EP2638102A1

EP2638102A1 - Process for producing expandable thermoplastic beads with improved expandability

Info

Publication number: EP2638102A1
Application number: EP11778907.3A
Authority: EP
Inventors: Holger RUCKDÄSCHEL; Carsten Schips; Klaus Hahn; Jens Assmann; Maximilian Hofmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-11-11
Filing date: 2011-11-07
Publication date: 2013-09-18
Also published as: JP2013542302A; KR20130103571A; KR101869577B1; CN103347942A; MX2013005234A; EP2452968A1; JP5873098B2; WO2012062682A1; TW201226457A; BR112013011444A2; CN103347942B; CA2817678A1

Abstract

A process for producing expandable, thermoplastic polymer beads comprising cavities via extrusion of a polymer melt comprising blowing agent through a die plate and pelletization in a chamber comprising liquid under a pressure in the range from 1.5 to 15 bar, wherein the polymer melt comprising blowing agent comprises from 0.1 to 5% by weight of a nucleating agent D), from 1 to 10% by weight of a blowing agent E) which in essence remains within the polymer beads, from 0.01 to 5% by weight of a co-blowing agent F) forming the cavities, based in each case on the polymer melt comprising blowing agent, and also the expandable thermoplastic polymer bead material which can be obtained by the process, comprising cavities with an average diameter in the range from 0.1 to 50 µm.

Description

Process for producing expandable thermoplastic particles with improved expandability

description

The invention relates to a process for producing hollow, expandable, thermoplastic polymer particles by extrusion of a blowing agent-containing polymer melt through a die plate and granulation in a liquid-filled chamber under a pressure in the range of 1, 5 to 15 bar.

Expandable particle foams can be prepared by the suspension process, by post-impregnation of polymer granules or by the melt extrusion process. With regard to possible starting materials and additives, the melt extrusion process is particularly versatile.

Methods for producing expandable polymers by the melt impregnation method are known. The application for various polymer systems has now been demonstrated for several materials, for example for acrylonitrile-containing styrene copolymers (WO 2009/000872) and for elasticized expandable particle foams (WO 2009/1 12549).

The properties of particulate foams are highly dependent on the cell structure, e.g. Cell size or cell size distribution. By influencing the cell size, thus, for example, the thermal, mechanical, optical and haptic properties are changeable. Due to the given procedural constraints, the cell structure can only be controlled to a limited extent without a change in the material composition.

For this reason, nucleating agents, for example inorganic additives and organic nucleating agents, such as waxes, are frequently used to control the cell size, which provide an interface with the system and thus reduce the energy barrier for the heterogeneous nucleation at the phase interface between polymer and nucleating agent.

However, such nucleating agents are only partially suitable due to their sometimes low efficiency and their negative influence on the mechanical properties or the fire properties of the foam. For example, by the addition of inorganic, particulate nucleating agents such as talc, toughness, e.g. characterized by the bending work or crack resistance, can be reduced. In order to improve the binding of the inorganic nucleating agents and thus the mechanical properties again, it is possible to use phase promoters or surface-modified fillers which, however, in turn have a lower nucleation efficiency.

In addition, the organic nucleating agents should have low solubility in the polymer to be nucleated to allow for phase separation. Thus, for example, olefinic waxes are excreted for use in olefinic polymers. Organic nuclei such as olefinic waxes, eg Luwax®, are not suitable for all materials. Even in toughened styrene foams olefinic nucleating agents can not be used because they do not phase-separate in the material, but migrate into the polyolefin phases. Thus, no effective nucleation can be achieved.

An increase in cell density can also be achieved by the use of poorly soluble propellants. However, such blowing agents require very high solution pressures and exhibit a long residence time in the prefoamed particles or foamed moldings, i. they have both process and application specific disadvantages.

The use of organic blowing agents and inert gases to control the foam structure and foam properties of expandable polymers has been described only to a limited extent. The following summarizes some relevant patents which include both foam extrusion, expandable and expanded particles.

The production of foam particles using water as blowing agent is described in WO 2004/022636. To improve water compatibility, work is carried out with solubility modifiers such as ethanol and acetone. In addition, further blowing agents such as pentane, butane and / or C0 ₂ are used. The aim of adding water is primarily the reduction of organic propellants in the expandable granules, an influence on the cell size is not described.

The preparation and use of slightly foamed, expandable styrene polymers is described in DE 198 190 58. By varying the process parameters in the suspension and in the melt impregnation using pentane as the blowing agent foamed bulk densities that are 0.1 to 20% below the bulk density of non-foamed materials. By foaming grobzelligere foams are to be able to be produced. The achievement of a homogeneous foaming of the material depends very much on the selected process conditions and can not be varied as desired.

The use of multiple blowing agents in multi-phase polymer systems is described in WO 2005/092959. The goal is the production of nanoporous foams by selective impregnation of a nanoscale structure with a blowing agent and the subsequent foaming. An essential prerequisite for achieving the fine-cell structure is a multiphase blend structure.

The use of blowing agent combinations is described for example in EP-A 846 141. In the continuous process for the production of expandable Styrolpoly- merisaten C ₃ - C ₇ - hydrocarbons are added individually or in admixture with C0 ₂ as a blowing agent. The process comprises the bulk polymerization of the styrene polymer to a certain extent, dispersing the resulting prepolymer in liquid form in aqueous phase with suspension stabilizer and the subsequent polymerization. The blowing agents may be added at each of the process steps. When using C0 ₂ also advantageously C0 ₂ - absorber are used. A specific function of the C0 ₂ during or after the manufacturing process will not be described.

The pre-expansion of vinylaromatic polymers to a bulk density of 200-600 g / l and the subsequent post-expansion of the material after impregnation with inorganic gases, especially with 0 ₂ - or N ₂ -containing gases, is described in EP-A 987 292. The steps of pre-expansion and post-impregnation take place separately in time. The post-impregnation step is required for expansion in all cases.

A process for the preparation of expandable polymer granules, especially based on polystyrene, is described in EP-B 1 000 1 15. After impregnation of the polymers with suitable blowing agents, atomization and subsequent cooling of the resulting granules takes place. Hydrocarbons, chlorofluorohydrocarbons, C0 ₂ , N2 and air or noble gases are mentioned as possible blowing agents. When using CO2, N2 and air, no special effects are described.

The use of small amounts of CO2 in addition to aliphatic hydrocarbons is described in US 2,864,778 for the preparation of expandable styrenic polymers. By adding CO2 before or during the polymerization in the suspension process, finer-celled foams can be produced. The necessary proportion is described as very small. Effects occur according to the examples already at 0.4 wt .-% and lower proportions. Other systems for obtaining fine-celled products, as well as other processes for producing expandable styrene polymers, are not described.

The use of gases, especially N 2 and air, to make foams of expandable styrenic polymers and interpolymers is described in US 3,328,497. The described process involves the partial expansion of the expandable polymer, which includes an organic blowing agent having a boiling point below 80 ° C, and the rapid transfer to an atmosphere of elevated gas pressure and low temperature. The foam is obtained in a final step by further expansion in a closed mold at elevated temperatures. The loading of the granules with the gases described is carried out analogously to EP 987 292 after the pre-expansion of the materials, special effects on the cellulosity are not described.

For the production of foam particles from ethylene-based resins is described in US

5,391, 581 describes the use of propellant mixtures of aliphatic hydrocarbons or alicyclic hydrocarbons and CO2. By using CO2 and additionally introduced, inorganic nucleating agents, the cell size of the expanded granules can be adjusted homogeneously, however, an additional expansion prior to molding as opposed to expandable particles is not possible. The extrusion of foam boards (XPS) of styrene-based polymer systems using multiple blowing agents is described in US 2006/0022366. In combination with isobutane, n-pentane, isopentane or mixtures thereof, water, CO.sub.2, ethers or dialkyl carbonates having a boiling point below 140.degree. C. are advantageously used as the blowing agent. The use of the abovementioned blowing agents and the faster permeation after foaming compared to air produces a negative pressure which is advantageous for further shaping processes.

US 2007/0049649 describes a process for the production of foamed, microvoided polymer particles, in which the polymer is processed and extruded with a gas under high pressure or a liquid in the supercritical state in an extruder into a homogeneous single-phase mixture.

EP-A 0 761 729 describes expandable styrene resin particles having less than 100 microvoids of about 0.1 to 30 μm diameter, which are obtained by suspension polymerization in the presence of a persulfate and an electrolyte.

The object of the present invention was to find a process for the production of expandable thermoplastic polymer particles having improved expandability, which nevertheless allow faster prefoaming and controlled adjustment of the cell structure with reduced propellant contents.

Accordingly, a process has been found for the preparation of cavities containing expandable thermoplastic polymer particles by extrusion of a blowing agent-containing polymer melt through a die plate and granulation in a liquid-filled chamber under a pressure in the range of 1, 5 to 15 bar, wherein the propellant-containing polymer melt

0.1 to 5 wt .-%, preferably 0.3 to 1, 0 wt .-% of a nucleating agent D),

From 1 to 10% by weight, preferably from 2 to 6% by weight, of a blowing agent E remaining essentially in the polymer particles,

From 0.01 to 5% by weight, preferably from 0.05 to 1% by weight, of a co-propellant F forming the cavities,

in each case based on the propellant-containing polymer melt contains. Surprisingly, it has been found that by using volatile, liquid / gaseous cavities forming co-blowing agent F) a cellular structure can be adjusted in the expandable granules, with the aid of which the subsequent foaming process can be improved and the cell size can be controlled. Suitable nucleating agents D) are inorganic or organic nucleating agents. Suitable inorganic nucleating agents are, for example, talc, silica, mica, clay, zeolites or calcium carbonate. Suitable organic nucleating agents are, for example Waxes such as the polyethylene waxes marketed under the name Luwax®. Talc is preferably used.

As propellant (component E) 1 to 10 weight percent, preferably 3 to 8 weight percent, based on the sum of all components A) to F) of the blowing agent-containing polymer melt, a physical blowing agent used. The propellants may be gaseous or liquid at room temperature (20 to 30 ° C) and atmospheric pressure. They should have a boiling point below the softening temperature of the polymer blend, usually in the range of -40 to 80 ° C, preferably in the range of -10 to 40 ° C. Suitable blowing agents are, for example, halogenated or halogen-free, such as aliphatic C3 to C7 hydrocarbons, alcohols, ketones or ethers. Suitable aliphatic propellants are, for example, aliphatic C 3 -C -hydrocarbons, such as n-propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, neopentane, cycloaliphatic hydrocarbons, such as cyclobutane and cyclopentane, halogenated hydrocarbons, such as methyl chloride, ethyl chloride, methylene chloride, trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, chlorodifluoromethane, dichlorotetrafluoroethane and mixtures thereof. The halogen-free blowing agents are preferably isobutane, n-butane, isopentane, n-pentane, neopentane, cyclopentane and mixtures thereof.

Propellant retention after storage can be improved and lower minimum bulk densities can be achieved if the propellant preferably contains from 25 to 100 percent by weight, more preferably from 35 to 95 percent by weight based on the propellant, isopentane or cyclopentane. Particular preference is given to using mixtures of from 30 to 98% by weight, in particular from 35 to 95% by weight, of isopentane and from 70 to 2% by weight, in particular from 65 to 5% by weight, of n-pentane.

The propellants E) used are preferably aliphatic C ₃ -C ₇ -hydrocarbons or mixtures thereof, particularly preferably isobutane, isopentane, n-pentane and mixtures thereof. The propellant-containing polymer melt preferably contains less than 0.5% by weight of water.

The method for adjusting this cavity morphology may also be referred to as pre-nucleation, the cavities being formed essentially by the co-propellant F). The cavities forming co-blowing agent F) differs from the actual blowing agent E in its solubility in the polymer. In the preparation, first blowing agent E) and co-blowing agent F) are completely dissolved in the polymer at sufficiently high pressure. Subsequently, the pressure is reduced, preferably within a short time, and thus reduces the solubility of the co-blowing agent F). This results in a phase separation in the polymeric matrix and a vorukleierter structure arises. The actual blowing agent E) remains largely dissolved in the polymer due to its higher solubility and / or its low diffusion rate. Simultaneous to the pressure reduction is preferably a temperature reduction performed in order to prevent excessive nucleation of the system and to reduce outdiffusion of the actual propellant E). This is achieved by co-blowing agent F) in conjunction with optimum granulation. Preferably, the co-blowing agent F) escapes to at least 80 wt .-% within 24 h from the expandable thermoplastic particles when stored at 25 ° C, atmospheric pressure and 50% relative humidity. The solubility of the co-blowing agent F) in the expandable thermoplastic particles is preferably below 0.1 wt .-%. Co-propellants F) are preferably used which additionally have a higher diffusion rate and / or an increased permeability and / or an increased vapor pressure than the actual propellant E); most preferably, the co-propellants F) have several of the characteristics. In order to additionally support the nucleation process, small amounts of conventional nucleating agents, for example inorganic particles such as talc, may be used.

In all cases, the added amount of co-propellant F) used in the pre-nucleation should exceed the maximum solubility at the present process conditions. Therefore, preference is given to using co-blowing agents F) which have a low but sufficient solubility in the polymer. These include in particular gases such as nitrogen, carbon dioxide, air or noble gases, more preferably nitrogen, whose solubility in many polymers is reduced at low temperatures and pressures. But there are also other liquid additives conceivable. Particular preference is given to using inert gases such as nitrogen and carbon dioxide. In addition to their suitable physical properties, both gases are distinguished by low costs, good availability, easy handling and inert or inert behavior. For example, in the presence of the two gases, in almost all cases, no degradation of the polymer takes place. Since the gases themselves are extracted from the atmosphere, they also have an environmentally neutral behavior.

The amount of co-propellant F) used should be: (i) sufficiently small to dissolve at the given melt temperatures and pressures in the melt impregnation until granulation; (ii) be sufficiently high to segregate and nucleate at the granulation water pressure and granulation temperature from the polymer. In a preferred embodiment, at least one of the blowing agents used is gaseous at room temperature and under atmospheric pressure.

Preference is also given to using a co-blowing agent F) which, after being pre-nucleated, completely escapes from the expandable granules within a short time and thus does not influence the further foaming process. Nitrogen, carbon dioxide, argon, helium or mixtures thereof are particularly preferably used as co-blowing agent F). Particular preference is given to using talc as nucleating agent D) in combination with nitrogen as co-blowing agent F). Metallic barrels and octabins are used, among other things, for the transport and storage of the expandable granules. When using barrels, it must be ensured that the release of the co-propellant F) can possibly build up pressure in the drum. As packaging, therefore, preferably open containers such as octabins or barrels are to be used, which allow a pressure reduction by permeation of the gas from the barrel. In this case, barrels that allow the co-propellant F) to diffuse out and minimize or prevent the actual propellant E) from diffusing out are particularly preferred. This can for example be made possible by the vote of the sealing material on the blowing agent or co-blowing agent F). Preferably, the permeability of the sealing material for the co-propellant F) is at least a factor of 20 higher than the permeability of the Dichtungsmateri- as for the propellant E).

By Vornukleierung, for example, by adding small amounts of nitrogen and carbon dioxide, a cellular morphology can be adjusted in the expandable, propellant-containing granules. The average cell size in the center of the particles may be larger than in the peripheral areas, the density in the peripheral areas of the particles may be higher. As a result, blowing agent losses are minimized as much as possible.

By Vornukleierung a significantly better cell size distribution and a reduction of the cell size after pre-foaming can be achieved. In addition, the required amount of blowing agent for achieving a minimum bulk density is lower and the storage stability of the material is improved. Small amounts of nitrogen or carbon dioxide when added to the melt can lead to a significant shortening of the prefoaming at a constant blowing agent content or to a significant reduction in blowing agent quantities with constant foaming times and minimum foam densities. In addition, the pre-nucleation improves product homogeneity and process stability.

Further impregnation of the polymer granules according to the invention with blowing agents is furthermore possible much faster than with granules of identical composition and more compact, ie. H. noncellular structure. On the one hand, the diffusion times are lower, on the other hand, similar to directly impregnated systems, lower blowing agent quantities are required for foaming.

Finally, by Vornukleierung the blowing agent content, which is required to achieve a certain density, reduced, and thus the demolding times in the molding or block production can be reduced. Thus, the processing costs can be reduced and the product quality can be improved. The pre-nucleation can generally be applied to all expandable particles. Preferred is the application to materials with high demands on the mechanical properties and to systems in which standard used nucleating agents show only minor effects. For example, in the case of elasticized foams, the fine-celledness could be markedly improved by adding nitrogen or carbon dioxide.

The principle of pre-nucleation can be used both for suspension technology and for melt impregnation technology for the production of expandable particles. Preference is given to the use in the melt extrusion process, in which the addition of the co-blowing agent F) is granulated by the pressure-assisted underwater granulation after the exit of the lubricant-laden melt. By selecting the granulation parameters and the co-propellant F), the microstructure of the granules can be controlled as described above.

The admixture of the blowing agent E) and co-blowing agent F) in the polymer melt can be effected via dynamic mixers, for example extruders or static mixers.

For higher amounts of co-blowing agent F), for example in the range of 1 to 10 wt .-% based on the propellant-containing polymer melt, a lowering of the melt temperature or the melt viscosity and thus a significant increase in throughput is possible. Thus, a gentle incorporation of thermolabile additives, such as flame retardants, the polymer melt is possible. The composition of the expandable thermoplastic particles is not altered thereby, since the co-blowing agent substantially escapes during melt extrusion. To utilize this effect, CO2 is preferably used. At N2 the effects on the viscosity are lower. Nitrogen is therefore used predominantly to set the desired cell structure.

The liquid-filled chamber for granulating the expandable thermoplastic polymer particles is preferably operated at a temperature in the range of 20 to 80 ° C, more preferably in the range of 30 to 60 ° C.

As a thermoplastic polymer z. Styrene polymers, polyamide (PA), polyolefins such as polypropylene (PP) or polyethylene (PE), polyacrylates such as polymethyl methacrylate (PMMA), polycarbonate (PC), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyethersulfone ( PES), polyether ketones (PEK) or polyether sulfides (PES) or mixtures thereof.

Preference is given to styrene copolymers, such as styrene-butadiene block copolymers, styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), acrylonitrile-styrene-acrylic ester (ASA), methyl methacrylate-butadiene-styrene (US Pat. MBS), methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) polymers, radically polymerized glassy polystyrene (GPPS), impact modified polystyrene (HIPS) or anionically polymerized polystyrene (A-PS) or anionically polymerized impact polystyrene (A-IPS ) used. The composition of the polymer granules can be selected according to the desired properties of the particle foam molding. Styrene-butadiene block copolymers as styrene copolymer component are particularly suitable for improving the elasticity and the resilience of the particle foam molding. With acrylonitrile-containing Styrolcopoly- meren, such as SAN and ABS, the oil resistance and solvent resistance, especially with respect to aromatic solvents and the heat resistance can be improved.

Particularly preferably, a propellant-containing polymer melt is used in the process according to the invention, which

A) from 45 to 97.79 weight percent of a styrenic polymer,

B1) from 1 to 45% by weight of a polyolefin having a melting point in the range from 105 to 140 ° C,

B2) from 0 to 25% by weight of a polyolefin having a melting point below 105 ° C., C1) from 0.1 to 25% by weight of a styrene-butadiene or styrene-isoprene block copolymer,

C2) 0 to 10% by weight of a styrene-ethylene-butylene block copolymer,

D) 0.1 to 5% by weight of a nucleating agent,

E) 1 to 10% by weight of a blowing agent remaining essentially in the polymer particles,

F) 0.01 to 5% by weight of a co-propellant forming the cavities,

in each case based on the propellant-containing polymer melt contains.

Component A

The polymer particles contain 45 to 97.8% by weight, more preferably 55 to 78.1% by weight of a styrene polymer A), such as standard (GPPS) or impact polystyrene (H IPS) or styrene-acrylonitrile copolymers (SAN). or acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof. The expandable thermoplastic polymer particles used to produce the foam particles P1 preferably contain styrene polymer A) as standard polystyrene (GPPS). Particularly preferred are standard polystyrene types having weight average molecular weights in the range of 120,000 to 300,000 g / mol, in particular 190,000 to 280,000 g / mol, determined by gel permeation chromatography; and a melt volume rate MVR (200 ° C / 5 kg) according to ISO 1 13 in the range of 1 to 10 cm ^3/10 min, for example PS 158 K, 168 N or 148 G of BASF SE. To improve the fusion of the foam particles during processing to the molded part, easily flowing types, for example Empera® 156L (Innovene), can be added Components B

As components B), the thermoplastic polymer particles comprise polyolefins B1) having a melting point in the range from 105 to 140 ° C. and polyolefins B2) having a melting point below 105 ° C. The melting point is the melting peak determined by DSC (Dynamic Scanning Calorimetry) at a heating rate of 10 ° C./minute.

The thermoplastic polymer particles contain 1 to 45 weight percent, preferably 4 to 35 wt .-%, particularly preferably 7 to 15 weight percent of a polyolefin B1). As polyolefin B1) is preferably a. Homo- or copolymers of ethylene and / or propylene having a density in the range of 0.91 to 0.98 g / L (determined according to ASTM D792), in particular polyethylene used. In particular injection molding grades come into consideration as polypropylenes. Suitable polyethylenes are commercially available homopolymers of ethylene, such as PE-LD (injection molding types), LLD, -HD, or copolymers of ethylene and propylene (for example Moplen® RP220 and Moplen® RP320 from Basell or Versify® types from Dow) , Ethylene and vinyl acetate (EVA),

Ethylene acrylate (EA) or ethylene-butylene acrylate (EBA) in question. The melt volume index MVI (190 ° C / 2.16 kg) of the polyethylenes is usually in the range of 0.5 to 40 g / 10 min, the density in the range of 0.91 to 0.95 g / cm ³ . In addition, blends with polyisobutene (PIB) (eg Oppanol® B150 from BASF Aktengesellschaft) can be used. Particularly preferred is LLDPE having a melting point in the range of 1 10 to 125 ° C and a density in the range of 0.92 to 0.94 g / L used.

Also suitable as component B1) are olefin block copolymers which are composed of a polyolefin block PB1 (hard block) and a polyolefin block PB2 (soft block), as described, for example, in WO 2006/099631. The polyolefin block PB1 preferably consists of 95 to 100% by weight of ethylene. The PB2 block is preferably composed of ethylene and α-olefin, where as α-olefins styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1, 5-hexadiene or mixtures thereof. Preferred as PB2 block is an ethylene-α-olefin copolymer block with 5 to 60 wt .-% α-olefin, in particular an ethylene-octene copolymer block. Preference is given to multiblock copolymers of the formula (PB 1 -PB 2) n, where n is an integer from 1 to 100. The blocks PB1 and PB2 essentially form a linear chain and are preferably distributed alternately or statistically. The proportion of PB2 blocks is preferably 40 to 60% by weight, based on the olefin block copolymer. Particular preference is given to olefin block copolymers having alternating, hard PB1 blocks and soft, elastomeric PB2 blocks, which are commercially available under the name INFUSE®.

With a lower proportion of polyolefin B1), the blowing agent retention capacity increases significantly. This significantly improves the shelf life and the processability of the expandable, thermoplastic polymer particles. In the range from 4 to 20% by weight of polyolefin, expandable thermoplastic polymer particles having a long storage life are obtained, without the elastic see characteristics of the particle foam produced therefrom deteriorate. This is shown for example in a low Entformungsrest z _res t in the range of 25 to 35%.

As polyolefin B2), the expandable, thermoplastic polymer particles contain 0 to 25 weight percent, preferably 1 to 15 wt .-%, particularly preferably 5 to 10 weight percent of a polyolefin B2) having a melting point below 105 ° C. The polyolefin B2) preferably has a density in the range of 0.86 to 0.90 g / L (determined according to ASTM D792). For this purpose, in particular thermoplastic elastomers based on olefins (TPO) are suitable. Particular preference is given to ethylene-octene copolymers which are obtainable, for example, commercially under the designation Engage® 841 1 from Dow. Expandable, thermoplastic polymer particles containing the component B2) show a significant improvement in the bending work and tear resistance after processing into foam moldings.

Components C

It is known from the field of multiphase polymer systems that most polymers are immiscible or only slightly miscible with each other (Flory), so that depending on the temperature, pressure and chemical composition for segregation in respective phases. If incompatible polymers are covalently linked to one another, the segregation does not take place on a macroscopic level, but only on a microscopic level, ie. on the length scale of the individual polymer chain. In this case we therefore speak of microphase separation. This results in a variety of mesoscopic structures, e.g. lamellar, hexagonal, cubic, and bicontinuous morphologies strongly related to lyotropic phases.

For specific adjustment of the desired morphology, compatibilizers (components C) are used. An improvement in the compatibility is achieved according to the invention by using a mixture of styrene-butadiene or styrene-isoprene block copolymers as component C1) and styrene-ethylene-butylene block copolymers (SEBS) as component C2).

The compatibilizers lead to improved adhesion between polyolefin-rich and styrene-polymer-rich phases and improve even in small amounts, the elasticity of the foam significantly compared to conventional EPS foams. Investigations of the domain size of the polyolefin-rich phase showed that the compatibilizer stabilized small droplets by reducing the interfacial tension.

Particularly preferably, the expandable thermoplastic polymer particles consist of a multiphase propellant-containing polymer mixture having at least one continuous phase and at least two disperse phases P1 and P2 distributed in the continuous phase, wherein a) the continuous phase consisting essentially of the components A,

b) the first disperse phase P1 consisting essentially of the components B1 and B2 and c) the second disperse phase P2 consisting essentially of the component C1.

The components C2) preferably form a phase interface between the disperse phase P1 and the continuous phase.

This additional disperse phase makes it possible to keep the domain size of the disperse phase <2 μιτι at a higher soft phase fraction. With the same expandability, this leads to a higher bending work in the paricle foam.

Preferably, in the expandable, thermoplastic polymer particles, the sum of components C1) and C2) is in the range from 3.5 to 30 percent by weight, particularly preferably in the range from 6.8 to 18 percent by weight.

Preferably, the weight ratio of the sum of the components B1) and B2) to the component C2) in the expandable, thermoplastic polymer particles is in the range from 5 to 70.

The weight ratio of components C1) to C2) in the expandable thermoplastic polymer particles is preferably in the range of 2 to 5.

The expandable thermoplastic polymer particles contain as component C1) 0.1 to 25 weight percent, preferably 1 to 15 weight percent, in particular 6 to 9.9 weight percent of a styrene-butadiene or styrene-isoprene block copolymer.

For example, styrene-butadiene or styrene-isoprene block copolymers are suitable for this purpose. The total diene content is preferably in the range from 20 to 60% by weight, particularly preferably in the range from 30 to 50% by weight, the total styrene content is correspondingly preferably in the range from 40 to 80% by weight, particularly preferably in the region of 50 to 70% by weight.

Preferred compatibilizers are styrene-butadiene-styrene (SBS) triblock copolymers having a butadiene content of from 20 to 60% by weight, preferably from 30 to 50% by weight, which may be partially hydrogenated or non-hydrogenated for example, under the name Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1 101, Kraton® D 1 155, Tuftec® H 1043 or Europren® SOL T6414 commercially. These are SBS block copolymers with sharp transitions between B and S blocks. As component C2), the expandable, thermoplastic polymer particles contain from 0.1 to 10% by weight, preferably from 1 to 9.9% by weight, in particular from 0.8 to 5% by weight, of a styrene-ethylene-butylene block copolymer (SEBS). Suitable styrene-ethylene-butylene Block copolymers (SEBS) are, for example, those which are obtainable by hydrogenation of the olefinic double bonds of the block copolymers C1). Suitable styrene-ethylene-butylene block copolymers are, for example, the commercially available Kraton® G types, in particular Kraton® G 1650.

The process of the invention expandable thermoplastic polymer particles with cavities having a mean diameter in the range of 0.1 to 50 μιτι, preferably 1 to 30 μιτι available. Preferably, the expandable thermoplastic polymer particles have a mean diameter in the range of 0.2 to 2.5 mm and 50 to 300, preferably 70 to 150 cavities / mm ² cross-sectional area. The number of cavities can be done, for example, by counting a thin film through the polymer particles under an optical microscope. Its bulk density is preferably in the range of 500 to 590, preferably 520 to 580 kg / m ³ .

The prebuilt structure of the expandable granules allows for easier foamability, a controlled adjustment of the cell size and thus a substantial improvement in the processing and foam properties.

To improve processability, the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.

The resulting round or oval particles are preferably foamed to a diameter in the range of 0.2 to 10 mm. Its bulk density is preferably in the range of 10 to 100 g / l.

The welding of the prefoamed foam beads to the molded part and the resulting mechanical properties are improved in particular by coating the expandable thermoplastic polymer particles with a glyceryl stearate. Particularly preferred is a coating of 50 to 100 wt .-% glyceryl tristearate (GTS), 0 to 50 wt .-% glycerol monostearate (GMS) and 0 to 20 wt .-% silica used.

The expandable, thermoplastic polymer particles can by means of hot air or water vapor to foam particles having a density in the range of 8 to 200 kg / m ³ , preferably in the range of 10 to 80 kg / m ³ , in particular in the range of 10 to 50 kg / m Pre-foamed ³ and then welded in a closed mold to foam moldings. Usually, an overpressure in the range of 0.5 to 1, 5 bar, in particular 0.7 to 1, 0 bar applied.

By applying the concept, the blowing agent contents can be significantly reduced compared to standard EPS in order to achieve comparable densities. which can be saved blowing agent. Lower minimum bulk density n can thus be achieved with the same blowing agent content. In addition, pre-granulated granulates can be impregnated much more easily with propellants, for example in the case of loss of propellant due to storage or transport. Since the pre-nucleation can be carried out by means of nitrogen or other inert gases previously obtained from the atmosphere, it is a comprehensive and resource-saving concept for improving the expandability of thermoplastic particle foams and for better adjustment of the cell structure.

In larger quantities, the cavities forming co-blowing agent F) generally have a strong plasticizing effect. As a result of the viscosity-lowering effect of the co-blowing agent F), the throughput can be increased with an identical temperature control or the melt temperature can be reduced at an identical throughput while the recipe is otherwise identical. The pressure drop in pressure-consuming apparatus such as perforated plates or mixers remains identical because the material has an identical melt viscosity. In the first case, the temperature load of the material can thus be reduced and also thermally sensitive materials such as flame retardants can be incorporated. In the second case, through the increase in throughput with identical equipment / pressure stage of the apparatus, a more economical production of the expandable particles is possible. Another aspect is that the proportion of the actual propellant without changing the

Melt viscosity can be reduced without having to adjust the throughput of the system or the process control. Due to the higher solubility in polymers, carbon dioxide is to be preferred as the plasticizing co-blowing agent F). The expandable thermoplastic obtained by the process according to the invention

Polymer particles can be made into higher cell count foams, i. fine cell structure are processed. The homogeneous foam structure improves the mechanical properties and thermal insulation of the foams. Another effect is the reduction of energy costs in foam processing. Due to the faster pre-foaming higher throughputs can be achieved. Due to the lower blowing agent contents in combination with the pre-nucleating, the demolding times can be significantly reduced and the cycle times during foaming shortened.

Examples of starting materials: Component A:

Polystyrene with a melt viscosity index MVI (200 ° C./5 kg) of 2.9 cm / 10 min (PS 158K from BASF SE, Mw = 280,000 g / mol, viscosity number VN 98 ml / g) Component B:

B1: polyethylene LLDPE (LL1201 XV, Exxon Mobile, density 0.925 g / L, MVI = 0.7 g / 10 min, melting point 123 ° C)

B2: polyethylene ethylene-octene copolymer (Dow Engage® 8402, density 0.880 g / l, MVI = 18 g / 10 min, melting point 72 ° C.)

Component C:

C1 .1: Styrolux® 3G55, styrene-butadiene block copolymer from BASF SE,

C1 .2 Styroflex® 2G66, thermoplastic elastic styrene-butadiene block copolymer (S-TPE) from BASF SE,

C2: Kraton G 1651, styrene-ethylene-butylene block copolymer from Kraton Polymers LLC

Component D:

D nucleating agent: talc

Component E:

E Propellant mixture of 95% by weight of isopentane and 5% by weight of n-pentane component F:

F co-propellant nitrogen (example B1-B17), carbon dioxide (example B19-B36)

Production of the expandable granules B1 - B1 1

The production of the expandable granules was carried out by a melt impregnation method using static mixing apparatus. For this purpose, the polymers were first plasticized in an extruder and conveyed via a melt pump into a series of static mixers and heat exchangers. At the entrance of the first static mixer, technical iso-pentane (95% iso-pentane / 5% n-pentane) was added together with the co-propellant F) and the melt was impregnated. The corresponding formulations are shown in Table 1. Subsequently, the melt temperature was reduced via a heat exchanger and homogenized the melt temperature over another static mixer. Pressure was applied by another melt pump to granulate the material via a perforated plate (49 holes a 0.60 mm) with a pressurized underwater granulation (water pressure 12 bar, water temperature 50 ° C.). The average particle size was about 1.25 mm. The total throughput was 70 kg / h. The melt temperature at the nozzle exit was approx. 203 ° C.

Table 1: Composition (parts by weight) of the expandable granules B1-B1 1 B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B1 1

Component A 70.2 70.25 70.2 70.15 70.1 70.05 70 70.1 70.1 71, 3 71, 2

Component B1 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7 1 1, 7

Component B2 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9

Component C1 .1 7.8 7.8 7.8 7.8

Component C1 .2 7.8 7.8 7.8 7.8 7.8 7.8 7.8

Component C2 1, 0 1, 0 1, 0

Component D 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

(Talc)

Component E 5.9 5.8 5.8 5.8 5.8 5.8 5.8 5.8 5.8 4.8 4.8

(Propellant)

Component F 0.05 0.10 0.15 0.20 0.25 0.30 0.20 0.20 0.05 0.10

(Nitrogen)

Analysis of Expandable Granules The transmission electron micrographs (TEM) show the cellular structures of the propellant-containing granules in the form of spheroidal cells (dark areas, FIG. 1), which later contribute to better expansion capability and a finer cell structure in the foam. The cells of the propellant loaded granules are in the order of less than 50 μιτι, in the images are cell sizes to 1 μιτι clearly visible.

Processing and characterization of expandable granules

The coating components used were 70% by weight of glycerol tristearate (GTS) and 30% by weight of glycerol monostearate (GMS).

The propellant-containing granules were prefoamed in an EPS prefoamer foam beads low density (15 - 25 g / L) and processed in an EPS molding machine at an overpressure of 0.7 - 1, 1 bar to form parts. Various mechanical measurements were carried out on the moldings. In the examples according to the invention a clear elastification is observed in comparison to pure EPS, which is recognizable by the very high recovery capacity. The compressive strength was determined at 10% compression according to DIN-EN 826 and the bending strength according to DIN-EN 12089. The bending work was determined from the measured values for flexural strength.

Table 2 shows the processing parameters such as pre-foaming time and demolding time. It can be clearly seen that the addition of nitrogen results in a reduction of the pre-foaming time and demolding time. The cell size could be significantly reduced become. In addition, it was possible to significantly reduce the blowing agent content compared to the reference without impairing the properties.

Table 2: Processing and properties of the foam particles obtained from Example B1-B15

Preparation of the expandable granules B 12 - B 17

The production of the expandable granules was carried out by a melt impregnation process. For this purpose, first polystyrene 158 K (component A) were plasticized in an extruder. The melt was impregnated in the extruder with technical iso-pentane (95% iso-pentane / 5% n-pentane) together with the co-blowing agent F) and homogenized. The corresponding Signatures are shown in Table 3. Through a melt pump at the extruder head pressure was applied to granulate the material through a perforated plate (2 holes ä 0.65 mm) with a pressurized underwater granulation (water pressure 12 bar, water temperature 47 ° C). The average particle size was about 1.25 mm. The total throughput was 4.5 kg / h. The melt temperature at the nozzle exit was approx. 210 ° C.

Table 3: Composition of the expandable granules, processing and properties of the foam particles obtained from Example B12 - B17

Fig. 1 and Fig. 2 show transmission electron micrographs in different magnification of a thin section through an expandable granules of Example 13 with the homogeneously distributed cavities in the interior of the granules.

Production of expandable granules

The production of the expandable granules was carried out by a melt impregnation method using static mixing apparatus. For this purpose, the polymers were first plasticized in an extruder and metered via a melt pump into a series of static mixers and heat exchangers. At the entrance of the first static mixer, technical iso-pentane (95% iso-pentane / 5% n-pentane) was added together with the co-propellant F) and the melt was impregnated. The corresponding formulations can be found in the table. Subsequently, the melt temperature was reduced via a heat exchanger and homogenized the melt temperature over another static mixer. Pressure was applied by another melt pump to granulate the material through a perforated plate (2 holes of 0.65 mm) with pressure-controlled underwater granulation (water pressure see table, water temperature 47 ° C.). The mean particle size was about 1 .25 mm. The total throughput was 4.5 kg / h. The melt temperature at the nozzle exit was approx. 207 ° C.

Preparation of the expandable granules Example 19 to 36

The production of the expandable granules was carried out by a melt impregnation method using static mixing apparatus. An overview of the composition of the materials is given in Tab. 4 - the proportions of the polymers or the talc (components A-D) were identical to Examples 12 and 1, the proportion of the blowing agent E) and the co-blowing agent F) was varied. For this purpose, the polymers were first plasticized in an extruder and metered via a melt pump into a series of static mixers and heat exchangers. At the entrance of the first static mixer technical iso-pentane (95% iso-pentane / 5% n-pentane) was added together with the co-propellant F) and the melt impregnated. The procedure was analogous to Example 12 and Example 9, wherein instead of nitrogen C02 as component F) was used to reduce the temperature load. The corresponding formulations can be found in the table. Subsequently, the melt temperature was reduced via a heat exchanger and homogenized the melt temperature over another static mixer. Pressure was applied by another melt pump to granulate the material through a perforated plate (2 holes of 0.65 mm) with pressure-controlled underwater granulation (water pressure see table, water temperature 47 ° C.). The mean particle size was about 1 .25 mm. The total throughput was 4.5 kg / h.

To demonstrate the plasticizing effect and the possible throughput increases or reduced melt temperatures, the pressure loss via a static mixer was used in each case as a measure of the melt viscosity. The static mixer used had a diameter of 25 mm and an L / D ratio of 15. The pressure loss thereby scales with the viscosity in the laminar range as follows: where Re, Ne, ^, w _j | _ and D denote the Reynolds number, the Ne number, the mean shear viscosity, the mean flow rate, the length of the static mixer, and the diameter of the static mixer. For static mixers of type CSE-X 8, the product of Ne and Re is constant and is 1200. The average flow rate is: where V _j m _j P and A are the volumetric flow rate, mass flow rate, melt density, and cross-sectional area of the mixer. The mean shear viscosity of the

Polymer melt, ^, at the mean shear rate, ^, is calculated as:

Based on these principles, the shear viscosity of the melt was determined at different temperatures and throughputs (Table 4). The influence of CO 2 on the viscosity and on the pressure loss (on the static mixer / additive mixer) in Examples 19 to 36 is given in each case. The pressure loss is a technically limiting quantity since only a maximum pressure loss at the mixer and a total pressure in the system are permissible , By using C02, with identical pressure loss to the system containing only pentane, the temperature load can be reduced (24/25, 33/34) or the throughput increased (26/27, 35/36). The foaming behavior is not adversely affected by the use of C02.

Example CompoTotal pentane C02 Pressure-average VisTemperAnent throughput Losslessness Tire without

propellant

(kg / h) (wt%) (wt%) (bar) (Pa.s) (° C)

B19 B12 4.5 6.5% 0.0% 26 1 .276 183

B20 B12 4.5 3.8% 0.0% 65 3.212 183

B21 B12 4.5 3.8% 0.5% 56 2,756 183

B22 B12 4.5 3.8% 1, 0% 47 2.304 182

B23 B12 4.5 3.7% 2.8% 30 1 .467 183

B24 B12 4.5 3.8% 1, 0% 64 3,140 175

B25 B12 4.5 3.7% 2.8% 66 3.238 158

B26 B12 6.2 3.8% 1, 0% 62 2,208 183

B27 B12 1 1, 0 3.7% 2.8% 64 1 .285 183

B28 B1 4.5 6.1% 0.0% 48 2.314 187

B29 B1 4.5 6.1% 0.5% 44 2.127 186

B30 B1 4.5 6.0% 0.9% 40 1 .906 186

B31 B1 4.5 6.0% 1, 4% 36 1 .703 186

B32 B1 4.5 6.0% 1, 8% 32 1 .546 186

B33 B1 4.5 6.0% 0.9% 46 2,207 178

B34 B1 4.5 6.0% 1, 8% 47 2.255 169

B35 B1 6.1 6.0% 0.9% 48 1 .699 186

B36 B1 8.0 6.0% 1, 8% 46 1 .241 186

Claims

claims

A process for producing hollow, expandable, thermoplastic polymer particles by extrusion of a blowing agent-containing polymer melt through a die plate and granulation in a liquid-filled chamber under a pressure in the range of 1, 5 to 15 bar, characterized in that the propellant-containing polymer melt

0.1 to 5% by weight of a nucleating agent D),

From 1 to 10% by weight of a blowing agent E remaining essentially in the polymer particles,

0.01 to 5 wt .-% of a cavities forming co-blowing agent F), each based on the blowing agent-containing polymer melt containing.

A method according to claim 1, characterized in that the blowing agent-containing polymer melt as nucleating agent D) talcum, silica, mica, clay, zeolites, calcium carbonate or a polyethylene wax.

A method according to claim 1 or 2, characterized in that the blowing agent-containing polymer melt contains as blowing agent E) an aliphatic C ₃ - C ₇ hydrocarbon or mixtures thereof.

Method according to one of claims 1 to 3, characterized in that the blowing agent-containing polymer melt as the cavities forming co-blowing agent F) nitrogen, carbon dioxide, argon, helium or mixtures thereof.

Method according to one of claims 1 to 4, characterized in that the propellant-containing polymer melt contains less than 0.5 wt .-% water.

Method according to one of claims 1 to 5, characterized in that the liquid-filled chamber is operated at a temperature in the range of 20 to 80 ° C.

Method according to one of claims 1 to 5, characterized in that, the propellant-containing polymer melt

A) from 45 to 97.79 weight percent of a styrenic polymer,

C2) 0 to 10% by weight of a styrene-ethylene-butylene block copolymer,

D) 0.1 to 5% by weight of a nucleating agent, E) 1 to 10% by weight of a blowing agent remaining essentially in the polymer particles,

F) 0.01 to 5% by weight of a co-propellant forming the cavities,

in each case based on the propellant-containing polymer melt contains.

Expandable thermoplastic polymer particles with cavities having a mean diameter in the range of 0.1 to 50 μιτι, obtainable according to one of claims 1 to 7.

Expandable thermoplastic polymer particles according to claim 8, characterized in that they have an average diameter in the range of 0.2 to 2.5 mm and 50 to 300 Hohlräumn / mm ² cross-sectional area.

0. Expandable thermoplastic polymer particles according to claim 8 or 9, characterized in that they have a bulk density in the range of 500 to 590 kg / m ³ .