymer coating preferably comprises flame retardants such as expandable graphite, borates, in particular zinc borates, melamine compounds or phosphorus compounds or intumescent compositions which expand, swell or foam under the action of elevated temperatures, generally above 80-100° C., and in the process form an insulating and heat-resistant foam which protects the underlying thermally insulating foam particles against fire and heat. The amount of flame retardants or intumescent compositions is generally 2-99%, preferably from 5 to 98%, based on the polymer coating.
When flame retardants are used in the polymer coating, it is also possible to achieve satisfactory fire protection when using foam particles which do not comprise any flame retardants, in particular do not comprise any halogenated flame retardants, or to make do with smaller amounts of flame retardant, since the flame retardant in the polymer coating is concentrated at the surface of the foam particles and under the action of heat or fire forms a solid framework.
The polymer coating particularly preferably comprises intumescent compositions which comprise chemically bound water or eliminate water at temperatures above 40° C., e.g. alkali metal silicates, metal hydroxides, metal salt hydrates and metal oxide hydrates, as additives.
Foam particles provided with this coating can be processed to give foam moldings which have increased fire resistance and have a burning behavior conforming to class B in accordance with DIN 4102.
Suitable metal hydroxides are, in particular, those of groups 2 (alkaline earth metals) and 13 (boron group) of the Periodic Table. Preference is given to magnesium hydroxide and aluminum hydroxide. The latter is particularly preferred.
Suitable metal salt hydrates are all metal salts into whose crystal structure water of crystallization is incorporated. Analogously, suitable metal oxide hydrates are all metal oxides which comprise water of crystallization incorporated into the crystal structure. The number of molecules of water of crystallization per formula unit can be the maxi-mum possible or be below this, e.g. copper sulfate pentahydrate, trihydrate or monohydrate. In addition to the water of crystallization, the metal salt hydrates and metal oxide hydrates can also comprise water of constitution.
Preferred metal salt hydrates are the hydrates of metal halides (in particular chlorides), sulfates, carbonates, phosphates, nitrates or borates. Suitable metal salt hydrates are, for example, magnesium sulfate decahydrate, sodium sulfate decahydrate, copper sulfate pentahydrate, nickel sulfate heptahydrate, cobalt(II) chloride hexahydrate, chromium(III) chloride hexahydrate, sodium carbonate decahydrate, magnesium chloride hexahydrate and the tin borate hydrates. Magnesium sulfate decahydrate and tin borate hydrates are particularly preferred.
Further possible metal salt hydrates are double salts such as alums, for example those of the general formula: MIMIII(SO4)2.12H2O.MI can be, for example, a potassium, sodium, rubidium, cesium, ammonium, thallium or aluminum ion. MIII can be, for example, aluminum, gallium, indium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, rhodium or iridium.
Suitable metal oxide hydrates are, for example, aluminum oxide hydrate and preferably zinc oxide hydrate or boron trioxide hydrate.
A preferred polymer coating can be obtained by mixing of from 40 to 80 parts by weight, preferably from 50 to 70 parts by weight, of a water glass solution having a water content of from 40 to 90% by weight, preferably from 50 to 70% by weight,
from 20 to 60 parts by weight, preferably from 30 to 50 parts by weight, of a water glass powder having a water content of from 0 to 30% by weight, preferably from 1 to 25% by weight, and
from 5 to 40 parts by weight, preferably from 10 to 30 parts by weight, of a polymer dispersion having a solids content of from 10 to 60% by weight, preferably from 20 to 50% by weight,
or by mixing of
from 20 to 95 parts by weight, preferably from 40 to 90 parts by weight, of an aluminum hydroxide suspension having an aluminum hydroxide content of from 10 to 90% by weight, preferably from 20 to 70% by weight,
from 5 to 40 parts by weight, preferably from 10 to 30 parts by weight, of a polymer dispersion having a solids content of from 10 to 60% by weight, preferably from 20 to 50% by weight.
In the process of the invention, the pressure can be produced, for example, by de-creasing the volume of the mold by means of a movable punch. In general, a pressure in the range from 0.5 to 30 kg/cm2 is set here. The mixture of coated foam particles is for this purpose introduced into the open mold. After closing the mold, the foam particles are pressed by means of the punch, with the air between the foam particles escaping and the volume of interstices being reduced. The foam particles are joined by means of the polymer coating to give the foam molding.
The mold is structured in accordance with the desired geometry of the foam body. The degree of fill depends, inter alia, on the desired thickness of the future molding. In the case of foam boards, it is possible to use a simple box-shaped mold. In the case of more complicated geometries, in particular, it may be necessary to compact the bed of particles introduced into the mold and in this way eliminate undesirable voids. Compaction can be achieved by, for example, shaking of the mold, tumbling motions or other suitable measures.
To accelerate setting, hot air can be injected into the mold or the mold can be heated. According to the invention, no steam is introduced into the mold so that no water-soluble constituents of the polymer coating of the foam particles are washed out and no condensate water can be formed in the interstices. However, any heat transfer media such as oil or steam can be used for heating the mold. The hot air or the mold is for this purpose advantageously heated to a temperature in the range from 20 to 120° C., preferably from 30 to 90° C.
As an alternative or in addition, sintering can be carried out with injection of microwave energy. In general, microwaves having a frequency in the range from 0.85 to 100 GHz, preferably from 0.9 to 10 GHz, and irradiation times of from 0.1 to 15 minutes are used here.
When hot air having a temperature in the range from 80 to 156° C. is used or microwave energy is injected, a gauge pressure of from 0.1 to 1.5 bar is usually established, so that the process can also be carried out without external pressure and without decreasing the volume of the mold. The internal pressure generated by the microwaves or elevated temperatures allows the foam particles to undergo slight further expansion, with these also being able to fuse together as a result of softening of the foam particles themselves in addition to adhesive bonding via the polymer coating. The interstices between the foam particles disappear as a result. To accelerate setting, the mold can in this case, too, be additionally heated by means of a heat transfer medium as de-scribed above.
Double belt plants as are used for the production of polyurethane foams are also suit-able for the continuous production of the foam moldings of the invention. For example, the prefoamed and coated foam particles can be applied continuously to the lower of two metal belts, which may, if appropriate, have perforations, and be processed with or without compression by the metal belts moving together to produce continuous foam boards. In one embodiment of the process, the volume between the two belts is gradually decreased, as a result of which the product between the belts is compressed and the interstices between the foam particles disappear. After a curing zone, a continuous board is obtained. In another embodiment, the volume between the belts can be kept constant and the foam can pass through a zone heated by hot air or microwave irradiation in which the foam particles undergo after-foaming. Here too, the interstices disappear and a continuous board is obtained. It is also possible to combine the two continuous process embodiments.
The thickness, length and width of the foam boards can vary within wide limits and is limited by the size and closure force of the tool. The thickness of the foam boards is usually from 1 to 500 mm, preferably from 10 to 300 mm.
The density of the foam moldings in accordance with DIN 53420 is generally from 10 to 120 kg/m3, preferably from 20 to 70 kg/m3. The process of the invention makes it possible to obtain foam moldings having a uniform density over the entire cross section. The density of the surface layers corresponds approximately to the density of the inner regions of the foam molding.
Owing to the high filler content, the foam moldings obtainable by the process of the invention display a very low thermal conductivity and a very good flame retardant action. Less flame retardant is therefore required in the coating. The adhesive bonding of the foam particles via the polymer coating results in high flexural strengths of the foam moldings.
The process of the invention is suitable for producing simple or complex foam moldings such as boards, blocks, tubes, rods, profiles, etc. Preference is given to boards or blocks which can subsequently be sawn or cut to produce boards. They can be used, for example, in building and construction for the insulation of exterior walls. They are particularly preferably used as core layer for the production of sandwich elements, for example structural insulation panels (SIPs) which are used for the construction of cold stores or warehouses.
Further possible applications are foam pallets as a replacement for wooden pallets, facing panels of ceilings, insulated containers, caravans. With a content of flame retardant, these are also suitable for airfreight.
40 parts of water glass powder (Portil N) were added a little at a time with stirring to 60 parts of a water glass solution (Woellner sodium silicate 38/40, solids content: 36%, density: 1.37, molar ratio of SiO2:Na2O=3.4) and the mixture was homogenized for about 3-5 minutes. 20 parts of an acrylate dispersion (Acronal S790, solids content: about 50%) were subsequently stirred in.
Polystyrene foam particles comprising 30% by weight of chalk (density: 12 g/l) 6% by weight of n-pentane and 30% by weight of chalk (Ulmer Weiβ XM) were mixed into a polystyrene melt of PS 158K from BASF Aktiengesellschaft having a viscosity number VN of 95 ml/g (MW=275 000 g/mol, polydispersity Mw/Mn=2.6). After cooling of the melt comprising blowing agent from an original 260° C. to 180° C., the mixture of polystyrene melt, blowing agent and filler was extruded at 60 kg/h through a die plate having 32 holes (diameter of the holes: 0.75 mm). Pressurized underwater pelletization gave compact pellets having a narrow size distribution.
These pellets were prefoamed in a stream of steam to give foam particles having a density of 12 g/l and temporarily stored for 24 hours before further processing.
Polystyrene foam particles comprising 40% by weight of aluminum hydroxide (density: 20 g/l)
6% by weight of n-pentane were mixed into a polystyrene melt of PS 158K from BASF Aktiengesellschaft having a viscosity number VN of 95 ml/g (MW=275 000 g/mol, polydispersity Mw/Mn=2.6). After cooling of the melt comprising blowing agent from an original 260° C. to a temperature of 180° C., a mixture of polystyrene melt and aluminum hydroxide was added via a side stream extruder and mixed into the main stream so that the end product comprised 40% by weight of aluminum hydroxide. The mixture of polystyrene melt, blowing agent and additives was extruded at 60 kg/h through a die plate having 32 holes (diameter of the holes: 0.75 mm). Pressurized underwater pelletization gave compact pellets having a narrow size distribution.
These pellets were prefoamed in a stream of steam to give foam beads having a density of 20 g/l and temporarily stored for 24 hours.
Polystyrene foam particles comprising 30% by weight of aluminum hydroxide (density: 20 g/l)
6% by weight of n-pentane were mixed into a polystyrene melt of PS 158K from BASF Aktiengesellschaft having a viscosity number VN of 95 ml/g (MW=275 000 g/mol, polydispersity Mw/Mn=2.6). After cooling of the melt comprising blowing agent from an original 260° C. to a temperature of 180° C., a mixture of polystyrene melt and aluminum hydroxide was added via a side stream extruder and mixed into the main stream so that the end product comprised 30% by weight of aluminum hydroxide. The mixture of polystyrene melt, blowing agent and additives was extruded at 60 kg/h through a die plate having 32 holes (diameter of the holes: 0.75 mm). Pressurized underwater pelletization gave compact pellets having a narrow size distribution.
These pellets were prefoamed in a stream of steam to give foam beads having a density of 15 g/l and temporarily stored for 24 hours prior to further processing.
Pressing with Reduction in Volume:
Polystyrene foam particles comprising 30% by weight of chalk (density: 12 μl) were coated with the coating mixture in a weight ratio of 1:3 in a mixer. The coated polystyrene foam particles were introduced into a Teflon-coated mold which had been heated to 70° C. and pressed by means of a punch to 50% of the original volume. After curing at 70° C. for 30 minutes, the foam molding was removed from the mold. The molding was conditioned further by storing it at ambient temperature for a number of days. The density of the stored molding was 75 g/l.
Example 1 was repeated using polystyrene foam particles comprising 40% by weight of aluminum hydroxide and having a density of 20 g/l which had been coated with the coating mixture in a weight ratio of 1:2 in a mixer. The density of the stored molding was 80 μl.
Polystyrene foam particles comprising 30% by weight of aluminum hydroxide and having a density of 20 g/l were mixed with recycled EPS particles in a ratio of 1:2 and coated with the coating mixture in a weight ratio of 1:2 in a mixer. The coated polystyrene foam particles were introduced into a Teflon-coated mold which had been heated to 70° C. and pressed by means of a punch to 40% of the original volume. After curing at 70° C. for 30 minutes, the foam molding was removed from the mold. The molding was conditioned further by storing it at ambient temperature for a number of days. The density of the stored molding was 70 g/l.
The foam moldings of Examples 1 to 3 do not drip in the burning test and do not soften backward under the action of heat. They are self-extinguishing and meet the requirements of burning test B2 or E.
Sandwich elements having metal covering layers were produced from the foam boards of Examples 1 to 3: boards having the dimensions 600×100×100 mm and a density as reported in the examples were provided on each side with a 50 μm thick layer of a polyurethane adhesive. Steel plates having a thickness of 1 mm in each case were applied to the adhesive. The adhesive was allowed to cure at 25° C. for 5 hours.
To test the burning behavior in the sandwich element, the element was fastened horizontally (metal surfaces above and below) and a gas burner was placed under the board. The gas flame of this was directed at the middle of the underside of the board, the flame had a height of about 5 cm and a flame temperature of about 600° C. The distance between the tip of the flame and the underside of the board was 0.2 cm.
Testing of the burning behavior indicated that after the flame had burned for 30 minutes, only a small part of the polystyrene foam between the metal plates had melted. The mechanical stability of the board was retained. The polystyrene foam did not drip and did not ignite. Smoke evolution was very slight.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2005 039 976.2 | Aug 2005 | DE | national |
| 06112263.6 | Apr 2006 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP06/65176 | 8/9/2006 | WO | 00 | 2/21/2008 |
