WO2002046284A1 - Foamed cellular particles of an expandable polymer composition - Google Patents
Foamed cellular particles of an expandable polymer composition Download PDFInfo
- Publication number
- WO2002046284A1 WO2002046284A1 PCT/US2001/048289 US0148289W WO0246284A1 WO 2002046284 A1 WO2002046284 A1 WO 2002046284A1 US 0148289 W US0148289 W US 0148289W WO 0246284 A1 WO0246284 A1 WO 0246284A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- foamed cellular
- polymer
- weight
- per cubic
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 458
- 229920000642 polymer Polymers 0.000 title claims abstract description 195
- 230000001413 cellular effect Effects 0.000 title claims abstract description 191
- 239000000203 mixture Substances 0.000 title claims description 131
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 120
- 239000006260 foam Substances 0.000 claims abstract description 64
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 207
- 238000000034 method Methods 0.000 claims description 75
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 60
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 42
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 40
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 36
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims description 36
- 239000008188 pellet Substances 0.000 claims description 35
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 30
- 238000001125 extrusion Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 238000000465 moulding Methods 0.000 claims description 21
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 20
- 239000001273 butane Substances 0.000 claims description 19
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 19
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 18
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 18
- 239000001282 iso-butane Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- -1 maleic anhydrided Chemical compound 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 13
- 229920002223 polystyrene Polymers 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229920005669 high impact polystyrene Polymers 0.000 claims description 12
- 239000004797 high-impact polystyrene Substances 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 claims description 3
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- ILEDWLMCKZNDJK-UHFFFAOYSA-N esculetin Chemical compound C1=CC(=O)OC2=C1C=C(O)C(O)=C2 ILEDWLMCKZNDJK-UHFFFAOYSA-N 0.000 claims 14
- UHUSDOQQWJGJQS-UHFFFAOYSA-N glycerol 1,2-dioctadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)OC(=O)CCCCCCCCCCCCCCCCC UHUSDOQQWJGJQS-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 abstract description 2
- 229920006248 expandable polystyrene Polymers 0.000 description 32
- 210000004027 cell Anatomy 0.000 description 17
- 239000007858 starting material Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 13
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- 239000000523 sample Substances 0.000 description 11
- 238000003988 headspace gas chromatography Methods 0.000 description 10
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- 239000011248 coating agent Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
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- 150000001993 dienes Chemical class 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 3
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- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
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- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 1
- YZQCRYHZKMFKDE-UHFFFAOYSA-N 1-octadecylperoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOOCCCCCCCCCCCCCCCCCC YZQCRYHZKMFKDE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- 125000001246 bromo group Chemical group Br* 0.000 description 1
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- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- DATIMHCCPUZBTD-UHFFFAOYSA-N pentane Chemical compound CCCCC.CCCCC DATIMHCCPUZBTD-UHFFFAOYSA-N 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920013637 polyphenylene oxide polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical class OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- 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
-
- 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
- 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
- C08J2325/08—Copolymers of styrene
Definitions
- the present invention relates to expandable polymer, e.g. polystyrene, particles used in making foamed articles. More particularly, the present invention relates to foamed cellular particles made from a polymer composition in the plant of the polymer producer and then packaged and shipped to the foam molder for making foamed articles.
- expandable polymer e.g. polystyrene
- styrene polymer particles have been rendered expandable by the use of a blowing agent ranging from about 4.0 to about 9.0 weight percent (wt.%) that is intimately mixed with a polymer.
- These expandable particles are generally made as solid relatively "high-density" beads of a relatively small size, e.g. beads having a diameter of from about 0.2 to 4.0 millimeters.
- these styrene polymer particles are made by the resin or polymer producer and have a bulk density of about 40 pounds per cubic foot (641 kilograms per cubic meter) .
- expandable particles are shipped to the foam molder where they generally are partially expanded to a bulk density of about 6.0 pounds per cubic foot (96.1 kilograms per cubic meter) or less. After suitable aging, these particles are injected into a steam heated mold and are further expanded and fused together to form a foam article with a bulk density of about 6.0 pounds per cubic foot or less .
- the most frequently used blowing agent is an organic blowing agent, for example a hydrocarbon liquid, such as n-pentane (normal pentane) , butane, isopentane, and mixtures of pentane, the most common being n-pentane and mixtures of pentane .
- n-pentane normal pentane
- butane isopentane
- mixtures of pentane the most common being n-pentane and mixtures of pentane .
- N-pentane and mixtures of pentane are flammable and volatile organic compounds, and therefore considered environmentally undesirable in certain geographical areas, especially in the quantities that are released during the expansion and molding processes . Furthermore, the residual pentane in the molded article continues to escape into the atmosphere after removal of the foam article from the mold.
- various inorganic blowing agents such as carbon dioxide, nitrogen, air and other pneumatogens have been used. The use of these inorganic blowing agents is disclosed in Meyer et al . U.S. Patent No.4, 911, 869.
- blowing agent not only does the type of blowing agent influence the rate and the quality of expansion of the polystyrene particles, but the amount of blowing agent in the polystyrene particles is also a factor.
- pentane is used as the blowing agent, the particles generally need to contain at least between 3.5 and 7.2% by weight of pentane when shipped to the foam molder. Lower pentane levels would tend to limit the ability of the particles to reach most bulk densities of commercial interest in a one-pass expansion process, the bulk density of commercial interest ranging from about 0.8 to 6.0 pounds per cubic foot (12.8 to 96.1 kilograms per cubic meter) . Higher pentane levels will result in production inefficiencies such as poor quality moldings and long molding cycles, not to mention the additional emissions of pentane into the environment .
- a multi-stage pre-expansion process i.e. a two-stage expansion.
- This multi-stage pre-expansion process is required when converting the expandable particles with relatively low levels of blowing agent, e.g. less than 4.0 % by weight pentane.
- the aim is to attain an intermediate density, e.g. less than 1.9 pounds per cubic foot (30.4 kilograms per cubic meter) in the first step.
- the particles are then expanded in a second step in order to lower the density of the particles to, for example, less than 0.80 pounds per cubic foot (12.8 kilograms per cubic meters) .
- the expandable particles When the expandable particles are manufactured by the polymer producer and shipped to the foam molder, they are transported and/or stored at varying temperatures for varying times, thereby resulting in varying amounts of pentane being retained in the particles. Those skilled in the art will appreciate that these varying amounts of pentane in the expandable particles may generally have a deleterious effect on the quality and consistency of the resulting foam article.
- blowing agents are emitted into the environment at the site of the foam molder during the expansion and molding processes.
- the foam molder may be required to use expandable particles with a limited hydrocarbon content. If pentane is used, the content may range between 3.5% to 5.0% by weight of the polymer.
- the foam molder may also be forced to limit the amount of emissions by investing in complicated equipment for collecting the emitted hydrocarbons. These regulatory restrictions tend to limit the total annualized production rate of foam articles for the foam molder.
- the number of foam articles produced in the foam molder' s plant in a given time will be dependent on the permissible regulatory levels for hydrocarbon emissions in a given geographical area. Additionally, since the foam molder generally has little reason to use the recovered hydrocarbon blowing agent emitted in the pre-expansion process and/or the foam molding process, he has little reason to invest in a system for recovering and/or recycling the blowing agent in his plant.
- a further drawback of the present practice in shipping expandable styrene polymer particles to the foam molder is that the expandable particles must be specially packaged during transport in order to lessen the amount of hydrocarbon emissions into the atmosphere.
- a still further drawback of the present practice in shipping expandable styrene polymer particles to the foam molder is the need to store the molded foam articles so that the residual hydrocarbon, i.e. pentane can dissipate prior to distribution of the foam articles.
- the blocks must be aged prior to hot-wire cutting into boards so as to allow the pentane to dissipate. If the blocks are insufficiently aged, fires can occur during the hot wire cutting process. If less pentane is in the particles during the molding processes, it is believed that less storage time would be required for the foam articles.
- a still further drawback of the present practice is the limited shelf life of the expandable styrene polymer particles.
- Product quality requirements for the particles such as the expansion rate and the potential for the particles to achieve the required low density levels, deteriorate over time due to the loss of blowing agent during shipment and/or storage. The latter occurs even when using special hydrocarbon-resistant plastic film liners inside the packages for shipping the particles.
- additional quality control measures must be taken by the particle manufacturer prior to shipping the expandable particles if the particles are held in inventory for an extended length of time, e.g. three months or longer.
- Some particle manufacturers use expensive refrigerated storage in an effort to extend the effective shelf life of the expandable particles, especially if pentane is used as the blowing agent .
- a further drawback of the present practice in shipping expandable styrene polymer particles to the foam molder is the weight restriction imposed by traffic and/or highway regulators.
- the transportation regulatory bodies may restrict overall vehicle gross weight limit of 80,000 pounds for tractor-trailers hauling expandable particles without special permits.
- the tractor-trailers generally have empty volumetric space. After the packages or cartons carrying the expandable particles are carefully loaded into the tractor- trailer so that the weight is evenly spread over the trailer's axles, dunnage, such as inflatable air bags, are placed in the empty volumetric space in order to prevent the packages or cartons from shifting during transit.
- Expandable polymer particles in the size range of commercial interest generally have a relatively high bulk density compared to most non-expandable thermoplastic commodity resins, such as polyethylene, polypropylene, and solid ("crystal") polystyrene. These non-expandable resins are often extruded into relatively large pellet sizes with an inefficient packing characteristic resulting in lower bulk densities compared to the typical expandable polymer particles, such as expandable polystyrene particles. Since the non-expandable resins do not contain a blowing agent, that in most instances is flammable, there is no concern with respect to fires or shelf life.
- Expandable particles are packaged in relatively small packages, e.g. cardboard cartons, containing from about 1,000 to about 2,000 pounds of expandable resin.
- the high bulk density of these expandable particles requires the cartons to be manufactured with heavier and thicker cardboard than would be required if the non-expandable resins of lower bulk density were being shipped by a tractor- trailer.
- the heavier and thicker cardboard cartons require stronger and more expensive wooden pallets to support the cartons on the tractor-trailer.
- plastic film liners are placed in the cartons in order to lessen the dissipation rate of the blowing agent and to contain the blowing agent if it is volatile or flammable.
- These film liners are often multi-layered, are of a multi- composition, and are designed to take into account the high bulk density of the particles and the type of blowing agent in the expandable particles .
- the use of inert blowing agents has been suggested and taught in the prior art in order to eliminate or alleviate some of the drawbacks of using a volatile-blowing agent in the expandable particles.
- the inert blowing agent e.g. carbon dioxide
- the inert blowing agent is incorporated into the particles immediately before the foaming step. This can be done as the particles are released from a heated impregnation vessel or when the particles are in an expander located in close proximity to the impregnation vessel .
- the expandable particles need to be re-inflated with an additional blowing agent, e.g. air, immediately prior to the molding process.
- an additional blowing agent e.g. air
- This may require the installation of large pressure vessels at the foam molder' s site and a source of compressed gas, such as air.
- German Patent Application DE 198 19 058 Al teaches expandable polystyrene particles that are slightly foamed with a bulk density of 0.1- 20% lower than the initial bulk density and with a coarse internal cell structure. Basically, this patent application teaches the production of coarse cells that would improve the thermal conductivity of the final molded foam article. It is believed by the inventors of the present invention, that the slight reduction in bulk density of the particles is not sufficient to significantly reduce the blowing agent content of the particles or to allow the use of less expensive standard resin packages or cartons. Additionally, if the cellular structure of the particles is "too coarse", this can result in long molding cycles and in poor physical strength properties in the formed foam articles.
- the invention has met the above needs.
- the invention provides a system whereby expandable polymer, e.g. styrene, particles that are intimately mixed or impregnated with a blowing agent, are formed into foamed cellular particles at the polymer producer's plant.
- the blowing agent may be a volatile organic compound (VOC) or a combination of a volatile organic compound and an inorganic compound, i.e. carbon dioxide, air, water, and nitrogen.
- VOC volatile organic compound
- the blowing agent is pentane or a mixture of pentane .
- foamed cellular particles have a reduced bulk density, an established cell structure with a substantially fixed number of cells, and a reduced amount of blowing agent.
- foamed cellular particles are packaged and shipped to the foam molder for the production of foam articles.
- the shipped particles contain a relatively low level of blowing agent for subsequent processing at the foam molder' s site for producing foam articles.
- the expandable polymer particles used as the starting material for producing the foamed cellular particles of the invention have a bulk density ranging from about 40 pounds per cubic foot (641 kilograms per cubic meter) to about 32 pounds per cubic foot (514 kilograms per cubic meter) and a blowing agent in an amount less than 10 wt %, preferably less than 9.0 wt %, and most preferably, ranging between 3.0 and 9.0 wt %, based on the weight of the polymer composition.
- These expandable polymer particles are heated at a temperature ranging between about 70°C and 110°C and at a pressure ranging between about 10 psi absolute (70kPa) and 24.7 psi absolute (170kPa) to form the foamed cellular particles.
- foamed cellular particles have an established cell structure with a fixed number of cells, the number of which generally will not be increased when the foamed cellular particles are subjected to subsequent expansion and/or molding processes in the production of foam articles.
- This cell structure is a "fine" cell structure with an average cell size ranging between about 5 microns and 100 microns, preferably between 10 and 60, and more preferably, between 10 and 50 microns.
- These foamed cellular particles have a bulk density ranging between about 34.3 pounds per cubic foot (550 kilograms per cubic meter) and 12.5 pounds per cubic foot (200 kilograms per cubic meter) , and a blowing agent level less than 6.0 wt %, based on the weight of the polymer composition.
- this blowing agent level ranges between about 2.0 and 5.0 wt %, and more preferably, ranges from about 2.5 and 3.5 wt % based on the weight of the polymer composition.
- the foamed cellular particles are packaged in available standard resin packages. These resin packages have a strength that is lower than the packages currently used for shipping conventional expandable polymer particles.
- the total shipment weight of the foamed cellular particles is substantially equal to the total shipment weight of the conventional expandable particles when being shipped by the same transportation means, e.g. tractor-trailer.
- the number of packages used in transporting the foamed cellular particles of the invention may be greater than the number of packages used for transporting the conventional expandable particles with a higher bulk density and a higher blowing agent level .
- the blowing agent in the foamed cellular particles will not as readily dissipate during transportation compared to the conventional expandable particles (non-expanded) containing higher levels of blowing agent.
- the conventional expandable particles which contain from about 3.5 wt % to 7.2 wt % pentane may have an effective shelf life of about 3 months.
- the foamed cellular particles of the invention have a longer shelf life than the conventional expandable particles .
- the blowing agent weight loss in the foamed cellular particles is about 15% to 50% lower compared to that of the expandable particles i.e. non-expanded particles in the same predetermined time at room temperature.
- VOC volatile organic compounds
- particles refer to beads i.e. spherical in shape, generally produced in a polymerization process or to pellets generally produced in an extrusion process.
- conventional expandable particles generally refer to expandable particles that have not been subjected to an expansion process, that are generally "high- density” beads having a diameter from about 0.2 to 4.0 millimeters, and that have a bulk density of about 40 pounds per cubic foot (641 kilograms per cubic meter) .
- foamed cellular particles are formed at the plant of the polymer producer by using expandable polymer particles as the starting material. These foamed cellular particles are then shipped to the foam molder for " use in a mold in the production of foam articles, such as cups, expanded blocks and/or shaped articles.
- the foamed cellular particles of the present invention have a sufficient amount of blowing agent such that they do not require any further pre-treatment nor do they need to be impregnated with any additional blowing agent at the foam molder' s site.
- the foamed cellular particles have a certain fixed or established cell structure such that the number of cells in each particle does not change significantly during shipment, storage, and/or the foam molding processes.
- the expandable polymer particles used to form the foamed cellular particles of the invention have a bulk density ranging between 40 pounds per cubic foot (641 kilograms per cubic meter) and 32.0 pounds per cubic foot (513 kilograms per cubic meter) . When these particles are heated, the bulk density of the particles is reduced to between 34.3 pounds per cubic foot (550 kilograms per cubic meter) and 12.5 pounds per cubic foot (200 kilograms per cubic meter) , preferably 25 pounds per cubic foot (400 kilograms per cubic meter) . At this bulk density, the cell size of the foamed cellular particles is relatively small.
- the average size of the cells of the foamed cellular particles ranges between about 5 to 100 microns, preferably between 10 and 60 microns, and most preferably between 10 to 50 microns.
- the average cell size is measured by cutting the foamed cellular particle in half and imaging each sample with a Hitachi S2500 electron microscope, using a 10 kilovolt energy beam, a 15 mm working distance, secondary electron detector imaging, and magnified from 100 to 1000 times.
- the foamed cellular particles of the invention have a reduced bulk density.
- This reduced bulk density can be interpreted to mean that for the same weight load capacity of the tractor- trailer, the number of packages used to ship the foamed cellular particles of the invention can be increased relative to the number of packages presently used to ship conventional expandable particles.
- the expandable polymer particles are packaged in a standardized resin package known to one skilled in the art to be a standard package holding about 1,000 to about 2,200 pounds. Since the tractor-trailer can haul about 30,000 to 50,000 pounds, about 45 to 80 cartons can be used to ship the conventional expandable particles. However, if the tractor-trailer has a maximum load of, for example, 42,000 pounds, then for 1,000 pound cartons of expandable particles, 42 cartons would be used to ship a full truck load.
- the foamed cellular particles of the present invention With the foamed cellular particles of the present invention, more cartons can now be shipped at the same total weight requirement as the conventional expandable particles. For example, for a 48 foot tractor-trailer, the entire space can be occupied with about 60 typical sized cartons containing foamed cellular particles of the invention with a bulk density of about 25 pounds per cubic foot (400 kilograms per cubic meter) while not exceeding the permissible gross vehicle weight limit of 80,000 pounds. The dunnage i.e. inflatable air bags can be eliminated since the tractor- trailer is now volumetrically full .
- the total shipping volume of the foamed cellular particles is not increased significantly compared to the conventional expandable particles, and therefore, the transportation costs for the foamed cellular particles will not increase.
- the average • particle size of the foamed cellular particles s is not increased significantly, i.e. not larger than 130% of the corresponding expandable polymer particles, i.e. the particles in an unexpanded state prior to being formed into foamed cellular particles .
- the polymer composition of the expandable particles which form the foamed cellular particles may be a polymer or a blend of polymers.
- the polymeric material may comprise a substantial portion typically not less than 70, preferably not less than 80 weight % of one or more styrenic monomers and a minor amount, typically less than 30, preferably less than 20 weight % of rubber, a polyphenylene oxide polymer or a high impact styrenic polymer.
- Suitable styrenic polymers comprise from 100 to 70 weight % of one or more C 8 - 12 vinyl aromatic monomers which are unsubstituted or substituted by one or more substituents selected from the group consisting of C x _ 6 , preferably C ⁇ _ 4 alkyl radicals and halogen atoms, preferably chlorine and bromine atoms, and from 0 to 30 weight % of one or more components selected from the group consisting of monomers selected from the vinyl group consisting of C 3 - s ethylenically unsaturated carboxylic acids, anhydrides, imides, and C ⁇ _ ⁇ 2 , preferably C ⁇ _ 4 alkyl and alkoxyalkyl esters 5 thereof, acrylonitrile and methacrylonitrile and optionally which may be grafted onto or occluded within one or more rubbers selected from the group consisting of (i) polymers of one or more C 4 - 5 conjugated diolefin monomers (diene
- Suitable vinyl aromatic monomers include styrene, alpha methyl styrene, para methyl styrene, chlorostyrene and bromo-styrene .
- Suitable ethylenically unsaturated carboxylic 30 acids include acrylic acid, methacrylic acid, and itaconic acid.
- Suitable anhydrides include maleic anhydride.
- Suitable imides include malimide.
- Suitable esters include methyl methacrylates, ethyl methacrylate, butyl acrylate, methyl acrylate, and ethyl acrylate .
- Suitable conjugated diolefins include butadiene (1, 4-butadiene) and isoprene.
- a preferred vinyl aromatic monomer is styrene .
- Suitable polymers include polystyrene, styrene acrylates, copolymers of styrene and esters of acrylic or methacrylic acid, copolymers of styrene and acrylonitrile (SAN) , high impact polystyrene (HIPS- i.e. styrene monomer polymerized and grafted onto and/or occluded within from about 2 to 12, preferably from 4 to 10 weight % of a diene rubber) , and styrene acrylonitrile copolymerized in the presence of from 2 to 12 , preferably from 4 to 10 weight % of diene rubber or a nitrile rubber (ABS) .
- ABS nitrile rubber
- the polymeric component may be blends of the above polymers provided the vinyl aromatic component is not less than about 70 weight %.
- the blends may also include up to about 30 weight % of polyphenylene oxide.
- the blend could be a blend of 70 or more weight % of styrene and up to 30 weight % of polyphenylene oxide.
- the blend could be a predominant amount of a styrene acrylate or methacrylate polymer (e.g. styrene methyl methacrylate) and one or more block copolymers of styrene and butadiene (some blends of which are sold by NOVA Chemicals as ZYLAR® resin) .
- the foamed cellular particles are made from expandable polymer particles that are made expandable by a blowing agent .
- blowing agents are well known to those skilled in the art and are typically acetone, methyl acetate, butane, n-pentane, hexane, isobutane, isopentane, neopentane, cyclopentane and cyclohexane .
- Other blowing agents used in making polymer particles expandable are HFC'S, CFC'S, and HCFC'S, and mixtures thereof.
- the blowing agent can be acetone, methyl acetate, butane, n-pentane, cyclopentane, isopentane, isobutane, neopentane, and mixtures thereof.
- a preferred blowing agent is normal pentane and mixtures of pentane.
- any of the preceding blowing agents may also be used in combination with carbon dioxide, air, nitrogen, and water.
- the blowing agent level of the expandable polymer particles generally will be less than 10.0 weight %, preferably less than 9.0 weight %, and most preferably will range from between about 3.0 wt % and about 9.0 wt %, based on the weight of the polymer composition. If the polymer of the particles is a styrenic polymer, then the weight -average mean molecular weight of the styrenic polymer is greater than 130,000.
- Expandable particles from which the foamed cellular particles of the invention may be obtained can be prepared by various methods . These include polymerization and extrusion processes . In the polymerization process, the polymer composition is polymerized to a conversion greater than 99%.
- the polymerization process may include bulk polymerization, solution polymerization, and suspension polymerization techniques.
- the blowing agent may be added before, during or after the polymerization process .
- a preferred polymerization process for the production of expandable particles is suspension polymerization.
- a polymer composition is polymerized in an aqueous suspension in the presence of from 0.1 to 1.0% by weight of a free radical initiator and the blowing agent .
- initiators are known to those skilled in the art. In this respect reference is made to e.g., U.S. Patent Nos . 2,656,334 and 3,817,965 and European Patent Application No. 488,040.
- the initiators disclosed in these references can also be used to make the expandable particles that in turn are used to make the foamed cellular particles of the present invention.
- Suitable initiators are organic peroxy compounds, such as peroxides, peroxy carbonates and peresters . Typical examples of these peroxy compounds are C 6 .
- acyl peroxides such as decanoyl peroxide, benzoyl peroxide, octanoyl peroxide, stearyl peroxide, peresters, such as t-butyl perbenzoate, t- butyl peracetate, t-butyl perisobutyrate, t- butylperoxy 2-ethylhexyl carbonate, carbonoperoxoic acid, 00- (1, 1-dimethylpropyl) O- (2-ethylhexyl) ester, hydroperoxides and dihydrocarbyl peroxides, such as those containing C 3 _ ⁇ 0 hydrocarbyl moieties, including di-isopropyl benzene hydroperoxide, di- t -butyl peroxide, dicumyl peroxide or combinations thereof.
- hydroperoxides and dihydrocarbyl peroxides such as those containing C 3 _ ⁇ 0 hydrocarby
- suspension polymerization is carried out in the presence of suspension stabilizers.
- Suitable suspension stabilizers are well known in the art and comprise organic stabilizers, such as poly (vinyl alcohol) , gelatine, agar, polyvinyl pyrrolidine, polyacrylamide; inorganic stabilizers, such as alumina, bentonite, magnesium silicate; surfactants, such as sodium dodecyl benzene sulfonate; or phosphates, like tricalciumphosphate , disodium-hydrogen phosphate, optionally in combination with any of the stabilizing compounds mentioned earlier.
- organic stabilizers such as poly (vinyl alcohol) , gelatine, agar, polyvinyl pyrrolidine, polyacrylamide
- inorganic stabilizers such as alumina, bentonite, magnesium silicate
- surfactants such as sodium dodecyl benzene sulfonate
- phosphates like tricalciumphosphate , disodium-hydrogen
- the amount of stabilizer may suitably vary from 0.001 to 0.9% by weight, based on the weight of the aqueous phase .
- the expandable particles may also contain an anti-static additive; a flame retardant; a colorant or dye; a filler material, such as carbon black, titanium dioxide, aluminum, and graphite, which are generally used to reduce thermal conductivity; stabilizers; and plasticizers, such as white oil or mineral oil.
- the particles may suitably be coated with coating compositions comprised of white oil or mineral oil, silicones, metal or glycerol carboxylates, suitable carboxylates being glycerol mono-, di- and tri-stearate, zinc stearate, calcium stearate, and magnesium stearate; and mixtures thereof. Examples of such compositions have been disclosed in GB Patent No. 1,409,285 and in Stickley U. S. Patent No. 4,781,983.
- the coating composition can be applied to the particles via dry coating or via a slurry or solution in a readily vaporizing liquid in various types of batch and continuous mixing devices. This coating aids in preventing the formation of agglomerates during the production of the foamed cellular particles. This increases the prime conversion of expandable particles into foamed cellular particles. Once foamed cellular particles are formed, they may also be optionally coated with additional coatings of similar compositions.
- the coating composition may be applied to the expandable polymer particles, or to the foamed cellular particles or to both the expandable polymer particles and to the foamed cellular particles.
- these coating compositions can reduce agglomeration during the final pre-expansion step and can also affect molding properties such as the pressure decay time or molding cycle cool time.
- the coating composition may also aid in acquiring higher expansion rates for the foamed cellular particles compared to the expansion rate for conventional expandable polystyrene (EPS) (Experiment 9) .
- EPS expandable polystyrene
- Addition of coatings such as mineral oil or white oil at the molders' location is also possible. For example mineral oil can be added just following pre-expansion and/or just prior to foam molding. This technology is sometimes used with conventional expandable polystyrene products and is known to those skilled in the art.
- the expandable polymer particles, and therefore the foamed cellular particles may contain various additives, such as chain transfer agents, suitable examples including C 2 - 15 alkyl mercaptans, such as n-dodecyl mercaptan, t-dodecyl mercaptan, t-butyl mercaptan and n-butyl mercaptan, and other agents such as pentaphenyl ethane and the dimer of ⁇ -methyl styrene.
- the expandable polymer particles may contain cross-linking agents, such as butadiene and divinylbenzene, and nucleating agents, such as polyolefin waxes.
- the polyolefin waxes i . e . , polyethylene waxes, have a weight average molecular weight of 500 to 5,000, which are typically finely divided through the polymer matrix in a quantity of 0.01 to 1.0% by weight, based on the amount of polymer composition.
- the particles may also contain from 0.1 to 0.5% by weight, talc, organic bromide-containing compounds, and polar agents as described in e.g. WO 98/01489 which comprise isalkylsulphosuccinates, sorbital-C 8 - C 2 o - carboxylates, and C 8 - C 2 o- alkylxylene sulphonates . Nucleating agents are particularly useful because they tend to improve the formation of cells .
- the polymer composition of the invention may be comprised of a styrenic monomer with an amount of an acrylate monomer in an amount in a range of about 0.3 to about 5.0 weight percent based on the amount of styrenic monomer.
- Suitable acrylate monomers include, but are not limited to, methyl acrylate, ethyl acrylate, n- butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, 2 -methoxyethyl acrylate, n-octyl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, benzyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n- butyl methacrylate, 2-ethylhexyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, and the like, and mixtures thereof.
- a preferred acrylate monomer is n-butyl acrylate.
- Such acrylate monomers are known to lower the T g of the polymer which, in turn, improves the expandability of the polymer particles whereby the expandable particles require a lower amount e.g. less than 2.5 weight percent of blowing agent, eg. pentane.
- blowing agent eg. pentane.
- the method for copolymerizing styrene monomer and acrlyate monomer is taught in U.S. Patent No. 5,240,967 to Sonnenberg, et al . that is now assigned to the assignee of this patent application. All the teachings of this '967 patent are incorporated herein by reference.
- the suspension polymerization is suitably carried out in the plant of a polymer producer in a one-step or a two-step time/temperature- controlled process.
- a pre- programmed time/temperature reaction cycle is used over the range of 80°C to 140°C, depending on the type and amount of initiator used in the polymerization process and depending on the desired molecular weight, molecular weight distribution, and styrene residual of the polymer.
- Products of commercial interest typically contain less than 1,000 parts per million (PPM) residual styrene and have a weight-average molecular weight greater than 130,000.
- particle size is also important for the expandable particles .
- Products of commercial interest range from about 0.2 mm. to about 3.0 mm.
- the polymer composition may comprise a styrenic monomer in an amount ranging from 70 to 100, preferably, from 80 to 100 weight percent, based on the polymer composition where the styrenic monomer may be admixed with a at least a vinyl group monomer such as those listed herein above in an amount ranging from about 30 to 0 weight %, preferably, 20 to 0 weight %, based on the polymer composition.
- the polymer composition may comprise a styrenic monomer in an amount ranging from 70 to 100 weight % based on the polymer composition admixed with at least one polymer selected from the group consisting of polyphenylene oxide, butadiene rubber, and high impact polystyrene in an amount ranging from 30 to 0 weight % based on the polymer composition.
- the expandable polymer particles of a polymer composition for use in the invention can be also formed via an extrusion process.
- the polymer composition may comprise a styrenic polymer in an amount ranging from 70 to 100 weight % based on the polymer composition admixed with at least one vinyl group polymer in an amount ranging from 30 to 0 weight % based on the polymer composition.
- the polymer composition may comprise a styrenic polymer in an amount ranging from 70 to 100 based on the polymer composition admixed with at least one polymer in an amount ranging from about 30 to 0 weight % based on the polymer composition and selected from the group consisting of polyphenylene oxide, butadiene rubber, and high impact polystyrene .
- the polyphenylene oxide, butadiene rubber, and high impact polystyrene of the polymer composition preferably is added to improve the performance properties of the polymer composition, e.g. mechanical, thermal, physical, and chemical properties.
- This additional polymer may be added before or during the suspension polymerization or the extrusion processes, or the components of the polymer composition may be mixed together by a static or dynamic mixer in a well-known manner in situ prior to the start of the polymerization and/or extrusion processes .
- Suitable polyphenylene oxides used herein may be those described, for example, in EP-A-350137, EP-A-403023 and EP-A- 391499.
- a single-screw or a multi-screw extruder may be used.
- One method for preparing foamed particles involves injecting the blowing agent into the extruder, extruding pellets, and either letting the pellets expand or expanding the pellets through a process well known to those in the art . More particularly, the blowing agent is mixed into the molten polymer composition, which is drawn through a plurality of holes in the die face to produce strands .
- the extruded strands are cut into expandable polymer particles by a conventional under-water face-cutting apparatus or cooled in a water bath and subsequently cut by a pelletizing chopper into pellets having a length ranging from about 0.2 mm to about 3.00 mm.
- Foamed cellular particles are then formed from these expandable particles via a heating/pressure process described herein.
- Another method for preparing foamed particles via an extrusion process involves the extrusion of the molten polymer composition through the die face, chopping the strands into pellets, and impregnating the pellets. Foamed cellular particles from these expandable particles are then formed via a heating/pressure process described herein.
- a further variation of the extrusion process involves the expandable particles being formed into foamed cellular particles at the die face instead of downstream from the extruder.
- heat from the extruder that is inherent in the strand or pellet will cause the blowing agent to vaporize and to expand within the matrix of the strand or pellet to form the foamed cellular particles of the invention.
- the temperature in the extruder may range between 200 and 250°C and its pressure may range between 300 psia and 3,000 psia. It will be appreciated that the amount of blowing agent and heat in the extruder, and the type of cooling means used at the die face can be controlled to obtain the desired bulk density of and the desired amount of blowing agent in the foamed cellular particles of the invention.
- the expandable particles may be formed in an extruder where a polymerization process forms the polymer composition.
- the components of the polymer composition along with an initiator and other additives may be introduced into the extruder.
- This process generally will include the step of admixing a styrenic monomer in an amount ranging between about 70 and 100 weight % based on the amount of monomer composition with at least one vinyl group monomer in an amount ranging between 30 and 0 weight % based on the monomer composition.
- the blowing agent can be mixed into the molten composition before it is drawn through the die face to produce strands which are then cut into pellets or the pellets can be impregnated with the blowing agent which are subsequently formed into foamed cellular particles or foamed cellular particles can be formed at the die face .
- the expandable particles have a bulk density ranging between 40 pounds per cubic foot (641 kilograms per cubic meter) and 32.0 pounds per cubic foot (513 kilograms per cubic meter) .
- These particles are heated between 70 °C and 110 °C, preferably between 80°C to 110 °C and are simultaneously subjected to a pressure of 10.1 psi absolute (70 kPa) to about 24.7 psi absolute (170 kPa) , preferably 95 kPa to 110 kPa absolute, for a time ranging from 1 minute to 60 minutes to form foamed cellular particles.
- the foamed cellular particles have a reduced bulk density ranging between about 34.3 pounds per cubic foot (550 kilograms per cubic meter) and 12.5 pounds per cubic foot (200 kilograms per cubic meter) .
- the bulk density of the foamed cellular particles ranges between 28.1 pounds per cubic foot (450 kilograms per cubic meter) and 21.9 pounds per cubic foot (350 kilograms per cubic meter) , and more preferably, the bulk density is about 25 pounds per cubic foot (400 kilograms per cubic meter) .
- the blowing agent level of the foamed cellular particles is less than 6.0 weight % based on the weight of the polymer composition, preferably ranges between 2.0 wt % and 5.0 wt %, and more preferably ranges between about 2.5 weight % and 3.5 weight %.
- the foamed cellular particles have an average particle size ranging between about 0.2 and 3 mm, preferably between about 0.3 and 2 mm. Each particle has an average cell size ranging between about 5 and 100 microns, preferably between 10 and 60 microns, and most preferably between 10 and 50 microns .
- the heating process utilized in the invention in forming the foamed cellular particles from the expandable solid particles may be carried out in a fluidized bed in a batch or continuous heating process, with or without mechanical agitation or vibration.
- Other suitable heating methods may include contact heating, non-contact heating, infrared heating, microwave heating, dielectric heating, and radio frequency heating.
- Pre-expander equipment as generally used for the processing of expandable particles is suitable for the preparation of the foamed cellular particles of the invention.
- An example of such a pre-expander is Hirsch® 3000 provided by the Hirsch Company.
- the foamed cellular particles of the invention have been found to exhibit equivalent or superior expandability characteristics compared to the conventional expandable particles . This includes the expansion throughput rates and the ability of the foamed particles to achieve a required final low density, i.e. about 0.8 to 6.0 pounds per cubic foot (12 to 30 kilograms per cubic meter) for the foamed articles at the foam molder' s plant when using conventional expansion and molding equipment .
- the shelf life of the polymer particles can be correlated to the rate at which the blowing agent dissipates from the particles. It is the inventors' belief that the foamed cellular particles of the invention have a longer shelf life compared to the conventional expandable particles.
- the foamed cellular particles of the invention are placed in a pentane-resistant plastic bag that is closed at the top by a wire tie.
- the bag is supported in a carton and then shipped to the foam molder.
- the cartons for the foamed cellular particles can have a material compressive strength of 10,000 pounds. It is believed that this material strength can be less than that being used when shipping conventional expandable particles in specialized cartons with a material strength of about 12,000 pounds. This would be possible since the foamed cellular particles in their low bulk density form weigh less per unit volume than the expandable particles .
- the foamed cellular particles When being shipped, the foamed cellular particles will have a total shipment weight substantially equal to the total shipment weight of the expandable particles. If the total maximum weight a tractor-trailer can transport is 30,000 to 50,000 pounds, the number of cartons used in transporting the foamed cellular particles may range respectively between 45 and 80.
- the properties of the foam articles i.e. forming expandable particles into foamed cellular particles at the polymer producer' s site and then shipping the foamed cellular particles to a foam molder for the subsequent production of foamed articles, the properties of the foam articles, such as mechanical strength and particle fusion, will be at acceptable levels.
- the foamed cellular particles of the invention can be pre- expanded and molded into foam articles by conventional steam expansion and molding methods, and as mentioned herein above, and with conventional equipment without the need to impregnate the foamed cellular particles with an additional amount of blowing agent.
- the foam articles will have a bulk density ranging between about 0.50 pounds per cubic foot (8.0 kilograms per cubic meter) and about 6.0 pounds per cubic foot (96.1 kilograms per cubic meter) .
- the hydrocarbon blowing agents emitted during the production of the foamed cellular particles of the invention can be captured, condensed and recycled into the processes for manufacturing the expandable polymer particles or burned at the polymer producer's plant. The methods and equipment for doing this are conventional.
- the levels of VOC emissions in forming foamed cellular particles of the invention can be controlled within the allowed regulatory standards for the respective geographical area, and that at the foam molder' s plant, these levels are reduced.
- the experimental foamed cellular particles were prepared in a lab or pilot plant and were evaluated with some small-scale commercial equipment. Batch expansion was done by using either a non-agitated, 2 -gallon batch expander with a perforated screen bottom supporting the particles that were subjected to steam at atmospheric pressure or by using a Hirsch® 3000 pressure expander (Preex 3000) .
- the pentane percentage was measured by headspace gas chromatography, the method of which is well known to those skilled in the art.
- the headspace unit is a Hewlett Packard Model 7694 gas chromotograph auto-sampler with a heated transfer line and septum needle termination. The oven temperature was 125°C. The temperatures for both the transfer line and the sample loop were 150°C.
- the gas chromatograph is a Hewlett Packard Model 5890 with split/splitless capillary inlet and a flame ionization detector.
- the column used in the gas chromatography was a J&W, DB-1, with a 30m x .53 mm capillary and a 1.50 urn film-thickness. Bulk density was measured using a 25 millimeter graduated cylinder and a certified analytical balance.
- Example 1 This Example 1 illustrates that the blowing agent retention of the foamed cellular particles of the invention may be increased compared to a control comprised of conventional expandable particles.
- expandable polystyrene particles were used as the control and as the starting material in the production of the experimental foamed cellular particles.
- the expandable polystyrene particles were produced using a "two-step" process with an initial suspension polymerization followed by a subsequent impregnation process.
- the resulting expandable particles contained hexabromo- cyclododecane as a fire retardant and a mixture of normal pentane, isopentane, and cyclopentane as the blowing agent along with other typical additives, such as a lubricant coating, e.g. glycerol-monostearate .
- a sample of expandable polystyrene particles contained a total pentane content of 4.24 wt % as measured by headspace gas chromatography. These expandable particles had a bulk density of 37.85 pounds per cubic foot (606 kilograms per cubic meter) and an average particle size of 0.886 mm. The particles were placed on a tray in a single layer and left for 19 days at room temperature. The total pentane content in the expandable particles after 19 days decreased from 4.24 wt % to 2.71 wt % based on the weight of the polymer. This was a reduction of 36% total pentane content in the particles.
- foamed cellular polystyrene particles were prepared from the same starting material as the control .
- one pound (454 grams) of the expandable particles was placed in a fluid bed dryer with a glass body (Lab-Line Hi-Speed Fluid Bed Dryer Model #23850 (1985)) and was subjected to atmospheric pressure with an inlet air temperature of 85 °C for 25 minutes.
- the resulting foamed cellular particles had a bulk density of 26.37 pounds per cubic foot (422 kilograms per cubic meter) and a total pentane content of 3.86 wt % as measured by headspace gas chromatography (GC) .
- the average particle size was 1-.155 mm.
- the particles were arranged in a single layer on a tray and left for 19 days at room temperature.
- the total pentane content in the particles after 19 days decreased from 3.86 wt % to 3.11 wt % based on the weight of the polymer. This was a reduction of 19% total pentane content in the particles.
- the experimental foamed cellular particles had a higher percent, i.e. 47% blowing agent retention capacity compared to the control particles.
- Example 2 illustrates that the expansion rate for the foamed cellular particles of the invention may be at least comparable to the expansion rate for the control expandable particles.
- the expandable particles were taken from the same batch of expandable polystyrene particles used in Example 1.
- For the control 3.5 pounds (1589 grams) of pre-weighed expandable polystyrene particles were used. These particles had an initial bulk density of 38.05 pounds per cubic foot (609.5 kilograms per cubic meter) .
- These particles contained 4.30 wt % pentane as measured by headspace gas chromatography.
- pre-puff particles i.e. particles that are expanded prior to aging and molding.
- the bulk density of the pre-puff particles was 0.88 pound per cubic foot (14.1 kilograms per cubic meter) .
- Foamed cellular particles of the invention were formed in a batch-wise process by placing 10 pounds (4.54 kilograms) of expandable particles similar to those used in the control in a fluid bed dryer that was 1.229 ft in diameter. The batch time was 20 minutes and the temperature was 87°C. The resulting bulk density of these foamed cellular polystyrene particles was 18.41 pounds per cubic foot (295 kilograms per cubic meter) . These foamed cellular particles contained 3.48 wt. % pentane as measured by headspace gas chromatography. The foamed cellular particles were then pre- expanded in batch form in the pressure expander at a steam pressure of 0.33 bar and a throughput rate of 113 pounds/hour. The resultant pre-puff bulk density was 0.88 pounds per cubic foot (14.1 kilograms per cubic meter) . This is equivalent to the bulk density obtained for the control sample even though the foamed cellular particles contained 19% less pentane than that of the control sample.
- the pre-puff particles of the control and the pre-puff particles produced from the foamed cellular particles were steam molded into a block in a commercially-available Wieser® molding machine with dimensions of 2490 mm x 640 mm x 740 mm.
- the two resulting blocks were aged and cut into boards using heated electric wires .
- Core samples were tested on an INSTRON 4204 Model instrument with Series IX Version 8.08.00 software using the following methods for obtaining density and compressive resistance measurements :
- Example 3 Commercially available expandable polystyrene particles were used for both the control and for the starting material for the production of foamed cellular particles.
- the expandable polystyrene particles were produced using a "one-step" suspension process in which pentane blowing agent was introduced into the on-going polymerization process.
- the resulting expandable particles contained hexabromo- cyclododecane as a fire retardant and 100% normal pentane as the blowing agent in addition to other conventional additives.
- a sample of the expandable polystyrene particles had a pentane content of 5.93 wt % as measured by headspace gas chromatography. These expandable particles had a bulk density of 36.88 pounds per cubic foot (591 kilograms per cubic meter) and an average particle size of 0.754 mm. The particles were placed on a tray in a single layer and left for 20 days at room temperature. The pentane content remaining in the particles after 20 days decreased from 5.93 wt % to 3.95 wt%. This was a 33% pentane reduction in the particles.
- foamed cellular polystyrene particles were prepared from the same starting material as the control.
- One pound (454 grams) of the expandable polystyrene particles was placed in the fluid bed dryer used in Experiment 1 and the particles were subjected to atmospheric pressure with an inlet air temperature of 78 °C for 50 minutes.
- the resulting foamed cellular particles had a bulk density of 24.22 pounds per cubic foot (388 kilograms per cubic meter) and a pentane content of 4.66 wt %.
- the average particle size was 0.863 mm.
- the particles were arranged in a single layer on a tray and left for 20 days at room temperature .
- the pentane content in the particles after 20 days had decreased from 4.66 wt % to 3.46 wt %. This was a 26%
- Example 4 The control expandable polystyrene particles with a pentane level of 5.93 wt % and the experimental foamed cellular particles of the invention with a pentane level of 4.66 wt % used in Example 3 were also used in Example 4. Fifty (50) grams of the particles were added to a non-agitated, 2 -gallon batch expander with a perforated screen bottom. Atmospheric steam was introduced through the screen into the bottom of the expander and the particles were expanded for 2 minutes. Each experiment was done in duplicate. Through visual inspection, the control samples, i.e. the expandable polystyrene particles, exhibited significant agglomeration and "lumping" during expansion. This was expected since the expander was not agitated. Contrary to this, the experimental foamed cellular particles were free flowing and displayed no agglomeration during batch expansion even though the expander was not agitated. Table 1 contains the data for this Example 4 :
- Example 5 illustrates that the blowing agent retention of the foamed cellular particles of the invention may be increased compared to a control comprised of expandable particles that are produced in an extrusion process .
- expandable polystyrene extruded pellets were used as the control and as the starting material in the production of experimental foamed cellular particles of the invention.
- the expandable polystyrene particles were produced using an extrusion process in which pentane as the blowing agent was mixed with polystyrene and extruded through a die and the strands cooled and cut to produce expandable cylindrical pellets.
- the resulting expandable pellets contained carbon black and 100% isopentane as the blowing agent along with other conventional additives, such as a lubricant coating.
- the expandable polystyrene pellets contained 4.68 wt % isopentane as measured by headspace gas chromatography. These cylindrical expandable particles had a bulk density of 32.79 pounds per cubic foot (525.2 kilograms per cubic meter) and an average length of 2.23 mm. and an average diameter of 0.62 mm. These particles were placed on a tray in a single layer and left for 21 days at room temperature. The total isopentane content in the control particles after 21 days decreased from 4.68 wt % to 4.54 wt %. This is a reduction of 3% of the isopentane content in the particles.
- the experimental foamed cellular polystyrene particles were prepared from the same starting material as the control.
- One pound (454 grams) of experimental particles was prepared at atmospheric pressure with an inlet air temperature of 80 °C for 25 minutes in a fluid bed dryer with a glass body (Lab-Line Hi- Speed Model #23850) .
- the resultant foamed cellular particles had a bulk density of 23.75 pounds per cubic foot (380.4 kilograms per cubic meter) and a total isopentane content of 4.34 wt % as measured by headspace gas chromatography.
- the average particle was approximately spherical in shape with an approximate diameter of 1.14 mm.
- the particles were arranged in a single layer on a tray, and were left for 21 days at room temperature.
- the total isopentane content in the particles after 21 days had decreased from 4.34 wt % to 4.27 wt %.
- the total isopentane content in the particles was reduced 1.6%.
- the experimental foamed cellular particles had a higher, i.e. 46% blowing agent retention capacity compared to the control particles .
- the amount of blowing agent that is lost in the particles over time has a deleterious effect on the expansion and molding performance of expandable particles.
- the foamed cellular particles of the invention indicate a tendency to improve the amount of blowing agent retained in the particles.
- Example 6 This Example illustrates that the blowing agent retention of the foamed cellular particles of the invention compared to a control of expandable particles may be increased.
- impregnated, extruded pellets made from high-impact polystyrene were used as the starting material.
- the rubber content was 3.5%.
- expandable high-impact polystyrene extruded pellets were used for both the control and for the starting material for the production of experimental foamed cellular particles.
- the expandable high-impact polystyrene was produced using an extrusion process in which pentane used as the blowing agent was mixed with high-impact polystyrene and extruded through a die and the strands were cooled and cut to form expandable cylindrical pellets.
- the resulting expandable pellets contained 40% normal pentane (n-pentane) and 60% isopentane as the blowing agent along with other conventional additives, for example, a lubricant coating.
- a sample of expandable polystyrene pellets contained a total pentane content of 3.89 wt % as measured by headspace gas chromatography.
- These cylindrical expandable particles had a bulk density of 33.24 pounds per cubic foot (532 kilograms per cubic meter) with an average length of 2.09 mm. and an average diameter of 0.56 mm.
- the particles were placed on a tray in a single layer for 21 days at room temperature.
- the total pentane content in the particles after 21 days decreased from 3.89% to 3.40%. This was a reduction of 12.6% total pentane content in the particles .
- the experimental foamed cellular particles were prepared from the same starting material as the control of this Example.
- One pound (454 grams) of experimental particles was prepared at atmospheric pressure with an inlet air temperature of 90 °C for 25 minutes in a fluid bed dryer used in Example 1.
- the resulting foamed cellular particles had a bulk density of 25.32 pounds per cubic foot (405 kilograms per cubic meter) and a total pentane content of 3.55 wt % as measured by headspace gas chromatography.
- the average particle size was 1.15 mm in diameter and was approximately spherical in shape.
- the particles were arranged in a single layer on a tray 21 days at room temperature .
- the total pentane content in the particles after 21 days decreased from 3.55 to 3.41%.
- Example 5 This was a reduction of 3.9% total pentane content in the particles .
- the experimental foamed cellular particles had 69% better blowing agent retention than the control particles .
- the amount of blowing agent that is lost in the particles over time has a deleterious effect on the expansion and molding performance of expandable particles.
- This Example 6 also gives an indication that the foamed cellular particles of the invention have a tendency to improve the amount of blowing agent retained in the particles .
- Example 7 Example 7
- This Example 7 demonstrates the production of foamed cellular particles using direct steam contact in a mechanically agitated device instead of using hot air in a fluidized bed.
- the starting material was expandable polystyrene (EPS) containing 2.99% normal pentane, 0.33% cyclopentane, and 0.01% isopentane.
- EPS expandable polystyrene
- the material had a starting bulk density of approximately 39 pounds per cubic foot .
- the material was coated with a surface coating of 500 ppm zinc stearate.
- a Hirsch ® Vacutrans 3000-H batch pre-expander was used to produce the foamed cellular particles. The conditions used were:
- the resulting foamed cellular particles had an average particle size of 1.148 mm and contained 2.86% normal pentane, 0.39% cyclopentane, and 0.02% isopentane.
- Example 8 A copolymer of styrene and n-butyl acrylate was used as the expandable particle starting material. The expandable particles were prepared in a suspension polymerization process with a monomer blend of 98.5 weight percent styrene and 2.5 weight percent n-butyl acrylate based on the copolymer weight, not including the blowing agent . The copolymer was then suspension impregnated with normal pentane as the blowing agent . Suitable suspending agents, surfactants, and time/temperature exposure were used to conduct the impregnation process as are known to those skilled in the art .
- the foamed cellular particles were produced in a fluid bed dryer with a glass body (Lab-Line Hi-Speed Bed Dryer Model #23850 (1985)).
- the resulting material had a pentane content of 3.4%.
- EPS expandable polystyrene
- This Example 9 demonstrates the superior expandability of the foamed cellular particles versus conventional expandable polystyrene (EPS) particle when evaluated at equivalent pentane blowing agent contents.
- EPS polystyrene
- the control sample was conventional expandable polystyrene with a bulk density of 39 pounds per cubic foot, an average bead size of 0.95 mm., and a total pentane content of 3.0%.
- the experimental sample was foamed cellular particles formed in accordance with the teachings of the present invention. This example sample had a bulk density of 25 pounds per cubic foot, an average bead size of 1.11 mm., and a total pentane content of 2.98%.
- Both samples were surface-coated with the same type of composition in similar amounts.
- the composition was a mix of glycerol mono- stearate, glycerol tri-stearate, calcium stearate, and silicone fluid.
- Both samples were expanded in a Hirsch ® Vacutrans 3000-H batch pre-expander to a final "prepuff" bulk density of 1.8 pounds per cubic foot . The expansion conditions and results are shown in the Table 3.
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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HU0303866A HUP0303866A3 (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
BR0115923-2A BR0115923A (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles, system for extending the shelf life of expandable polymeric particles, foamed article, process for preparing foamed cellular particles, and system for optimizing loading and packaging of polymeric particles for use in the production of foamed articles. |
JP2002548013A JP2004529215A (en) | 2000-12-04 | 2001-11-30 | Expanded cellular particles of expandable polymer composition |
EP01991069A EP1352022A4 (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
MXPA03004908A MXPA03004908A (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition. |
CA002430615A CA2430615A1 (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
AU2002230822A AU2002230822A1 (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
KR10-2003-7007364A KR20030059827A (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
NO20032500A NO20032500L (en) | 2000-12-04 | 2003-06-03 | Foamed cellular particles of an expandable polymer composition |
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Application Number | Priority Date | Filing Date | Title |
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US25114000P | 2000-12-04 | 2000-12-04 | |
US60/251,140 | 2000-12-04 | ||
US25420500P | 2000-12-08 | 2000-12-08 | |
US60/254,205 | 2000-12-08 |
Publications (1)
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WO2002046284A1 true WO2002046284A1 (en) | 2002-06-13 |
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ID=26941435
Family Applications (1)
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---|---|---|---|
PCT/US2001/048289 WO2002046284A1 (en) | 2000-12-04 | 2001-11-30 | Foamed cellular particles of an expandable polymer composition |
Country Status (13)
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US (1) | US20020117769A1 (en) |
EP (1) | EP1352022A4 (en) |
JP (1) | JP2004529215A (en) |
KR (1) | KR20030059827A (en) |
CN (1) | CN1237099C (en) |
AU (1) | AU2002230822A1 (en) |
BR (1) | BR0115923A (en) |
CA (1) | CA2430615A1 (en) |
HU (1) | HUP0303866A3 (en) |
MX (1) | MXPA03004908A (en) |
NO (1) | NO20032500L (en) |
PL (1) | PL363223A1 (en) |
WO (1) | WO2002046284A1 (en) |
Cited By (1)
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FR2858977A1 (en) * | 2003-08-21 | 2005-02-25 | Bp Chem Int Ltd | Expandable polystyrene composition in the form of beads used for production of expanded products such as insulation and packaging, contains styrene polymer, blowing agent and plasticiser |
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- 2001-11-30 PL PL01363223A patent/PL363223A1/en not_active Application Discontinuation
- 2001-11-30 CN CNB018199569A patent/CN1237099C/en not_active Expired - Fee Related
- 2001-11-30 MX MXPA03004908A patent/MXPA03004908A/en unknown
- 2001-11-30 US US10/021,716 patent/US20020117769A1/en not_active Abandoned
- 2001-11-30 BR BR0115923-2A patent/BR0115923A/en not_active IP Right Cessation
- 2001-11-30 WO PCT/US2001/048289 patent/WO2002046284A1/en not_active Application Discontinuation
- 2001-11-30 EP EP01991069A patent/EP1352022A4/en not_active Withdrawn
- 2001-11-30 KR KR10-2003-7007364A patent/KR20030059827A/en not_active Application Discontinuation
- 2001-11-30 CA CA002430615A patent/CA2430615A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
AU2002230822A1 (en) | 2002-06-18 |
CN1237099C (en) | 2006-01-18 |
KR20030059827A (en) | 2003-07-10 |
CA2430615A1 (en) | 2002-06-13 |
HUP0303866A2 (en) | 2004-03-01 |
EP1352022A1 (en) | 2003-10-15 |
HUP0303866A3 (en) | 2008-03-28 |
BR0115923A (en) | 2004-01-20 |
NO20032500D0 (en) | 2003-06-03 |
US20020117769A1 (en) | 2002-08-29 |
CN1478120A (en) | 2004-02-25 |
MXPA03004908A (en) | 2004-05-24 |
PL363223A1 (en) | 2004-11-15 |
JP2004529215A (en) | 2004-09-24 |
EP1352022A4 (en) | 2004-03-24 |
NO20032500L (en) | 2003-06-03 |
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