US20100143697A1 - Elastic particle foam based on polyolefin/styrene polymer mixtures - Google Patents
Elastic particle foam based on polyolefin/styrene polymer mixtures Download PDFInfo
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- US20100143697A1 US20100143697A1 US12/595,275 US59527508A US2010143697A1 US 20100143697 A1 US20100143697 A1 US 20100143697A1 US 59527508 A US59527508 A US 59527508A US 2010143697 A1 US2010143697 A1 US 2010143697A1
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- 239000002245 particle Substances 0.000 title claims abstract description 112
- 239000006260 foam Substances 0.000 title claims abstract description 69
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 40
- 229920002959 polymer blend Polymers 0.000 title claims description 26
- 229920000098 polyolefin Polymers 0.000 title claims description 21
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 70
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 15
- 210000004027 cell Anatomy 0.000 claims abstract description 14
- 210000000170 cell membrane Anatomy 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 63
- 239000004604 Blowing Agent Substances 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 17
- 238000010097 foam moulding Methods 0.000 claims description 16
- 238000005453 pelletization Methods 0.000 claims description 15
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 11
- 230000000717 retained effect Effects 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000002667 nucleating agent Substances 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229940075529 glyceryl stearate Drugs 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 14
- -1 polyethylene Polymers 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 229940075507 glyceryl monostearate Drugs 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 6
- 239000000454 talc Substances 0.000 description 6
- 229910052623 talc Inorganic materials 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920002633 Kraton (polymer) Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 4
- 210000002421 cell wall Anatomy 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011326 mechanical measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920002438 Oppanol® B 150 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000005035 Surlyn® Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052756 noble gas Chemical class 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/10—Applying counter-pressure during expanding
-
- 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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- 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
- C08J9/224—Surface treatment
-
- 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
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
-
- 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
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
Definitions
- the invention relates to thermoplastic particle foams which have cells having a mean cell size in the range from 20 to 500 ⁇ m and in which the cell membranes have a nanocellular or fibrous structure having pore or fiber diameters below 1500 nm, and also to processes for producing them.
- Expandable polymer mixtures comprising styrene polymers, polyolefins and, if appropriate, solubilizers such as hydrogenated styrene-butadiene block copolymers are known from, for example, DE 24 13 375, DE 24 13 408 or DE 38 14 783.
- the foams which can be obtained therefrom are said to have better mechanical properties, in particular a better elasticity and a reduced brittleness at low temperatures, and also insensitivity toward solvents such as ethyl acetate and toluene, compared to foams composed of styrene polymers.
- the blowing agent retention capability and the foamability of the expandable polymer mixtures to low densities are not sufficient for processing.
- WO 2005/056652 describes particle foam moldings which have a density in the range from 10 to 100 g/l and can be obtained by fusion of prefoamed foam particles produced from expandable, thermoplastic polymer beads.
- the polymer beads comprise mixtures of styrene polymers and other thermoplastic polymers and can be obtained by melt impregnation and subsequent underwater pelletization under pressure.
- elastic particle foams comprising expandable interpolymer particles are known (e.g. US 2004/0152795 A1).
- the interpolymers can be obtained by polymerization of styrene in the presence of polyolefins in aqueous suspension and form an interpenetrating network of styrene polymers and olefin polymers.
- the blowing agent diffuses rapidly out of the expandable polymer particles, so that they have to be stored at low temperatures and display satisfactory foamability for only a short time.
- WO 2005/092959 describes nanoporous polymer foams which can be obtained from multiphase polymer mixtures which comprise blowing agent and have domains in the range from 5 to 200 nm.
- the domains preferably comprise core-shell particles which can be obtained by emulsion polymerization and in which the solubility of the blowing agent is at least twice as high as in the adjoining phases.
- thermoplastic particle foams we have accordingly found the above-described thermoplastic particle foams.
- thermoplastic particle foams preferably have cells having a mean cell size in the range from 50 to 250 ⁇ m and a nanocellular structure or a fibrously elongated, disperse phase structure in the cell walls of the thermoplastic particle foams having a mean pore or fiber diameter in the range from 10 to 1000 nm, particularly preferably in the range from 100 to 500 nm.
- FIG. 1 shows a section through the cells of a thermoplastic particle foam according to the invention.
- FIG. 2 shows a section magnified by 10 ⁇ of the cell structure having a nanocellular cell wall shown in FIG. 1 .
- the polymer matrix of the thermoplastic particle foams preferably comprises a continuous phase which is rich in styrene polymer and a disperse polyolefin-rich phase.
- thermoplastic particle foams particularly preferably comprise a polymer matrix comprising
- thermoplastic particle foams of the invention can be obtained by a process which comprises
- the polymer mixture can in step b), firstly be pelletized and the pellets can subsequently be after-impregnated with a blowing agent in an aqueous phase under superatmospheric pressure at elevated temperature to produce expandable thermoplastic polymer particles. These can subsequently be isolated after cooling to below the melting point of the polymer matrix or can be obtained directly as prefoamed polymer particles (step c) by depressurization.
- the polymer mixture having a continuous phase and a disperse phase can be produced by mixing two incompatible thermoplastic polymers, for example in an extruder.
- the polymer mixture preferably comprises from 45 to 98.9% by weight, particularly preferably from 55 to 89.9% by weight, of a thermoplastic polymer A), in particular a styrene polymer such as general purpose polystyrene (GPPS) or high-impact polystyrene (HIPS) or a styrene-acrylonitrile copolymer (SAN) or acrylonitrile-butadiene-styrene copolymer (ABS).
- GPPS general purpose polystyrene
- HIPS high-impact polystyrene
- SAN styrene-acrylonitrile copolymer
- ABS acrylonitrile-butadiene-styrene copolymer
- the polymer mixture preferably comprises from 1 to 45 percent by weight, in particular from 4 to 37% by weight; of a likewise thermoplastic polymer B) which is incompatible with the thermoplastic polymer A).
- a polyolefin e.g. homopolymers or copolymers of ethylene and/or propylene, in particular polyethylene, especially when a styrene polymer is used as polymer A).
- polypropylenes it is possible to use, in particular, injection-molding grades such as Adstif® RA 748 T or impact-modified grades such as Clyrell® EM 2484 from Basell.
- polyethylenes it is possible to use commercially available ethylene homopolymers such as LDPE (injection-molding grades), LLDPE and HDPE or copolymers of ethylene and propylene (e.g. Moplen® RP220 and Moplen® RP320 from Basell), ethylene and oktene (Engage®) or ethylene and vinyl acetate (EVA), polyethylene acrylates (EA) such as Surlyn® grades 1901 and 2601 from DuPont or ethylene-butylene acrylates (EBA) such as Lucofin® 1400 HN, 1400 HM from Lucobit AG.
- LDPE injection-molding grades
- Moplen® RP220 and Moplen® RP320 from Basell
- Engage® ethylene and oktene
- EVA ethylene and vinyl acetate
- EA polyethylene acrylates
- the melt volume index MVI (190° C./2.16 kg) of the polyethylenes is usually in the range from 0.5 to 40 g/10 min and the density is in the range from 0.86 to 0.97 g/cm 3 , preferably in the range from 0.91 to 0.95 g/cm 3 .
- PIB polyisobutene
- compatibilizers component C
- component C compatibilizers
- the compatibilizer leads to improved adhesion between the polyolefin-rich phase and the polystyrene-rich phase and even in small amounts significantly improves the elasticity of the foam compared to conventional EPS foams.
- Studies on the domain size of the polyolefin-rich phase showed that the compatibilizer stabilizes small droplets by reducing the interfacial tension.
- An electron micrograph of a section through an expandable polystyrene/polyethylene comprising blowing agent shows disperse polyethylene domains in the polystyrene matrix.
- Suitable compatibilizers are, for example, hydrogenated or unhydrogenated styrene-butadiene or styrene-isoprene block copolymers.
- 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, and the total styrene content is accordingly preferably in the range from 40 to 80% by weight, particularly preferably in the range from 50 to 70% by weight.
- Suitable styrene-butadiene block copolymers comprising at least two polystyrene blocks S and at least one styrene-butadiene copolymer block S/B are, for example, star-shaped branched block copolymers as are described in EP-A 0654488.
- Further suitable compatibilizers are block copolymers having at least two hard blocks S 1 and S 2 comprising vinylaromatic monomers together with at least one random soft block B/S comprising vinylaromatic monomers and diene located between them, with the proportion of the hard blocks being above 40% by weight, based on the total block copolymer, and the 1,2-vinyl content of the soft block B/S being below 20%, as are described in WO 00/58380.
- Linear styrene-butadiene block copolymers of the general structure S-(S/B)-S which have one or more blocks (S/B) random having a random styrene/butadiene distribution located between the two S blocks are also suitable as compatibilizers.
- Such block copolymers can be obtained by anionic polymerization in a nonpolar solvent with addition of a polar cosolvent or a potassium salt, as described, for example, in WO 95/35335 or WO 97/40079.
- the vinyl content is the relative proportion of 1,2 linkages of the diene units, based on the sum of the 1,2,1,4-cis and 1,4-trans linkages.
- the 1,2-vinyl content of the styrene-butadiene copolymer block (S/B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
- SBS styrene-butadiene-styrene
- SBS styrene-butadiene-styrene
- additives nucleating agents, plasticizers; flame retardants, soluble and insoluble inorganic and/or organic dyes and pigments, fillers or coblowing agents can be added to the multiphase polymer mixture in amounts which do not impair domain formation and the foam structure resulting therefrom.
- nucleus formers or nucleating agents it is possible to additionally add, for example, polyolefin waxes or talc in amounts of from 0 to 5% by weight, preferably from 0.5 to 3% by weight, based on the polymers A) to C).
- blowing agent (component D) in step b) preference is given to using from 1 to 15 percent by weight, preferably from 3 to 10 percent by weight, based on the polymer mixture of A) to C), of a physical blowing agent such as C 3 -C 8 -hydrocarbons, alcohols, ketones, ethers or halogenated hydrocarbons. Preference is given to using isobutane, n-butane, isopentane, n-pentane or isohexane.
- Suitable coblowing agents are ones having a lower selectivity of the solubility in the phase forming the domains, for example gases such as CO 2 , N 2 , fluorinated hydrocarbons or noble gases. These are preferably used in amounts of from 0 to 10% by weight, based on the polymer mixture.
- thermoplastic polymer A) which forms the continuous phase for example polystyrene
- a polymer B) which forms the disperse phase and, if appropriate, compatibilizer C) to produce the polymer mixture in step a) and the polymer melt is subsequently conveyed through one or more static and/or dynamic mixing elements and impregnated with the blowing agent in step b).
- the melt laden with blowing agent can subsequently be extruded through an appropriate die and cut to give foam boards, extrudates or particles.
- the melt coming out of the die can also be cut directly by means of underwater pelletization (UWP) to give expandable polymer particles or polymer particles which have been partially foamed to a chosen extent.
- UWP underwater pelletization
- the underwater pelletization is generally carried out at pressures in the range from 1.5 to 10 bar.
- the die plate generally has a plurality of nests having a plurality of holes.
- expandable polymer particles having the preferred average particle diameters in the range from 0.5 to 1.5 mm. 0.8 mm are obtained.
- Expandable polymer particles having a narrow particle size distribution and an average particle diameter in the range from 0.6 to 0.8 mm lead to better filling of automatic molding machines when the moldings have a finely structured shape. Furthermore, a better molding surface having a lower volume of interstices is achieved.
- the round or oval particles obtained are preferably foamed to a diameter in the range from 0.2 to 10 mm.
- Their bulk density is preferably in the range from 10 to 100 g/l.
- the mean diameter of the disperse phase of the polymer mixture produced in step a) is preferably in the range from 1 to 2000 nm, particularly preferably in the range from 100 to 1500 nm.
- a preferred polymer mixture in step a) is produced by mixing
- the invention also provides the expandable, thermoplastic polymer particles which can be obtained as intermediate products in step b) and comprise a polymer matrix comprising
- the finished expandable thermoplastic polymer particles can be coated with glycerol esters, antistatics or anticaking agents.
- the fusion of the prefoamed foam beads to produce the molding and the mechanical properties resulting therefrom are improved, in particular, by coating the expandable thermoplastic polymer particles with a glyceryl stearate.
- a coating comprising from 50 to 100% by weight of glyceryl tristearate (GTS), from 0 to 50% by weight of glyceryl monostearate (GMS) and from 0 to 20% by weight of silica.
- the expandable, thermoplastic polymer particles of the invention can be prefoamed by means of hot air or steam to produce foam particles having a density in the range from 8 to 200 kg/m 3 , preferably in the range from 10 to 50 kg/m 3 , and subsequently fused in a closed mold to produce foam moldings.
- Component A polystyrene PS 158K from BASF SE
- Component B polyethylene
- Component D blowing agent: pentane S (20% of isopentane, 80% of n-pentane)
- Nucleating agent talc (HP 320, Omyacarb)
- LLDPE LLDPE
- PS 158K polystyrene
- SBS block copolymer SBS block copolymer
- talc HP 320, Omyacarb
- polystyrene PS 158 K 2.2% by weight of talc (HP 320, Omyacarb), based on the polymer matrix, were added as nucleating agent in the form of a masterbatch with 2.2% by weight of polystyrene PS 158 K to the main melt stream laden with blowing agent via a side extruder.
- the melt was extruded through a heated perforated plate (4 holes having a diameter of 0.65 mm and a perforated plate temperature of 280° C.).
- the pellets comprising blowing agent were prefoamed to give foam beads having a low density (15-25 g/l) in an EPS prefoamer and processed at a gauge pressure of 0.7-1.1 bar in an automatic EPS molding machine to produce moldings.
- Expandable thermoplastic mixtures having the composition in parts by weight indicated in Table 1 were produced in a manner analogous to Example 1. The density and cell count of the foam particles after prefoaming are reported in Table 2.
- the blowing agent content of the minipellets was determined immediately after production and after storage for 7 days on filter paper at room temperature and atmospheric pressure by means of GC analysis.
- the compression set ⁇ res is the percentage by which the height of the deformed body has decreased from the original height after 75% deformation.
- significant elasticization compared to pure EPS is observed, as can be seen from the very high recovery after compression.
- the transmission electron micrograph shows the cell structure ( FIG. 1 ) with nanocellular cell walls and struts ( FIG. 2 ) which contribute to the elasticization.
- the pores have a size in the order of from 200 to 500 nm and correspond to the PE domains of the minipellets laden with blowing agent.
- Example 1 Composition of the expandable thermoplastic mixtures (parts by weight) C
- Example 2 Example 3 PS 158K 97.8 71.8 59.8 46.8 PE 22 33 44 3G55 4 6 8 Talc 2.2 2.2 2.2 2.2 Blowing agent content 6.8 6.5 6.5 8.2 (s-pentane) Blowing agent content 5.7 4.8 4 3 (s-pentane) after 7 days
- Example 1 To improve the fusion of the foam particles, 0.3% by weight of a coating agent was applied to the surface of the pellets comprising blowing agent from Example 1 in a Lödige mixer. After a storage time of 4 hours, the coated pellets comprising blowing agent were prefoamed and fused to form moldings as in Example 1.
- glyceryl tristearate As coating components, glyceryl tristearate (GTS) was used for Example 4 and a mixture of 60% by weight of GTS, 30% by weight of glyceryl monostearate (GMS) and 10% by weight of silica was used for Example 5.
- the coating agent had a positive effect on the fusion of the prefoamed foam beads to produce the molding.
- the flexural strength of the moldings obtained in Examples 4 and 5 could be increased to 220 and 227 kPa, respectively, compared to 150 kPa for the moldings obtained from the uncoated pellets in Example 1.
- the components A to C were melted at 220-240° C./130 bar in a ZSK 18 twin-screw extruder from Leitritz. 8 parts by weight of pentane S (20% of isopentane, 80% of n-pentane) were subsequently injected as blowing agent into the polymer melt and incorporated homogenously into the polymer melt by means of two static mixers. The temperature was subsequently reduced to 180°-185° C. via a cooler. 2.2 parts by weight of talc (HP 320, Omyacarb) as nucleating agent were metered in the form of a 50% strength by weight polystyrene masterbatch through a side extruder into the main melt stream laden with blowing agent.
- the melt was extruded at 4 kg/h through a heated perforated plate (4 holes having a diameter of 0.65 mm and a perforated plate temperature of 280° C.).
- the proportions by weight of the components A to C are shown in table 4.
- a ZE 40 twin-screw extruder from Leitritz, the components A to C were melted at 240-260° C./140 bar and admixed with 2.2 parts by weight of talc (HP 320, Omyacarb) as nucleating agent. 8 parts by weight of pentane S (20% of isopentane, 80% of n-pentane) were subsequently injected as blowing agent into the polymer melt and incorporated homogenously into the polymer melt by means of two static mixers. The temperature was subsequently reduced to 180°-195° C. via a cooler.
- the polymer melt was pressed at 50 kg/h and 200-220 bar through a perforated plate maintained at 240-260° C. (hole diameter of 0.6 mm with 7 nests ⁇ 7 holes or hole diameter of 0.4 mm with 7 nests ⁇ 10 holes).
- the proportions by weight of the components A to C are shown in table 4.
- the pellets comprising blowing agent were prefoamed to foam beads having a low density (15-25 g/l prefoamed) in an EPS prefoamer and processed at a gauge pressure of 0.7-1.1 bar in an automatic EPS molding machine to produce moldings.
- the compression set ⁇ res is the percentage by which the height of the deformed body has decreased from the original height after 75% deformation.
- significant elasticization compared to pure EPS is observed, as can be seen from the very high recovery after compression.
- the transmission electron micrograph shows the disperse distribution of the polyethylene in the minipellets comprising blowing agent, which contributes to elasticization of the foam after foaming.
- the PE domains of the minipellets laden with blowing agent have a size in the order of from 200 to 1000 nm.
- glyceryl tristearate GTS
- GMS glyceryl monostearate
- the small particle sizes of 0.8 mm showed an improvement in the processability to produce the molding in respect of demolding times and filling performance of the tool.
- the surface of the molding became more homogenous than in the case of particles having a diameter of 1.1 mm.
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Applications Claiming Priority (3)
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| PCT/EP2008/002774 WO2008125250A1 (de) | 2007-04-11 | 2008-04-08 | Elastischer partikelschaumstoff auf basis von polyolefin/styrolpolymer-mischungen |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| PCT/EP2008/002774 A-371-Of-International WO2008125250A1 (de) | 2007-04-11 | 2008-04-08 | Elastischer partikelschaumstoff auf basis von polyolefin/styrolpolymer-mischungen |
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| US13/669,747 Expired - Fee Related US8568633B2 (en) | 2007-04-11 | 2013-01-29 | Elastic particle foam based on polyolefin/styrene polymer mixtures |
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| US8729143B2 (en) | 2008-12-30 | 2014-05-20 | Basf Se | Elastic particle foam based on polyolefin/styrene polymer mixtures |
| US8741973B2 (en) | 2009-03-05 | 2014-06-03 | Basf Se | Elastic expanded polymer foam based on polyolefin/styrene polymer mixtures |
| US20170009038A1 (en) * | 2014-03-27 | 2017-01-12 | Jsp Corporation | Polyolefin resin foam particles, foam-particle moulded body, and composite stacked body including said moulded body |
| WO2018019995A1 (en) | 2016-07-29 | 2018-02-01 | Versalis S.P.A. | Block expandable polymeric compositions |
| US10920033B2 (en) | 2016-07-29 | 2021-02-16 | Versalis S.P.A. | Expandable vinyl aromatic composition containing functionalized ethylene-vinyl acetate copolymer |
| US11458710B2 (en) | 2018-08-10 | 2022-10-04 | Jsp Corporation | Laminated article |
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| CA2718001A1 (en) * | 2008-03-13 | 2009-09-17 | Basf Se | Elastic molded foam based on polyolefin/styrene polymer mixtures |
| BRPI0923911A2 (pt) * | 2008-12-30 | 2016-01-12 | Basf Se | partícula de polímero termoplástico, expansível, e, processo para a produção de partículas de polímero termoplástico, expansível. |
| WO2010076185A1 (de) * | 2008-12-30 | 2010-07-08 | Basf Se | Expandierbare, thermoplastische polymerpartikel auf basis von polyolefin/styrolpolymer-mischungen mit iso-pentan oder cyclopentan als treibmittel |
| EP2486094A1 (de) * | 2009-10-09 | 2012-08-15 | Basf Se | Polymermischungen von polystyrol mit styrol-butadien-blockcopolymeren |
| WO2011118706A1 (ja) * | 2010-03-26 | 2011-09-29 | 積水化成品工業株式会社 | 発泡性ポリスチレン系樹脂粒子とその製造方法、ポリスチレン系樹脂予備発泡粒子、ポリスチレン系樹脂発泡成形体、熱可塑性樹脂予備発泡粒子とその製造方法、及び熱可塑性樹脂発泡成形体 |
| JP5704831B2 (ja) * | 2010-03-26 | 2015-04-22 | 積水化成品工業株式会社 | 気泡含有発泡性ポリスチレン系樹脂粒子とその製造方法、ポリスチレン系樹脂予備発泡粒子及びポリスチレン系樹脂発泡成形体の製造方法 |
| JP5603628B2 (ja) * | 2010-03-26 | 2014-10-08 | 積水化成品工業株式会社 | 発泡性ポリスチレン系樹脂粒子とその製造方法、ポリスチレン系樹脂予備発泡粒子の製造方法及びポリスチレン系樹脂発泡成形体の製造方法 |
| EP2431148A1 (en) | 2010-09-17 | 2012-03-21 | Technisch Bureel Panigo N.V. | Production of laminated styrene-polymerised sheets |
| EP2452968A1 (de) * | 2010-11-11 | 2012-05-16 | Basf Se | Verfahren zur Herstellung von expandierbaren thermoplastischen Partikeln mit Verbesserter Expandierbarkeit |
| WO2012089574A1 (de) | 2010-12-28 | 2012-07-05 | Basf Se | Schaumstoffplatte auf basis von styrolpolymer-polyolefin-mischungen |
| DE102012110159A1 (de) * | 2012-10-24 | 2014-04-24 | Michael Kellerer | Verfahren und Vorrichtung zur Herstellung eines Mauersteins mit Dämmfüllung sowie derartiger Mauerstein |
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| US10781336B2 (en) | 2015-05-22 | 2020-09-22 | Basf Coatings Gmbh | Aqueous basecoat material for producing a coating |
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| BR112019005807A2 (pt) | 2016-10-20 | 2019-06-25 | Basf Coatings Gmbh | método para produzir um revestimento, revestimento, substrato, e, uso de um revestimento. |
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| JP7420951B2 (ja) | 2019-12-18 | 2024-01-23 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | 構造化し且つ任意にコーティングした物品の製造方法及び該方法から得られた物品 |
| WO2023036854A1 (en) | 2021-09-13 | 2023-03-16 | Basf Coatings Gmbh | Coating composition comprising a sustainable pigment and method of coating a substrate using the same |
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| JP2024537324A (ja) | 2021-10-11 | 2024-10-10 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング | コーティングされた非架橋ポリマー材料の製造方法 |
| IT202300001389A1 (it) * | 2023-01-30 | 2024-07-30 | Versalis Spa | Granuli espandibili e manufatti da essi ottenuti. |
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- 2008-04-08 BR BRPI0809543-4A2A patent/BRPI0809543A2/pt not_active IP Right Cessation
- 2008-04-08 DE DE200850002220 patent/DE502008002220D1/de active Active
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- 2008-04-08 JP JP2010502453A patent/JP5570413B2/ja not_active Expired - Fee Related
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8729143B2 (en) | 2008-12-30 | 2014-05-20 | Basf Se | Elastic particle foam based on polyolefin/styrene polymer mixtures |
| US8741973B2 (en) | 2009-03-05 | 2014-06-03 | Basf Se | Elastic expanded polymer foam based on polyolefin/styrene polymer mixtures |
| US20170009038A1 (en) * | 2014-03-27 | 2017-01-12 | Jsp Corporation | Polyolefin resin foam particles, foam-particle moulded body, and composite stacked body including said moulded body |
| WO2018019995A1 (en) | 2016-07-29 | 2018-02-01 | Versalis S.P.A. | Block expandable polymeric compositions |
| US10920033B2 (en) | 2016-07-29 | 2021-02-16 | Versalis S.P.A. | Expandable vinyl aromatic composition containing functionalized ethylene-vinyl acetate copolymer |
| RU2750889C2 (ru) * | 2016-07-29 | 2021-07-05 | ВЕРСАЛИС С.п.А. | Вспениваемые винилароматические композиции, содержащие функционализованный сополимер этилена и винилацетата |
| US11078342B2 (en) | 2016-07-29 | 2021-08-03 | Versalis S.P.A. | Block expandable polymeric compositions |
| US11458710B2 (en) | 2018-08-10 | 2022-10-04 | Jsp Corporation | Laminated article |
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| AS | Assignment |
Owner name: BASF SE,GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SCHIPS, CARSTEN;HAHN, KLAUS;GRAESSEL, GEORG;AND OTHERS;SIGNING DATES FROM 20080422 TO 20080506;REEL/FRAME:023358/0705 |
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| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |