EP2222915A1 - Thermoplastic linoleum - Google Patents
Thermoplastic linoleumInfo
- Publication number
- EP2222915A1 EP2222915A1 EP08859529A EP08859529A EP2222915A1 EP 2222915 A1 EP2222915 A1 EP 2222915A1 EP 08859529 A EP08859529 A EP 08859529A EP 08859529 A EP08859529 A EP 08859529A EP 2222915 A1 EP2222915 A1 EP 2222915A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- thermoplastic
- molding composition
- vegetable oil
- shell
- 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.)
- Granted
Links
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 58
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 58
- 238000009757 thermoplastic moulding Methods 0.000 claims abstract description 53
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 42
- 239000008158 vegetable oil Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 37
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000005060 rubber Substances 0.000 claims description 6
- 125000002348 vinylic group Chemical group 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004863 Frankincense Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 240000000491 Corchorus aestuans Species 0.000 claims description 3
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 3
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- WEFHSZAZNMEWKJ-KEDVMYETSA-N (6Z,8E)-undeca-6,8,10-trien-2-one (6E,8E)-undeca-6,8,10-trien-2-one (6Z,8E)-undeca-6,8,10-trien-3-one (6E,8E)-undeca-6,8,10-trien-3-one (6Z,8E)-undeca-6,8,10-trien-4-one (6E,8E)-undeca-6,8,10-trien-4-one Chemical compound CCCC(=O)C\C=C\C=C\C=C.CCCC(=O)C\C=C/C=C/C=C.CCC(=O)CC\C=C\C=C\C=C.CCC(=O)CC\C=C/C=C/C=C.CC(=O)CCC\C=C\C=C\C=C.CC(=O)CCC\C=C/C=C/C=C WEFHSZAZNMEWKJ-KEDVMYETSA-N 0.000 claims description 2
- 239000004852 Asphaltite Substances 0.000 claims description 2
- 241000717739 Boswellia sacra Species 0.000 claims description 2
- 235000003717 Boswellia sacra Nutrition 0.000 claims description 2
- 240000007551 Boswellia serrata Species 0.000 claims description 2
- 235000012035 Boswellia serrata Nutrition 0.000 claims description 2
- 240000005209 Canarium indicum Species 0.000 claims description 2
- 240000008772 Cistus ladanifer Species 0.000 claims description 2
- 235000005241 Cistus ladanifer Nutrition 0.000 claims description 2
- 235000006965 Commiphora myrrha Nutrition 0.000 claims description 2
- 239000004859 Copal Substances 0.000 claims description 2
- 241000116713 Ferula gummosa Species 0.000 claims description 2
- 241000782205 Guibourtia conjugata Species 0.000 claims description 2
- 239000004869 Labdanum Substances 0.000 claims description 2
- 235000015511 Liquidambar orientalis Nutrition 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 244000062730 Melissa officinalis Species 0.000 claims description 2
- 235000010654 Melissa officinalis Nutrition 0.000 claims description 2
- 235000014150 Myroxylon pereirae Nutrition 0.000 claims description 2
- 244000302151 Myroxylon pereirae Species 0.000 claims description 2
- 235000007265 Myrrhis odorata Nutrition 0.000 claims description 2
- 240000008548 Shorea javanica Species 0.000 claims description 2
- 239000004870 Styrax Substances 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 241000779819 Syncarpia glomulifera Species 0.000 claims description 2
- 240000004824 Trimezia steyermarkii Species 0.000 claims description 2
- 239000004853 Utah resin Substances 0.000 claims description 2
- 239000004855 amber Substances 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000009136 dragon's blood Substances 0.000 claims description 2
- 239000004862 elemi Substances 0.000 claims description 2
- 239000004864 galbanum Substances 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 239000000865 liniment Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000013521 mastic Substances 0.000 claims description 2
- 239000001739 pinus spp. Substances 0.000 claims description 2
- 229940036248 turpentine Drugs 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 240000007311 Commiphora myrrha Species 0.000 claims 1
- 240000005428 Pistacia lentiscus Species 0.000 claims 1
- 229920001800 Shellac Polymers 0.000 claims 1
- 239000001157 myroxylon pereirae klotzsch resin Substances 0.000 claims 1
- 235000013874 shellac Nutrition 0.000 claims 1
- 239000004208 shellac Substances 0.000 claims 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims 1
- 229940113147 shellac Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- -1 for example Substances 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 229920000747 poly(lactic acid) Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000000944 linseed oil Substances 0.000 description 6
- 235000021388 linseed oil Nutrition 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920002530 polyetherether ketone Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920000638 styrene acrylonitrile Polymers 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229920002988 biodegradable polymer Polymers 0.000 description 3
- 239000004621 biodegradable polymer Substances 0.000 description 3
- 239000007799 cork Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002432 hydroperoxides Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000025 natural resin Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920001896 polybutyrate Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920005839 ecoflex® Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
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- 239000003365 glass fiber Substances 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
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- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
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- 240000009023 Myrrhis odorata Species 0.000 description 1
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- 239000004695 Polyether sulfone Substances 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000543354 Sideroxylon foetidissimum subsp. foetidissimum Species 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- XYXLRVFDLJOZJC-CVBJKYQLSA-L manganese(2+);(z)-octadec-9-enoate Chemical compound [Mn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O XYXLRVFDLJOZJC-CVBJKYQLSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical group C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000010104 thermoplastic forming Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N1/00—Linoleum, e.g. linoxyn, polymerised or oxidised resin
Definitions
- the present invention relates to a thermoplastic molding composition
- a thermoplastic molding composition comprising particles of at least one oxidatively crosslinked vegetable oil as core, which is enveloped by at least one thermoplastic, at least one other thermoplastic, at least one resin, at least one filler and optionally further additives, a process for preparing such a molding composition and a material containing a carrier layer and such a thermoplastic molding composition.
- Linoleum is a flooring developed by Frederick Walton in 1863, which consists mainly of oxidatively polymerized linseed oil, rosin, cork and wood flour, titanium oxide, dyes and a jute fabric. Advantages of linoleum are above all the resistance to oils, fats and tar. Linoleum is antistatic and has a mild fungicidal and bacteriostatic effect against various microorganisms. The cause of this effect is the permanent emission of small amounts of various aldehydes, such as hexanal, acrolein, acetaldehyde, etc., which come from the virtually never-ending Leinöloxidation in the air or are residues of the oxidation reaction in the manufacturing process.
- various aldehydes such as hexanal, acrolein, acetaldehyde, etc.
- linoleum Disadvantages of linoleum, for example, that this typical linoleum odor in sensitive people can be shown to trigger irritation of the mucous membranes and allergies. Furthermore, linoleum is not very puncture resistant and not suitable for use in damp rooms. In addition, linoleum is very sensitive to alkalis and is chemically degraded by them.
- thermoplastic molding compositions prepared from renewable raw materials should have at least 50% ingredients from natural sources.
- the cost of such new molding compounds should be comparable to those for synthetic molding compositions.
- the new thermoplastic molding compounds should comply with the regulations and requirements for plastics used in connection with foodstuffs.
- JP 03-241083 of Tajima Inc. discloses a floor covering and a method for its production.
- This floor covering is obtained by using a polymerisable vegetable oil, such as, for example, linseed oil, a thermoplastic elastomer, such as a styrene elastomer or styrene-butadiene block copolymer, a hardener, such as trimethylolpropane.
- pantrimethacrylate and a filler such as cork powder or wood chips are mixed, are brought into the desired shape and then irradiated with high-energy rays, for example with UV radiation.
- the object of the present invention is to provide a thermoplastic molding composition which consists to a major part of substances which are of natural origin, which has a stiffness which is comparable to that of impact-resistant polystyrene (HIPS), which can be produced inexpensively, and which comply with the regulations for use in the food sector.
- HIPS impact-resistant polystyrene
- thermoplastic molding composition containing a thermoplastic molding composition
- thermoplastic component A at least one further thermoplastic compatible with the at least one thermoplastic present in the shell of component A, as component B
- component C at least one resin associated with the at least one thermoplastic present in the shell of Component A is present, as component C,
- component D at least one filler as component D, and (E) optionally further additives as component E.
- the object according to the invention is achieved by a process for producing such a molding composition, by a material comprising a carrier layer and a thermoplastic molding composition, a floor covering containing such a material and by the use of the thermoplastic molding composition according to the invention in materials.
- thermoplastic molding composition according to the present invention will be described in detail below.
- Component A is a compound having Component A:
- thermoplastic molding composition in the thermoplastic molding composition according to the invention are as component A (A) particles of at least one oxidatively crosslinked vegetable oil as the core, which is surrounded by at least one thermoplastic, included.
- Suitable vegetable oils which are oxidatively crosslinked according to the invention and are present in this oxidatively crosslinked form in the particle according to component A in the thermoplastic molding composition are mentioned in Drying oils and related products, 2005, Verlag Wiley-VCH, Weinheim, pages 1 to 16th
- preferred vegetable oils are linseed oil, perilla oil, tung oil, oiticica oil, fish oils, safflower oil, sunflower oil, soybean oil, cottonseed oil and mixtures thereof.
- Flaxseed oil is preferably used. These oils can be obtained on an industrial scale by cold or hot pressing of the respective seeds. Optionally, a purification of the oils obtained by distillation.
- the crosslinking of the vegetable oil present in component A of the thermoplastic molding composition according to the invention is effected by oxidation, see also Drying oils and related products, 2005, Verlag Wiley-VCH, Weinheim, pages 1 to 16.
- the first step of the crosslinking reaction by oxidation is the formation of hydroperoxides in the allylic position with the double bonds.
- a radical is formed by dehydrogenation which is converted to hydroperoxide by addition of oxygen.
- an isomerization of the double bonds remaining in the molecule can take place.
- the next step in the cross-linking of the vegetable oils mentioned is the formation of a peroxy radical by degradation of the hydroperoxide.
- a free radical chain formation process is started, and oxygen bonds or carbon-carbon bonds are formed. Termination reactions in this process step is the recombination of radicals.
- hydroperoxides are not the first reaction step, but cyclic peroxides are formed by the direct attack of oxygen on the conjugated bond system. Reaction of these peroxides with allylic methylene groups or dissociation yields radicals that form carbon-oxygen and carbon-carbon bonds in a radical chain mechanism. This reaction can also be terminated by recombination of the radicals or disproportionation.
- oxidizing agents known to the person skilled in the art.
- the crosslinking of said vegetable oils by oxidation can be catalyzed by suitable catalysts.
- Suitable catalysts are all metals which can be present in different oxidation states and which can undergo redox reactions.
- Suitable metals for cross-linking vegetable oils are selected from the group consisting of cobalt, iron, manganese, cerium, lead, zirconium and mixtures of these metals.
- the oxidatively crosslinked vegetable oils, which are present in the core of the particles, can also by passing air at a temperature of generally 80 to 140 0 C, preferably 90 to 120 0 C are obtained.
- hydroperoxides are formed, which decompose into free radicals and thus increase the molecular weight by radical chain transfer reaction.
- the degree of crosslinking of the oxidatively crosslinked vegetable oils can be determined by rheological methods or by measuring the degree of swelling. These methods are known to the person skilled in the art.
- thermoplastic molding composition according to the invention, the particles which are used as component A, are enveloped by at least one thermoplastic.
- thermoplastic all polymers, i. Homopolymers and copolymers, referred to, which can be reversibly deformed in a certain temperature range, reversibly means that this process can be repeated as often as desired by cooling and reheating to the molten state, as long as not using thermal decomposition of the material by overheating ,
- thermoplastic molding composition As shell of the particles, which are present as component A in the thermoplastic molding composition according to the invention, it is generally possible to use all thermoplastics known to the person skilled in the art.
- the thermoplastics include e.g. Polyamides (PA), polyetheretherketones (PEEK), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polyurethane (PU), polyoxymethylene (POM), polyethersulfone (PES), poly-n-butylmethacrylate (PBMA) , Polymethyl methacrylate (PMMA), polyimides or styrene acrylonitrile (SAN).
- PA Polyamides
- PEEK polyetheretherketones
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PVC polyvinyl chloride
- PU polyurethane
- POM polyoxymethylene
- PES polyethersulfone
- PBMA poly-n-butylmethacrylate
- PMMA Polymethyl methacrylate
- SAN Polyimides or styrene acryl
- thermoplastics selected from the group consisting of homopolymers and copolymers composed of vinylic, aromatic monomers, ethylenically unsaturated monomers and / or dienes.
- Suitable vinylic, aromatic monomers correspond to the general formula (I)
- R 1 to R 8 are independently hydrogen, Ci-C 2 -alkyl, C 2 -C 2 -alkenyl, C 2 -C 20 - alkynyl, C 5 -C 2 may represent o-aryl, wherein the alkyl, alkenyl and alkynyl radicals may be linear or branched and may optionally be substituted by functional groups selected from the group consisting of amine, imine, ether, hydroxy, aldehyde, keto, carboxylic acid, carboxylic anhydride, nitrile group can.
- R 1 to R 3 are independently hydrogen or C 1 -C 20 -alkyl, more preferably hydrogen, methyl, ethyl or propyl, and R 4 to R 8 are independently hydrogen, methyl or ethyl. Most preferably, R 1 is hydrogen or methyl, and R 2 to R 8 are hydrogen.
- styrene, ⁇ -methylstyrene, para-methylstyrene, 1,1-diphenylethylene, para-tert-butylstyrene or mixtures are used as vinylic, aromatic monomers.
- Suitable ethylenically unsaturated monomers are generally selected from the group consisting of ⁇ , ⁇ -unsaturated mono- and dicarboxylic acids, their esters, anhydrides and nitriles.
- Preferred ⁇ , ß-unsaturated monocarboxylic acids are acrylic acid and methacrylic acid.
- esters of these ⁇ , ⁇ -unsaturated monocarboxylic acids are reaction products of said monocarboxylic acid with compounds bearing at least one OH function, i. with monohydric or polyhydric alcohols.
- Preferred methacrylic esters are C 1 -C 8 -alkyl esters of methacrylic acid, for example methyl methacrylate (MMA), ethyl methacrylate, n-, i-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate or 2-ethylhexyl methacrylate.
- MMA methyl methacrylate
- ethyl methacrylate ethyl methacrylate
- n- i-propyl methacrylate
- n-butyl methacrylate isobutyl methacrylate
- sec-butyl methacrylate tert-butyl methacrylate
- Preferred acrylic esters are C 1 -C 8 -alkyl esters of acrylic acid, for example methyl acrylate, ethyl acrylate, n-, i-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethylhexyl acrylate.
- Suitable nitriles of ⁇ , ⁇ -unsaturated monocarboxylic acids are acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.
- Suitable ⁇ , ⁇ -unsaturated dicarboxylic acids or ⁇ , ⁇ -unsaturated dicarboxylic anhydrides are, for example, maleic acid or maleic anhydride.
- all homo- or copolymerizable dienes may be present in the thermoplastic forming the shell of the particle in component A. Preference is given to using 1,3-dienes, more preferably 1,3-butadiene, 2,3-dimethylbutadiene, piperylene and / or isoprene.
- polystyrene is used as the shell of the particle present as component A.
- Polystyrene can be prepared by all methods known to those skilled in the art, for example cationic, anionic or free-radical initiated polymerization in emulsions, solutions or substance.
- the polystyrene which is present as a shell in the particle has a weight-average molecular weight of 80,000 to 300,000 g / mol, for example 100,000 to 200,000 g / mol.
- the shell of the particle present as component A is a copolymer composed of styrene and acrylonitrile.
- This so-called SAN copolymer generally has a weight-average molecular weight of 80,000 to 300,000 g / mol, for example 100,000 to 200,000 g / mol. Methods of making a suitable SAN copolymer are known to those skilled in the art.
- the binding of the at least one thermoplastic to the oxidatively crosslinked vegetable oil, which is present in the core can take place by interactions or by covalent bonds, in each case between the molecules of the thermoplastic and the molecules of the crosslinked vegetable oil in the core.
- the particle used as component A additionally contains a block or graft rubber.
- a block or graft rubber it is possible to use all block or graft rubbers known to the person skilled in the art. Preference is given to ABS copolymers, butadiene-styrene copolymers or block copolymers which have at least one hard block composed of at least one styrene monomer or a derivative thereof and at least one block composed of a styrene monomer and at least one diene, for example SBS copolymers Component A used. If rubbers are used according to the invention, they are preferably added in non-agglomerated form.
- ABS copolymers are copolymers composed of acrylic acid, butadiene and styrene.
- ABS copolymers are known to those skilled in the art.
- SBS copolymers are block copolymers made up of styrene and butadiene. SBS copolymers and processes for their preparation are described, for example, in WO 97/40079. These block polymers are prepared by anionic polymerization in a non-polar solvent, wherein the initiation takes place by means of organometallic compounds. Preference is given to compounds of the alkali metals, especially of lithium. Examples of initiators are methyllithium, ethyllithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyl lithium. The organometallic compound is added as a solution in a chemically inert hydrocarbon.
- the dosage depends on the desired molecular weight of the polymer, but is usually in the range of 0.002 to 5 mol%, based on the monomers.
- the solvents used are preferably aliphatic hydrocarbons such as cyclohexane or methylcyclohexane.
- the random blocks of the block copolymers which simultaneously contain styrene and diene are prepared by adding a soluble potassium salt, in particular a potassium alkoxide, in particular tertiary alkoxides having at least 7 carbon atoms.
- a soluble potassium salt in particular a potassium alkoxide, in particular tertiary alkoxides having at least 7 carbon atoms.
- Typical corresponding alcohols are, for example, 3-ethyl-3-pentanol and 2,3-dimethyl-3-pentanol. Tetrahydro-linalool (3,7-dimethyl-3-octanol) proved to be particularly suitable.
- other potassium salts which are inert to metal alkyls are also suitable in principle. These include dialkylpotassium amides, alkylated diarylpotassium amides, alkylthiolates and alkylated arylthiolates.
- the polymerization temperature can be between 0 and
- component A particles which contain flaxseed oil as vegetable oil, a SBS block copolymer as rubber and are coated with polystyrene.
- the particles used as component A contain linseed oil as vegetable oil, a graft rubber based on styrene and / or butadiene and a shell of a styrene-acrylonitrile copolymer.
- the particles which are present in the thermoplastic molding composition according to the invention as component A generally have a diameter of 1 to 100 .mu.m, preferably 1 to 10 .mu.m.
- the shell of the component present as component A generally has a layer thickness of 10 to 30 nm.
- the oxidatively crosslinked vegetable oil is present in an amount of from 10 to 60% by weight, preferably from 20 to 50% by weight, particularly preferably from 25 to 45% by weight, based in each case on the entire thermoplastic molding composition
- Component A is generally present in the thermoplastic molding composition in an amount of from 10 to 70% by weight, preferably from 40 to 60% by weight, in each case based on the total thermoplastic molding composition.
- Component B is a compound having Component B:
- thermoplastic molding composition according to the invention contains as component B at least one further thermoplastic which is compatible with the at least one thermoplastic present in the shell of component A.
- component B at least one further thermoplastic which is compatible with the at least one thermoplastic present in the shell of component A.
- thermoplastic in the sense of the present Invention means "compatible" that no incompatibility reactions between the two thermoplastics occur, for example, decomposition, segregation, chemical reactions, discoloration or negative influences on the mechanical properties of the thermoplastic molding composition according to the present invention.
- Thermoplastics suitable as component B are selected from the group consisting of copolymers of at least one vinylic, aromatic monomer and optionally at least one ⁇ , ⁇ -unsaturated monocarboxylic acid or the corresponding nitrile, for example polystyrene (PS) or styrene-acrylonitrile (SAN).
- PS polystyrene
- SAN styrene-acrylonitrile
- thermoplastics are selected from the group consisting of polycarbonates (PC), polyurethanes (PU), polyamides (PA), polyesters such as polyethylene terephthalates (PET) or polybutylene terephthalates (PBT), polyether ether ketones (PEEK), polyvinyl chlorides (PVC) , Polyurethanes (PU), polyoxymethylenes (POM), polyether sulfones (PES), poly-n-butyl methacrylates (PBMA), polymethyl methacrylates (PMMA), polyimides and biodegradable homo- and copolymers, for example polylactides or polybutyrate.
- PC polycarbonates
- PU polyurethanes
- PA polyamides
- PET polyethylene terephthalates
- PBT polybutylene terephthalates
- PEEK polyether ether ketones
- PVC polyvinyl chlorides
- POM polyoxymethylenes
- PES polyether sulfones
- the at least one further thermoplastic material used as component B is selected from the group consisting of polystyrenes, polyesters, styrene-acrylonitrile copolymers, polycarbonates, polyurethanes and biodegradable polymers, for example polylactides or polybutyrate.
- Polycarbonates are polymers that can be formally obtained by reaction of carbonic acid and compounds having at least two hydroxy functions. They are accessible, for example, by reacting the corresponding alcohols with phosgene or carbonic diesters in polycondensation and transesterification reactions.
- Polyesters suitable for the thermoplastic molding composition according to the invention are preferably selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and blends thereof. Polyesters can be obtained by reaction of diols with dicarboxylic acids or hydroxycarboxylic acids.
- Polyurethanes are copolymers obtained by polyaddition of compounds having at least two hydroxyl functions and compounds having at least two isocyanate groups.
- Examples of polyurethanes to be used according to the invention are those prepared from polyester and / or polyether diols and z. B. from 2,4- or 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and hexamethylene diisocyanate. It can be used linear or branched polyurethanes.
- a biodegradable polymer is used in the thermoplastic molding composition according to the invention in a preferred embodiment.
- Examples of biodegradable polymers are polylactides or polybutyrate.
- Polylactides, also called polylactic acids occur in the optically active D or L form due to the asymmetric carbon atom.
- Polylactides which can be used according to the invention can be prepared by all processes known to the person skilled in the art.
- Polylactides are accessible, for example, by the ionic polymerization of lactide, an annular combination of two lactic acid molecules. At temperatures between 140 and 180 0 C and the action of catalytically active tin compounds such as tin oxide, the formation of polylactide takes place in a ring-opening polymerization. Lactide itself can be produced by fermentation of molasses or by fermentation of glucose with the help of various bacteria. In addition, high molecular weight and pure polylactides can be produced by polycondensation directly from lactic acid.
- Component B may also be a mixture of said thermoplastics with one another or a mixture of said thermoplastics with each other with so-called “toughness boosters" as an additive, which are preferably selected from the group consisting of SBS copolymers, for example under the trade name Styroflex® or under Ecoflex® is a mixture of aromatic and aliphatic esters based on poly-epsilon-caprolactone and 1,4-butanediol. With regard to the SBS copolymers, the above applies.
- component B if the shell of the particle contains polystyrene, polystyrene is also used, optionally in admixture with an SBS copolymer.
- the component B if the shell of the particle includes styrene acrylonitrile, also styrene acrylonitrile, polyester, polyurethane or polylactide used, optionally in admixture with Ecoflex ®.
- thermoplastic material used as component B is in the thermoplastic molding composition of the present invention in an amount of 20 to 80 wt .-%, preferably 30 to 70 wt .-%, particularly preferably 40 to 60 wt .-%, each based on the Total mass of the thermoplastic molding compound, before.
- Component C is a thermoplastic molding composition of the present invention in an amount of 20 to 80 wt .-%, preferably 30 to 70 wt .-%, particularly preferably 40 to 60 wt .-%, each based on the Total mass of the thermoplastic molding compound, before.
- thermoplastic molding composition according to the present invention contains as component C at least one resin which is compatible with the at least one thermoplastic present in the shell of component A.
- thermoplastic molding composition of the present invention A selection of natural resins that can be used in the thermoplastic molding composition of the present invention is disclosed in: Natural Resins, Wiley-VCH Verlag, Weinheim, 2005, pages 1-19.
- Particularly preferred natural resins are selected from the group consisting of acaroid resin, amber, asphaltite, balsam of Peru, toru balsam, benzoin, Canada balm, Chinese or Japanese varnish, copal, damar, dragon's blood resin, elemi, frankincense (Olibanum), galbanum , Labdanum, Mastic, Myrrh, Sandarak, Schellak, Styrax, Utah resin, Venice turpentine, rosin and mixtures thereof. Particular preference is given to using rosin.
- Processes are obtained or isolated, for example by scoring the bark of the corresponding tree and collecting the resin or extraction of the wood of the corresponding tree with suitable solvents, such as naphtha.
- Suitable synthetically produced resins are generally copolymers, for example low molecular weight thermoplastic materials such as low molecular weight polyesters. These are known to the person skilled in the art.
- Component C is in the thermoplastic molding composition according to the invention generally in an amount of 1 to 30 wt .-%, preferably 5 to 20 wt .-%, particularly preferably 8 to 15 wt .-%, each based on the total mass of the thermoplastic molding composition according to the invention , in front.
- the thermoplastic molding composition according to the invention contains as component D at least one filler.
- component D all fillers known to those skilled in the art can be used, which are suitable for use in polymeric materials.
- suitable fillers are mineral fillers, salts, for example carbonates of the alkali and alkaline earth metals, such as calcium carbonate, or compounds such as titanium dioxide, zirconium dioxide and mixtures thereof.
- suitable fillers are selected from the group consisting of cork flour, such as recycled bottle corks, wood flour, such as sawdust.
- As a particularly preferred filler calcium carbonate is used.
- Component D is generally present in an amount of up to 50% by weight, preferably 20 to 30% by weight.
- Component E Further additives may optionally be present as component E in the thermoplastic molding composition according to the invention.
- Suitable further additives are, for example, dyes, UV stabilizers, bleaches, deodorants, antioxidants and mixtures thereof.
- component E is generally present in an amount of from 0.1 to 2% by weight, preferably from 1 to 2% by weight, based in each case on the entire thermoplastic molding composition.
- thermoplastic molding composition according to the invention The sum of the amounts of components A, B, C, D present in the thermoplastic molding composition according to the invention and optionally E is 100% by weight.
- the present invention also relates to a process for the preparation of a thermoplastic molding composition comprising particles of at least one oxidatively crosslinked
- Vegetable oil as a core which is enveloped by at least one thermoplastic than
- Component A at least one other thermoplastic which is compatible with the at least one thermoplastic present in the shell of component A, as
- Component B at least one resin which is compatible with the at least one thermoplastic present in the shell of component A, at least one filler as
- step (1) oxidation of the at least one vegetable oil in the solution or dispersion of step (1) to obtain particles which crosslinked the at least one oxidative one Vegetable oil contained as a core and are enveloped by at least one thermoplastic, and
- step (3) mixing the particles of step (2) with components (B), (C), (D) and optionally (E) to obtain the thermoplastic molding material.
- Step 1 :
- Step (1) of the method according to the invention comprises preparing a solution or a dispersion of at least one thermoplastic in the at least one vegetable oil.
- step (1) a solution or dispersion of the at least one thermoplastic in the at least one vegetable oil is prepared, depending on how soluble the at least one thermoplastic is in the at least one vegetable oil.
- a solution is prepared.
- the amount of at least one thermoplastic in the at least one vegetable oil is generally the amount which should also be present in the later component (A).
- thermoplastic molding composition according to the invention applies.
- the preparation of the solution or of the dispersion can be carried out by all methods known to the person skilled in the art.
- the at least one vegetable oil is heated before the at least one thermoplastic is added.
- the preparation of the solution or dispersion in step (1) of the method according to the invention is generally carried out at atmospheric pressure, however
- the process according to the invention can also be carried out at a pressure below atmospheric pressure or at a pressure above atmospheric pressure.
- Step (2) of the process of the invention comprises oxidizing the at least one vegetable oil in the solution or dispersion of step (1) to obtain particles comprising the at least one oxidatively crosslinked vegetable oil as the core and the at least one thermoplastic as the shell.
- the oxidation can be carried out by all methods known to the person skilled in the art. Suitable oxidizing agents are selected from the group consisting of oxidizing gases, such as oxygen, halogens, hydrogen peroxide, inorganic peroxides, organic peroxides, air, liquid or dissolved or dispersed oxidizing agents and mixtures of these oxidizing agents.
- the oxidation in step (2) of the process according to the invention takes place by flowing the solution or dispersion from step (1) with air.
- the temperature in step (2) of the process according to the invention is generally more than 1 10 0 C, preferably 115-150 0 C.
- step (2) of the process according to the invention is carried out in the presence of a catalyst.
- Suitable catalysts are metals and metal compounds which can be present in different oxidation states and can undergo redox reactions. Examples of metals that can be used as oxidation catalysts are selected from the group consisting of cobalt, iron, manganese, cerium, lead, zirconium and mixtures thereof.
- the oxidation in step (2) of the process according to the invention is preferably carried out in the presence of a manganese catalyst.
- Suitable compounds of the catalytically active compounds are organic and inorganic salts and complex compounds. Exemplary manganese oleate is called.
- the catalytically active metals are used in step (2) of the inventive method in an amount of 0.001 to 2 wt .-%.
- at least one further salt is used which serves for the regeneration of the catalytically active compound, for example a zinc salt, preferably a zinc alkoxide.
- This additional compound is used in the same amount as the catalytically active compound or in a 2, 3, 4 or 5-fold excess with respect to the catalytically active compound.
- the catalytically active metal compound is already admixed in step (1).
- the catalytically active metal is not removed, so that the resulting thermoplastic molding composition contains the corresponding amount of metal salt in addition to the components A to D and optionally E.
- the oxidation is generally carried out until the degree of crosslinking of the vegetable oil to be oxidatively crosslinked has reached the desired value. This can be determined by an increase in the viscosity of the solution or dispersion during the oxidation.
- the reaction time is generally between 0.1 and 8 hours, preferably between 0.5 and 6 hours, more preferably between 1 and 4 Hours.
- the reaction time for the oxidation step (2) depends on the vegetable oil used, the thermoplastic present, the oxidizing agent used, the catalyst used, and the concentration of the thermoplastic in the vegetable oil, and can be easily determined by those skilled in the art by observing the increase in viscosity be determined.
- thermoplastic molding composition After the oxidation has ended, particles have formed in the solution or dispersion, in the core of which at least one vegetable oil is present in oxidatively crosslinked form.
- the mechanism or the individual reaction steps have already been explained above with respect to the thermoplastic molding composition.
- the at least one thermoplastic is present in the shell of the particle produced in step (2), the molecular chains of this thermoplastic being covalently or coordinatively bound to the oxidatively crosslinked vegetable oil.
- the particle size and the layer thickness of the shell of at least one thermoplastic what has been said with regard to the thermoplastic molding composition according to the invention applies.
- Step (3) of the method of the invention comprises mixing the particles
- Step (2) with the components (B), (C), (D) and optionally (E) to obtain the molding material.
- Methods of mixing said components are known to those skilled in the art and are selected, for example, from compounding, extrusion or kneading.
- the mixing in step (3) takes place at a suitable temperature at which the individual components are miscible, for example 50 to 200 ° C.
- components (B), (C), (D) and, if appropriate, (E) the above applies with respect to the thermoplastic molding composition according to the invention.
- a thermoplastic molding composition according to the invention is produced by the process according to the invention.
- the present invention also relates to a material comprising a carrier layer or fibers and a thermoplastic molding composition according to the present invention.
- Fabrics made of synthetically produced or naturally available fibers can be used as the carrier layer.
- natural fibers are cotton, jute or linen.
- synthetically produced fibers are fibers of homopolymers and copolymers selected from the group consisting of polyesters, polyamides, polyolefins and blends of the abovementioned polymers. It can according to the invention also Glass fibers, preferably in conventional dimensions, are used, these according to the invention do not form tissue.
- the material according to the invention is obtained by applying the thermoplastic molding composition produced according to the invention as a melt or in solution or dispersion to the carrier layer or by mixing it with the glass fibers.
- the material produced according to the invention can be used as a floor covering, wall covering, for covering furniture, in the automotive sector, in wet rooms such as in the bathroom and toilet area, in housings or in components.
- the present invention also relates to a floor covering, wall covering, furniture, car parts, housings or components containing the material according to the invention. Furthermore, the present invention also relates to the use of the thermoplastic molding composition according to the present invention in materials.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08859529A EP2222915B1 (en) | 2007-12-13 | 2008-12-11 | Thermoplastic linoleum |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP07123091 | 2007-12-13 | ||
EP08859529A EP2222915B1 (en) | 2007-12-13 | 2008-12-11 | Thermoplastic linoleum |
PCT/EP2008/067316 WO2009074645A1 (en) | 2007-12-13 | 2008-12-11 | Thermoplastic linoleum |
Publications (2)
Publication Number | Publication Date |
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EP2222915A1 true EP2222915A1 (en) | 2010-09-01 |
EP2222915B1 EP2222915B1 (en) | 2011-04-20 |
Family
ID=40328562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08859529A Not-in-force EP2222915B1 (en) | 2007-12-13 | 2008-12-11 | Thermoplastic linoleum |
Country Status (6)
Country | Link |
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US (1) | US8466215B2 (en) |
EP (1) | EP2222915B1 (en) |
JP (2) | JP2011506664A (en) |
AT (1) | ATE506484T1 (en) |
DE (1) | DE502008003320D1 (en) |
WO (1) | WO2009074645A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101545606B1 (en) | 2007-07-10 | 2015-08-20 | 스티롤루션 유럽 게엠베하 | Flame-retardant elastic block copolymer |
EP2178970B1 (en) | 2007-07-10 | 2011-02-23 | Basf Se | Flame retardant thermoplastic molding compositions |
US8697795B2 (en) | 2010-08-25 | 2014-04-15 | Konrad Knoll | Thermoplastic linoleum |
WO2012025554A1 (en) * | 2010-08-25 | 2012-03-01 | Basf Se | Thermoplastic molding compound, method for producing same, and use thereof |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB452944A (en) * | 1934-06-30 | 1936-09-02 | Congoleum Nairn Inc | Improvements in or relating to mouldable compositions and the manufacture of linoleum or the like |
NL8600266A (en) | 1985-12-07 | 1987-07-01 | Dsm Resins Bv | RESIN COMPOSITION AND METHOD FOR PREPARING THIS RESIN COMPOSITION. |
DE3843482A1 (en) * | 1988-12-23 | 1990-06-28 | Huels Troisdorf | METHOD FOR THE PRODUCTION OF FLAT ENVIRONMENTS SUCH AS FLOORING OR WALL PAVING, IN PARTICULAR NATUROELENE |
NL8900009A (en) * | 1989-01-04 | 1990-08-01 | Stamicarbon | RESIN COMPOSITION AND METHOD FOR PREPARING THIS RESIN COMPOSITION. |
JPH0680235B2 (en) | 1990-02-19 | 1994-10-12 | 株式会社タジマ | Floor material and manufacturing method thereof |
JP3241083B2 (en) | 1992-03-25 | 2001-12-25 | 積水化学工業株式会社 | Pipe fittings |
DE19615533A1 (en) | 1996-04-19 | 1997-10-23 | Basf Ag | Thermoplastic molding compound |
DE19858141A1 (en) * | 1998-12-16 | 2000-06-21 | Basf Ag | Thermoplastic molding compounds |
DE19858173A1 (en) * | 1998-12-16 | 2000-06-21 | Targor Gmbh | Layered composite material based on thermoplastic polymers |
ATE284856T1 (en) * | 1999-06-18 | 2005-01-15 | Cambridge Biopolymers Ltd | OXIDATIVE BREAKDOWN OF UNSATURATED OILS AND PRODUCTS MADE THEREOF |
US6231970B1 (en) * | 2000-01-11 | 2001-05-15 | E. Khashoggi Industries, Llc | Thermoplastic starch compositions incorporating a particulate filler component |
DE10001476B4 (en) | 2000-01-15 | 2004-08-19 | Dreisol Gmbh & Co. Kg | Use of a vegetable oil for a coating agent |
DE10331888B4 (en) * | 2003-07-14 | 2005-11-10 | Clariant Gmbh | Elastic covering material with improved flame retardancy and a method for its production |
US7543638B2 (en) * | 2006-04-10 | 2009-06-09 | Schlumberger Technology Corporation | Low temperature oxidation for enhanced oil recovery |
US7799895B2 (en) | 2006-09-12 | 2010-09-21 | W.F. Taylor Co., Inc. | Low VOC bio-source adhesive |
-
2008
- 2008-12-11 US US12/747,369 patent/US8466215B2/en not_active Expired - Fee Related
- 2008-12-11 AT AT08859529T patent/ATE506484T1/en active
- 2008-12-11 DE DE502008003320T patent/DE502008003320D1/en active Active
- 2008-12-11 WO PCT/EP2008/067316 patent/WO2009074645A1/en active Application Filing
- 2008-12-11 EP EP08859529A patent/EP2222915B1/en not_active Not-in-force
- 2008-12-11 JP JP2010537448A patent/JP2011506664A/en not_active Ceased
-
2015
- 2015-02-23 JP JP2015032555A patent/JP2015129301A/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2009074645A1 * |
Also Published As
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WO2009074645A1 (en) | 2009-06-18 |
ATE506484T1 (en) | 2011-05-15 |
EP2222915B1 (en) | 2011-04-20 |
JP2015129301A (en) | 2015-07-16 |
JP2011506664A (en) | 2011-03-03 |
DE502008003320D1 (en) | 2011-06-01 |
US20100261824A1 (en) | 2010-10-14 |
US8466215B2 (en) | 2013-06-18 |
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