EP2638103A1 - Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierung - Google Patents
Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierungInfo
- Publication number
- EP2638103A1 EP2638103A1 EP11779437.0A EP11779437A EP2638103A1 EP 2638103 A1 EP2638103 A1 EP 2638103A1 EP 11779437 A EP11779437 A EP 11779437A EP 2638103 A1 EP2638103 A1 EP 2638103A1
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- EP
- European Patent Office
- Prior art keywords
- polymer particles
- impregnation
- thermoplastic polymer
- range
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
Definitions
- the invention relates to a process for producing expandable, thermoplastic polymer particles by post-impregnation of thermoplastic polymer particles containing at least one styrene polymer and at least one polyolefin, with a blowing agent.
- WO 2009/1 12549 A describes expandable thermoplastic polymer particles based on polyolefin / styrene polymer mixtures, which are obtained by melt impregnation and subsequent underwater granulation under pressure and can be processed into elastic foams.
- the Nachimlessnessgnians of styrene polymers for the production of expandable, polystyrene (EPS) is usually carried out in aqueous suspension at elevated temperatures in the presence of a blowing agent.
- EPS expandable, polystyrene
- GB 2 162 789 A describes a two-stage production process of expandable polystyrene pellets by extrusion and strand granulation of polystyrene pellets, optionally screening of the polystyrene pellets and impregnation of the polystyrene pellets with blowing agent in aqueous suspension.
- GB 1 092 032 describes the liquid phase impregnation of styrene polymers in pentane at temperatures between 65 and 95 ° C.
- finely divided inorganic substances such as calcium carbonate as a release agent prevents the agglomeration of the particles during the impregnation. The release agents must then be washed off again.
- a impregnation in the gas phase is unsuitable for styrene polymers, since it comes during the impregnation to a strong softening of the glassy polymer and the particles stick together.
- the reason is the reduction of the glass transition temperature during the blowing agent absorption and the associated softening of the polymer.
- the impregnation window is too narrow to economically load the granules in an appropriate time at elevated temperature. Loading is then only possible by adding inorganic release agents, which, however, adhere to the particles after the impregnation and worsen the welding of the foam particles during subsequent processing and thus lead to a deterioration of the mechanical properties.
- EP 1 535 955 B1 discloses the impregnation of polyolefin polymers by overlaying with pentane for the production of expandable polyolefin particles. Due to the crystallinity of the polyolefins, expandable polyolefin particles generally have a low blowing agent retention capacity.
- DE 44 29 844 A1 describes a process for the preparation of expanded polyolefin foam particles by impregnation of polyolefin particles with gaseous blowing agents in a fluidized bed and subsequent sudden relaxation of the contents of the impregnating reactor.
- EP 1 612 239 A1 describes expandable, styrene-modified olefin resin particles by impregnation with a blowing agent and subsequent impregnation under pressure with a surfactant for improving the antistatic properties.
- the expandable particles have low propellant retention and must therefore be immediately expanded into foam particles in a foamer.
- the object of the present invention was to find a simple and rapid process for the production of expandable thermoplastic particles, in particular multiphase mixtures of polyolefins and styrene polymers, in which the blowing agent is homogeneously incorporated in the impregnation.
- the expandable thermoplastic particles should have good blowing agent retention and, after foaming, lead to foam particles having a homogeneous cell structure.
- thermoplastic polymer particles containing at least one styrenic polymer and at least one polyolefin with a blowing agent has been found, wherein the post-impregnation is carried out predominantly in the gas phase.
- Impregnation refers to the loading of the polymer system with the blowing agent, the blowing agent being distributed in the polymer system. Impregnations can be carried out in the liquid and / or gaseous propellant phase. In addition, the phase transitions between gaseous and liquid phases may be fluid.
- the propellants used are preferably aliphatic C 3 -C 7 -hydrocarbons, in particular n-pentane and iso-pentane or mixtures thereof.
- the blowing agent In the gaseous blowing agent phase, the blowing agent is homogeneously distributed in the atmosphere and is absorbed very uniformly by the granules to be impregnated. This reduces local softening and thus sticking.
- the propellant uptake In the gaseous propellant phase, the propellant uptake can thus be better controlled. If the propellant is liquid during loading, the propellant uptake is more difficult to control and the gradient in the impregnation is higher. However, the effect can be compensated by appropriate temporal maturation. So it is possible to fill a gas-tight metal drum with granules and liquid pentane and gas-tight seal. By subsequent ripening, the blowing agent is distributed homogeneously over time and uniformly expandable granules are obtained.
- the impregnation vessel is characterized in that it is gas-tight for the propellant system used and builds up the associated vapor pressure at a given temperature.
- the impregnation vessel may e.g. be made of glass or metal.
- the gas phase impregnation can be carried out as follows.
- the filled with liquid pentane evaporator is brought to test temperature in a water bath.
- the valve is closed. In the evaporator, the temperature associated with the vapor pressure.
- the impregnation vessel is heated to 5 ° C, the heating tape to 10 ° C above the test temperature.
- the impregnation vessel is evacuated to less than 0.1 bar.
- the valve is opened.
- the pentane flows into the vessel in gaseous form and is absorbed by the granules.
- the valve is closed.
- the gaseous pentane present in the boiler's atmosphere is taken up by the polymer to the thermodynamic equilibrium.
- the granules are removed afterwards.
- the pentane content in the granules depends on the fumigation time and the test temperature.
- the impregnation is carried out predominantly in the gas phase, preferably exclusively in the gas phase.
- some of the thermoplastic particles to be impregnated may be in a liquid propellant phase.
- the filled with liquid pentane evaporator is brought to test temperature in a water bath.
- the valve is closed. In the evaporator, the temperature associated with the vapor pressure.
- the impregnation vessel is heated to a lower or the same temperature as the test temperature, the heating tape to 10 ° C above the test temperature.
- the impregnation vessel is evacuated to less than 0.1 bar. After reaching constant temperature values, the valve is opened.
- the pentane flows into the vessel in gaseous form, condenses there in part and is taken up by the granules. After a set time, the valve is closed. sen.
- the gaseous pentane present in the atmosphere of the boiler and the condensed pentane are taken up by the polymer until the thermodynamic equilibrium or until the termination of the experiment.
- the granules are removed afterwards.
- the pentane content in the granules depends on the fumigation time, the amount of pentane, the temperature difference and the test temperature.
- the impregnation vessel can also be filled with a defined amount of liquid pentane.
- the sieve bottom prevents direct contact between granules and pentane.
- the mesh size is smaller than the smallest granule diameter of the bed.
- the impregnation vessel is brought to test temperature which adjusts the associated vapor pressure.
- the gaseous pentane present in the atmosphere of the vessel is taken up by the polymer until the thermodynamic equilibrium or until the termination of the experiment. After a defined time, the remaining pentane is sucked off and the granules are removed.
- the pentane content in the granules depends on the amount of pentane, the fumigation time and the test temperature.
- the Nachimoniagn ist is preferably carried out at a temperature in the range of 30 to 80 ° C, more preferably 40 to 50 ° C.
- the gassing time is preferably in the range from 5 to 180 minutes, more preferably in the range from 50 to 100 minutes.
- the Nachimlessnessgn ist is preferably carried out in a fluidized bed.
- the inventive method is particularly suitable for thermoplastic polymer particles, the cavities having a mean diameter in the range of 0.1 to 50 ⁇ , preferably 1 to 30 ⁇ have.
- thermoplastic polymer particles used for the post-impregnation preferably have an average diameter in the range from 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 section 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 .
- thermoplastic polymer particles used for the post-impregnation preferably have at least one disperse polyolefin-rich phase P1 and a continuous styrene polymer-rich phase.
- thermoplastic polymer particles used for the post-impregnation contain
- thermoplastic polymer particles in each case based on the thermoplastic polymer particles used.
- the preferably used cavities containing polymer particles can by extrusion of a polymer melt through a nozzle plate and granulation in a liquid-filled chamber under a pressure in the range of 1, 5 to 15 bar, carried out, wherein the polymer melt
- nucleating agent D 0.1 to 5 wt .-%, preferably 0.3 to 1, 0 wt .-% of a nucleating agent D
- a cavities forming gas F selected from nitrogen, carbon dioxide, argon, helium or mixtures thereof
- thermoplastic polymer particles used for the post-impregnation are particularly preferably used in the process according to the invention, which are obtained by extrusion and granulation of a blowing agent-containing polymer melt
- 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,
- the aforesaid method for adjusting this cavity morphology may also be referred to as pre-nucleation, the cavities being formed essentially by the gas F).
- the gas forming the cavities F) differs from the actual blowing agent E in its solubility in the polymer.
- a blowing agent E) are completely dissolved in the polymer at sufficiently high pressure.
- the pressure is reduced, preferably within a short time, and thus reduces the solubility of the gas F).
- the blowing agent E) remains, if used, due to its higher solubility and / or its low diffusion rate predominantly dissolved in the polymer.
- 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).
- gases F) 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 gas F) has more of the characteristics.
- gases F 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 gas F) has more of the characteristics.
- small amounts of conventional nucleating agents for example inorganic particles such as talc, may be used.
- gas F used in the pre-nucleation should exceed the maximum solubility at the present process conditions. Therefore, preference is given to using gases F) which have a low but sufficient solubility in the polymer.
- gases F 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.
- inert gases such as nitrogen and carbon dioxide.
- nitrogen and carbon dioxide gases
- both gases are characterized by low costs, good availability, easy handling and reaction-free or inert behavior.
- the gases themselves are extracted from the atmosphere, they also have an environmentally neutral behavior.
- the amount of gas F) used should be: (i) sufficiently small to dissolve at the given melt temperatures and pressures during melt impregnation until granulation; (ii) be sufficiently high to segregate and nucleate at the granulation water pressure and granulation temperature from the polymer.
- at least one of the blowing agents used is gaseous at room temperature and under atmospheric pressure.
- gas F which completely escapes from the expandable granules within a short time after the initial nucleation.
- Nitrogen, carbon dioxide, argon, helium or mixtures thereof are particularly preferably used as gas F).
- corresponding pre-nucleated particles can be obtained by the suspension process, for example by suspension polymerization in the presence of persulfates and electrolytes, as described in EP-A 0 761 729.
- suitable pre-nucleated particles can also be obtained by drying water-containing EPS particles.
- Metallic barrels and octabins are used, among other things, for the transport and storage of the expandable granules.
- barrels it should be noted that the release of the gas F) can possibly build up pressure in the drum.
- 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.
- barrels which allow the gas 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 gas F).
- Vornukle muscles for example, by adding small amounts of nitrogen and carbon dioxide, a cellular morphology can be adjusted in the expandable, propellant-containing granules.
- the mean cell size in the center of the particles can be greater than in the edge regions and the density in the edge regions of the particles higher. As a result, blowing agent losses are minimized as much as possible.
- blowing agents 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.
- the diffusion times are lower, on the other hand, it requires analogous to directly impregnated systems lower blowing agent amounts for foaming.
- 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 waxes, such as the polyethylene waxes sold under the name Luwax®. Talc is preferably used.
- the thermoplastic polymer particles used for the post-impregnation are preferably coated with a processing aid.
- thermoplastic polymer particles used for the post-impregnation preferably contain the following components:
- the polymer particles contain 45 to 97.8 wt .-%, particularly preferably 55 to 78.1 wt .-% of a styrene polymer A), such as standard (GPPS) - or impact polystyrene (HIPS) or styrene-acrylonitrile copolymers (SAN) or Acrylonitrile-butadiene-styrene copolymers (ABS) or mixtures thereof.
- GPPS standard
- HIPS impact polystyrene
- SAN styrene-acrylonitrile copolymers
- ABS Acrylonitrile-butadiene-styrene copolymers
- the expandable, thermoplastic polymer particles used to produce the foam particles P1 preferably contain styrene polymer A) as standard polystyrene (GPPS).
- 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.
- easily flowing types for example Empera® 156L (Innovene), can be added.
- 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 means of DSC (differential 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).
- the polyolefin B1) used is preferably a homo- or copolymer of ethylene and / or propylene having a density in the range from 0.91 to 0.98 g / l (determined according to ASTM D792), in particular polyethylene.
- 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 .
- blends with polyisobutene eg Oppanol® B150 from BASF SE
- PIB polyisobutene
- Particularly preferred LLDPE used with 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.
- 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 ⁇ -olefin, where as ⁇ -olefins styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1, 5-hexadiene or mixtures thereof.
- PB2 block is an ethylene- ⁇ -olefin copolymer block with 5 to 60 wt .-% ⁇ -olefin, in particular an ethylene-octene copolymer block.
- 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.
- Particularly preferred are olefin block copolymers with alternating, hard PB1 blocks and soft, elastomeric PB2 blocks, which are commercially available under the name INFUSE®.
- 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).
- thermoplastic elastomers based on olefins (TPO) are suitable.
- TPO olefins
- 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.
- compatibilizers for specific adjustment of the desired morphology, compatibilizers (component 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).
- SEBS styrene-ethylene-butylene block copolymers
- 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.
- the expandable, thermoplastic polymer particles particularly preferably 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, where a) the continuous phase consists essentially of the components A,
- 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 component C2) preferably forms 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 ⁇ at a higher soft phase fraction. With the same expandability, this leads to a higher bending work in the particle foam.
- 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.
- the weight ratio of the sum of the components B1) and B2) to the component C2) in the expandable, thermoplastic polymer particles is preferably in the range from 5 to 70.
- the weight ratio of component C1) to C2) in the expandable, thermoplastic polymer particles is preferably in the range from 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 block copolymer or styrene-isoprene block copolymer.
- 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 unhydrogenated.
- SBS styrene-butadiene-styrene
- These are for example under the name Styroflex® 2G66, Styrolux® 3G55, Styroclear® GH62, Kraton® D 1 101, Kraton® D 1 155, Tuftec® H1043 or Europren® SOL T6414 commercially.
- SBS block copolymers with sharp transitions between B and S blocks.
- the expandable thermoplastic polymer particles contain 0 to 10% by weight, preferably 1 to 9.9% by weight, in particular 0.8 to 5% by weight, of a styrene-ethylene-butylene block copolymer (SEBS).
- SEBS styrene-ethylene-butylene block copolymers
- Suitable styrene-ethylene-butylene block copolymers (SEBS) are, for example, those 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 expandable, thermoplastic polymer particles generally contain 1 to 15 percent by weight, preferably 3 to 10 percent by weight, based on the sum of all components A) to E) of a physical blowing agent.
- 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 C 3 to Ce hydrocarbons, alcohols, ketones or ethers.
- Suitable aliphatic blowing agents are, for example, aliphatic C 3 to Ce 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 iso
- the propellants used are preferably aliphatic C 3 -C 7 -hydrocarbons, in particular n-pentane and iso-pentane or 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 expandable, thermoplastic polymer particles contain 0 to 5 weight percent, preferably 0.3 to 3 weight percent of a nucleating agent or nucleating agent, for example talc.
- additives plasticizers, halogen-containing or halogen-free flame retardants, soluble and insoluble inorganic and / or organic dyes and pigments or fillers may be added to the multiphase polymer mixture in amounts which do not affect the formation of domains and the resulting foam structure.
- the polymer mixture having a continuous and at least one disperse phase can be prepared by mixing two incompatible thermoplastic polymers, for example in an extruder.
- the expandable thermoplastic polymer particles according to the invention can be obtained by a process in which a) a polymer mixture having a continuous phase and at least one disperse phase is prepared by mixing components A) to C) and optionally E), b) impregnating this polymer mixture with a blowing agent D) and granulating it to form expandable thermoplastic polymer particles,
- the average diameter of the disperse phase of the polymer mixture prepared in step a) is preferably in the range from 1 to 2000 nm, particularly preferably in the range from 100 to 1500 nm.
- the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.
- the resulting expandable particles are 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 molding and the resulting mechanical properties are improved in particular by coating the expandable thermoplastic polymer particles with a glycerol stearate.
- the expandable thermoplastic polymer particles can be prefoamed by means of hot air or steam to form foam particles having a density in the range from 8 to 200 kg / m 3 , preferably in the range from 10 to 80 kg / m 3 , in particular in the range from 10 to 50 kg / m 3 and then welded in a closed mold to foam moldings.
- the processing pressure is chosen so low that domain structure is retained in the cell membranes, welded to particle foam moldings.
- blowing agent loading in a step separated from the preparation of the minigranules works very well in the gas phase or liquid propellant phase, whereas the impregnation under suspension conditions in an aqueous phase is unsatisfactory and difficult to control.
- the polyolefin / styrene polymer mixtures according to the invention By means of the polyolefin / styrene polymer mixtures according to the invention, it has now been possible to provide a polymer system which can be impregnated very well in a short time in the gas phase or liquid propellant phase without the polymer granules sticking together and thus remaining free-flowing. In this case, it is possible to dispense with the use of aqueous suspensions or inorganic coating compositions.
- the impregnated polymer granules according to the invention surprisingly have a good propellant-retaining capacity and can be temporarily stored for months before being processed in containers such as, for example, metal drums.
- the found polyolefin / styrene polymer blends combine the positive properties of styrene and polyolefin polymers in one system.
- the final expandable thermoplastic polymer particles may be coated by glycerol esters, antistatic agents or anticaking agents.
- Conventional coating compositions can be applied before or after impregnation in order to optimize the subsequent welding, but are not required for loading with the blowing agent.
- the resulting round or oval particles are 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 molding and the resulting mechanical properties are improved in particular by coating the expandable thermoplastic polymer particles with a glycerol stearate.
- the expandable thermoplastic polymer particles can be prefoamed by means of hot air or steam to form foam particles having a density in the range from 8 to 200 kg / m 3 , preferably in the range from 10 to 80 kg / m 3 , in particular in the range from 10 to 50 kg / m 3 and then welded in a closed mold to foam moldings.
- Polymer granules of multiphase polyolefin / styrene polymer mixtures can be extremely well in the gas phase impregnated with propellant, preferably pentane.
- propellant preferably pentane.
- the polymer melt is not loaded in an extruder with pentane, but the loading with the blowing agent takes place after the extrusion step in a subsequent impregnation step in the gas / liquid phase.
- the separation of the two process steps reduces the safety expenditure. Furthermore, the on-site impregnation significantly reduces pentane emissions and commercially available extruders can be used for the production of minigranulates.
- the polymer components without the actual propellant pentane are mixed together in an extruder and granulated.
- nucleating agents such as talc or nonflammable gases such as nitrogen or carbon dioxide are added in this step.
- nitrogen or carbon dioxide are added in this step.
- the addition of small amounts of nitrogen leads to the first gas bubbles in the granules during granulation and later favors a uniform foaming with a homogeneous cell structure.
- the propellant-free granules are then subsequently impregnated in the gas / liquid phase. Attempts to impregnate the minigranules in aqueous suspension did not work and led either to lenticular minigranules or inhomogeneous cell structures. The mechanical characteristics of the granules produced by suspension impregnation and samples processed into foam parts were poor.
- Component B is a compound having Component B:
- Component F Nitrogen N 2
- the raw material granules were obtained by extrusion of the components listed in Table 1 and subsequent underwater granulation.
- the average particle size was 1, 25 mm.
- the raw material granules E1 were produced by a melt impregnation process using a twin-screw extruder from Leistritz ZE 40 with static mixing apparatus.
- the polymer components according to Table 1 were first plasticized in the extruder and conveyed by means of a melt pump in a series of static mixers and heat exchangers, homogenized and extruded.
- technical iso-pentane 95% iso-pentane / 5% n-pentane
- the melt was reduced via a heat exchanger and homogenized the melt temperature over another static mixer.
- Pressure was applied by means of another melt pump to granulate the material through a perforated plate (49 holes a 0.60 mm) with a pressurized underwater granulation (water temperature 50 ° C.).
- the mean 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.
- the raw material pellets E2 were produced in a twin-screw extruder from Leistritz ZE 40 using static mixing apparatuses.
- the polymer components according to Table 1 were first plasticized in the extruder and dosed via a melt pump into a series of static mixers and heat exchangers. The corresponding formulations can be found in the table. Subsequently, the melt temperature was reduced via a heat exchanger and the melt temperature over another static mixer homogenized. Pressure was applied by another melt pump to granulate the material through a perforated plate (49 holes a 0.60 mm) with pressurized underwater granulation (water temperature 50 ° C.). The mean particle size was about 1 .25 mm. The total throughput was 70 kg / h. The melt temperature at the nozzle exit was about 201 ° C.
- the raw material pellets E3 were produced in a twin-screw extruder from Leistritz ZE 40 using static mixing apparatuses.
- the polymer components according to Table 1 were first plasticized in the extruder and dosed via a melt pump into a series of static mixers and heat exchangers.
- 0.2 wt .-% nitrogen gas generating gas was added to the polymer melt and homogenized in the melt.
- the melt temperature was reduced via a heat exchanger and homogenized the melt temperature over another static mixer.
- Pressure was applied by means of another melt pump to granulate the material via a perforated plate (49 holes a 0.60 mm) with pressurized underwater granulation (water temperature 50 ° C.).
- the mean particle size was about 1 .25 mm.
- the total throughput was 70 kg / h.
- the melt temperature at the nozzle exit was approx. 205 ° C.
- Table 1 Composition (parts by weight) of the raw material granules E1, E2 and E3
- An evaporator filled with 160 g of liquid pentane was heated to 40 ° C. in a water bath with the valve closed. In the evaporator, the temperature associated with the vapor pressure one.
- An impregnation vessel connected via a tempered pentane guide was filled with 1000 g raw material granules and evacuated to less than 0.1 bar. The impregnation vessel was heated to 45 ° C, the heating cable of the Pentantechnisch to 50 ° C above the water bath temperature. After reaching constant temperature values, the valve was opened. The pentane gaseously poured into the kettle and was taken up by the granules. After a set time, the valve was closed. The gaseous pentane present in the boiler's atmosphere was taken up by the polymer to the thermodynamic equilibrium. The granules were removed afterwards. The pentane content in the granules depends on the fumigation time and the test temperature.
- An evaporator (volume 3205.16 ml) was cooled to 15 ° C, evacuated and filled with 160.61 g of pentane. The water bath was brought to a test temperature of 39.9 ° C.
- the impregnation vessel (volume 6.41, Karl Kurt Juchheim, 1990) was filled with 1000.1 1 g of degassed raw material granules E1 (pentane content 0.1 1% pentane), the anchor stirrer in the vessel was switched on (26 U / min).
- the boiler and the Pentan technisch are evacuated to 0.02 bar.
- the temperature of the boiler was 38.1 ° C, that of the heating band was 50.0 ° C.
- the pressure in the evaporator is constantly set to 1, 500 bar.
- the valve was opened. The pressure dropped to 1, 075 bar and then rose again. The temperature in the boiler dropped to 36.9 ° C, then increased to 38 ° C. When closing the valve after 60 minutes, the pressure in the system was 1, 330 bar. The pressure in the boiler falls within 20 hours to 1, 226 bar, the temperature at the boiler was 38.0 ° C. The kettle was evacuated to 0.1 bar and vented. The granules were removed and foamed in the foam box (Rauscher). After 50 seconds, a foaming density of 18 g / l was achieved. The volatiles determined in the heating oven (120 ° C., 180 min) gave a pentane content of 9.01%.
- a dosing unit (volume 200 ml) was filled with 95.1 g of pentane
- the impregnation vessel (volume 6.41, Karl Kurt Juchheim, 1990) was filled with 1000.08 g of pre-nucleated non-pentane raw material granules E3, the anchor stirrer in the vessel was switched on (26 U
- the boiler was evacuated to 0.02 bar
- the temperature of the boiler was 44.5 ° C.
- a pressure of 5 bar was produced by means of nitrogen
- the valve was opened The pressure in the boiler rises to 1.
- An evaporator (volume 3205.16 ml) was cooled to 15 ° C, evacuated and filled with 161, 01 g of pentane. The water bath was brought to a test temperature of 40.1 ° C.
- the impregnation vessel (volume 6.41, Karl Kurt Juchheim, 1990) was filled with 1000.08 g of pre-nucleated non-pentane raw material granules E3, the anchor stirrer in the vessel was switched on (26 rpm).
- the kettle and the pent-up line were evacuated to 0.02 bar.
- the temperature of the boiler was 45,0 ° C, that of the heating band 50,3 ° C.
- the pressure in the evaporator was constant at 1, 535 bar. The valve was opened.
- the high amount of blowing agent on the surface of the bead would soften the plastic so much that the beads clump together.
- the pressure slowly decreased at a constant internal temperature. During this degradation, the plastic granules almost completely absorbed the propellant. Only after the pressure was constant, the pentane uptake was completed (impregnation time) and the cooling of the boiler was started (cooling time). From an internal temperature of 40 ° C, the stirrer was turned off. The sum of metering time, impregnation time, cooling time then gives the actual life of the suspension impregnation. After cooling to room temperature, the product was removed from the kettle and the precipitate was washed with water and processed under the same conditions as in the gas phase impregnation (see processing).
- the pentane-containing granules were coated with the coating components 70% by weight of glycerol tristearate (GTS) and 30% by weight of glycerol monostearate (GMS) and 10% by weight of silica in a tumble mixer.
- GTS glycerol tristearate
- GMS glycerol monostearate
- the propellant-containing granules were prefoamed in an EPS-DruckvorCumer the company Hirsch called PREEX 1000 foam beads with minimum attainable density.
- the bulk density of the pre-expanded beads was determined by filling up to the measuring mark and weighing back.
- the foam beads were processed in an EPS molding machine from Erlenbach type EHV-C -520-420 at a pressure of 0.9 bar autoclave vaporization with a steaming time of 2.5 seconds to form parts.
- the moldings were then cut open and the cells were counted on the cut surface under a microscope over a calibrated, 1 cm long scale per millimeter. The measurement was repeated 20 times at various points and from this the mean value was given as cells per mm for the cell number.
- the comparative experiments show that impregnation in suspension leads to agglomeration of the particles, lenticular minigranules or inhomogeneous cell structures in the prefoamed foam particles.
- the mechanical properties of the foam moldings obtainable from the comparative experiments are significantly worse than the inventive examples.
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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EP11779437.0A EP2638103A1 (de) | 2010-11-11 | 2011-11-08 | Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierung |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP10190888A EP2452969A1 (de) | 2010-11-11 | 2010-11-11 | Verfahren zur Herstellung von expandierbaren thermoplastischen Partikeln durch Nachimprägnierung |
PCT/EP2011/069681 WO2012062773A1 (de) | 2010-11-11 | 2011-11-08 | Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierung |
EP11779437.0A EP2638103A1 (de) | 2010-11-11 | 2011-11-08 | Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierung |
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EP2638103A1 true EP2638103A1 (de) | 2013-09-18 |
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EP10190888A Ceased EP2452969A1 (de) | 2010-11-11 | 2010-11-11 | Verfahren zur Herstellung von expandierbaren thermoplastischen Partikeln durch Nachimprägnierung |
EP11779437.0A Withdrawn EP2638103A1 (de) | 2010-11-11 | 2011-11-08 | Verfahren zur herstellung von expandierbaren thermoplastischen partikeln durch nachimprägnierung |
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EP10190888A Ceased EP2452969A1 (de) | 2010-11-11 | 2010-11-11 | Verfahren zur Herstellung von expandierbaren thermoplastischen Partikeln durch Nachimprägnierung |
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EP (2) | EP2452969A1 (de) |
CN (1) | CN103298868B (de) |
MX (1) | MX2013005233A (de) |
WO (1) | WO2012062773A1 (de) |
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ITRM20130410A1 (it) * | 2013-07-12 | 2015-01-13 | Maio Ernesto Di | Metodo per la preparazione di particelle micrometriche o nanometriche cave |
TWI656153B (zh) | 2013-10-11 | 2019-04-11 | 巴斯夫歐洲公司 | 膨脹熱塑性彈性體珠粒之製造 |
CA3046042A1 (en) * | 2016-12-07 | 2018-06-14 | Huntsman International Llc | Method for producing expanded thermoplastic polymers |
CN110290719B (zh) * | 2017-01-31 | 2022-02-08 | 彪马欧洲公司 | 一种运动鞋 |
CN109669029A (zh) * | 2017-10-17 | 2019-04-23 | 国家安全生产监督管理总局化学品登记中心 | 聚苯乙烯可发性测试方法 |
EP3639997A1 (de) * | 2018-10-15 | 2020-04-22 | Linde Aktiengesellschaft | Verfahren zum imprägnieren von polymergranulat |
CN116981553A (zh) * | 2021-03-15 | 2023-10-31 | 巴斯夫欧洲公司 | 制备膨胀热塑性弹性体颗粒的方法 |
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DE1302686B (de) | 1964-03-28 | |||
JPS58198541A (ja) | 1982-05-14 | 1983-11-18 | Sekisui Plastics Co Ltd | 発泡性粒子の製造法 |
GB2162789A (en) | 1984-07-16 | 1986-02-12 | Cosden Technology | Process for making expandable polystyrene |
DE4429844A1 (de) | 1994-08-23 | 1996-02-29 | Basf Ag | Verfahren zur Herstellung von expandierten Polyolefin-Partikeln |
JP3168882B2 (ja) | 1995-09-05 | 2001-05-21 | 三菱化学フォームプラスティック株式会社 | スチレン系発泡性樹脂粒子及びその製造方法 |
KR100660432B1 (ko) * | 2003-04-04 | 2006-12-22 | 세키스이가세이힝코교가부시키가이샤 | 발포성 스티렌 개질 올레핀계 수지입자, 예비발포 입자 및발포 성형체의 제조 방법 |
DE10356017A1 (de) | 2003-11-27 | 2005-07-07 | Basf Ag | Verfahren zur Herstellung expandierbarer Polyolefinpartikel mittels Kaltimprägnierung |
TWI375681B (en) | 2005-03-17 | 2012-11-01 | Dow Global Technologies Llc | Foams made from interpolymers of ethylene/α-olefins |
CA2718001A1 (en) | 2008-03-13 | 2009-09-17 | Basf Se | Elastic molded foam based on polyolefin/styrene polymer mixtures |
-
2010
- 2010-11-11 EP EP10190888A patent/EP2452969A1/de not_active Ceased
-
2011
- 2011-11-08 WO PCT/EP2011/069681 patent/WO2012062773A1/de active Application Filing
- 2011-11-08 MX MX2013005233A patent/MX2013005233A/es active IP Right Grant
- 2011-11-08 EP EP11779437.0A patent/EP2638103A1/de not_active Withdrawn
- 2011-11-08 CN CN201180064633.3A patent/CN103298868B/zh not_active Expired - Fee Related
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CN103298868A (zh) | 2013-09-11 |
CN103298868B (zh) | 2015-05-20 |
EP2452969A1 (de) | 2012-05-16 |
WO2012062773A1 (de) | 2012-05-18 |
MX2013005233A (es) | 2013-08-21 |
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