WO2023023088A1 - Foamable thermoplastic compositions, thermoplastic foams and methods of making same - Google Patents
Foamable thermoplastic compositions, thermoplastic foams and methods of making same Download PDFInfo
- Publication number
- WO2023023088A1 WO2023023088A1 PCT/US2022/040507 US2022040507W WO2023023088A1 WO 2023023088 A1 WO2023023088 A1 WO 2023023088A1 US 2022040507 W US2022040507 W US 2022040507W WO 2023023088 A1 WO2023023088 A1 WO 2023023088A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- foam
- cells
- thermoplastic
- blowing agent
- foams
- Prior art date
Links
- 239000006260 foam Substances 0.000 title claims abstract description 354
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 183
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims description 58
- 238000000034 method Methods 0.000 title description 54
- 210000004027 cell Anatomy 0.000 claims abstract description 228
- -1 polyethylene furanoate Polymers 0.000 claims abstract description 92
- 210000002421 cell wall Anatomy 0.000 claims abstract description 64
- 239000004604 Blowing Agent Substances 0.000 claims description 158
- OSHGZBCZUPGLPU-UHFFFAOYSA-N ethene furan-2-carboxylic acid Chemical group C=C.OC(=O)C1=CC=CO1 OSHGZBCZUPGLPU-UHFFFAOYSA-N 0.000 claims description 44
- 229920001864 tannin Polymers 0.000 claims description 15
- 239000001648 tannin Substances 0.000 claims description 15
- 235000018553 tannin Nutrition 0.000 claims description 15
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 description 66
- 125000004432 carbon atom Chemical group C* 0.000 description 35
- 239000004970 Chain extender Substances 0.000 description 34
- 238000005187 foaming Methods 0.000 description 27
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 19
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 18
- 229920001519 homopolymer Polymers 0.000 description 18
- 239000000155 melt Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 102100031663 Alpha-tocopherol transfer protein Human genes 0.000 description 11
- 108010039203 Tripeptidyl-Peptidase 1 Proteins 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 9
- 101001099372 Homo sapiens Peroxisome biogenesis factor 1 Proteins 0.000 description 8
- 102100038881 Peroxisome biogenesis factor 1 Human genes 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 101100207327 Arabidopsis thaliana TPPG gene Proteins 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 101100100084 Oryza sativa subsp. japonica TPP6 gene Proteins 0.000 description 4
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 4
- 239000012815 thermoplastic material Substances 0.000 description 4
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 4
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 3
- 101150080254 PEX22 gene Proteins 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000000914 diffusion-ordered spectroscopy Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 2
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 2
- BSRRYOGYBQJAFP-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluorobutane Chemical compound CC(F)C(F)(F)C(F)(F)F BSRRYOGYBQJAFP-UHFFFAOYSA-N 0.000 description 2
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 102100041019 Coordinator of PRMT5 and differentiation stimulator Human genes 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 101000748895 Homo sapiens Coordinator of PRMT5 and differentiation stimulator Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000002666 chemical blowing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentylidene Natural products CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical group Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 description 1
- NLOLSXYRJFEOTA-UHFFFAOYSA-N 1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C=CC(F)(F)F NLOLSXYRJFEOTA-UHFFFAOYSA-N 0.000 description 1
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- AHFMSNDOYCFEPH-UHFFFAOYSA-N 1,2-difluoroethane Chemical compound FCCF AHFMSNDOYCFEPH-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- JSECXTYNFBONSF-UHFFFAOYSA-N 3-chloro-1,1,1,2-tetrafluoropropane Chemical compound ClCC(F)C(F)(F)F JSECXTYNFBONSF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MEUAVGJWGDPTLF-UHFFFAOYSA-N 4-(5-benzenesulfonylamino-1-methyl-1h-benzoimidazol-2-ylmethyl)-benzamidine Chemical compound N=1C2=CC(NS(=O)(=O)C=3C=CC=CC=3)=CC=C2N(C)C=1CC1=CC=C(C(N)=N)C=C1 MEUAVGJWGDPTLF-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 102100040411 Tripeptidyl-peptidase 2 Human genes 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- AQBTWPYGBZJMLL-UHFFFAOYSA-N cyclohexane;terephthalic acid Chemical compound C1CCCCC1.OC(=O)C1=CC=C(C(O)=O)C=C1 AQBTWPYGBZJMLL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- NHGVZTMBVDFPHJ-UHFFFAOYSA-N formyl fluoride Chemical compound FC=O NHGVZTMBVDFPHJ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005067 haloformyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 108010039189 tripeptidyl-peptidase 2 Proteins 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/04—Linoxyn
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/04—Linoxyn
-
- 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
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Definitions
- This invention relates to foamable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles made from same.
- foams are used in a wide variety of applications, developing a foam that has excellent performance properties and is cost-effective to produce is a derisible but difficult goal to achieve. It is even more difficult to achieve this goal while at the same time developing a foam that is environmentally friendly.
- Producing environmentally friendly foams is especially difficult because they comprise both a blowing agent component and a resin component forming the foam structure, and each of these components has an impact on foam performance and on environmental properties.
- Environmental considerations include not only the recyclability and sustainability of the polymeric resin that forms the structure of the foam but also the low environmental impact of blowing agents used to form the foam, such as the Global Warming Potential (GWP) and Ozone Depletion Potential (ODP) of the blowing agent. It is therefore a major challenge to develop a foam that simultaneously has excellent performance and can be produced cost-effectively from an environmentally friend blowing agent and an environmentally friendly resin.
- GWP Global Warming Potential
- ODP Ozone Depletion Potential
- thermoplastic resins including polyester resins
- foams based on certain thermoplastic resins have been investigated for potential advantage from the perspective of being recyclable and/or sustainably- sourced.
- difficulties have been encountered in connection with the development of such materials.
- polyester resins that are truly recyclable can be produced from sustainable sources, and which are compatible with blowing agents that are able, in combination with the thermoplastic, to produce foams with good performance properties.
- the performance properties that are considered highly desirable include the production of high-quality closed cell foams that are low density (and therefore have a low weight in use) and, at the same time, have relatively high mechanical integrity and strength.
- thermoplastic resin With respect to the selection of thermoplastic resin, EP 3,231 ,836 acknowledges that while there has been interest in thermoplastic resins, in particularly polyester-based resins, this interest has encountered difficulty in development, including difficulty in identifying suitable foaming grades of such resins. Moreover, while EP 3,231,836 notes that certain polyethylene terephthalate (PET) resins, including recycled versions of PET, can be melt-extruded with a suitable physical and/or chemical blowing agent to yield closed-cell foams with the potential for low density and good mechanical properties, it is not disclosed that any such resins are at once are able to produce foams with good environmental properties and good performance properties, and are also able to be formed from sustainable sources.
- PET polyethylene terephthalate
- the ‘836 application identifies several possible polyester resins to be used in the formation of open-celled foams, including polyethylene terephthalate, poly butylene terephthalate, poly cyclohexane terephthalate, polyethylene naphthalate, polyethylene furanoate or a mixture of two or more of these. While the use of polyester materials to make foams that have essentially no closed cells, as required by EP ‘836, may be beneficial for some applications, a disadvantage of such structures is that, in general, open cell foams will exhibit relatively poor mechanical strength properties.
- plastics based on 2,5-furandicarboxylic-acid-based polyester have been noted to have some potential advantages in certain applications, such as having good gas barrier properties, there has also been a recognition of substantial problems with forming foam materials from such plastic materials.
- CN108410000 teaches that 2,5- furandicarboxylic-acid-based polyesters have foaming performance that is very poor and processing conditions that are extremely unfavorable. These problems are said to be addressed by using a glassy (i.e. , amorphous) polymer sheet and then exposing the sheet to a special, relatively complex and cumbersome dual blowing agent process.
- CN 108410000 suffers from several disadvantages, including requiring an undesirably long processing time to produce the specialized, treated preform and the use of a relatively complicated dual blowing agent process.
- This process is also highly disadvantageous in that it is not readily adaptable for use in connection with currently used commercial extrusion equipment, thus having an undesirably high new capital cost requirement to implement.
- CN 108484959 also recognizes that 2,5-furandicarboxylic-acid-based polyesters (such as PEF) have poor foamability and attempts to address this significant problem by forming a high melt viscosity polymer by blend-reacting 2,5-furandicarboxylic acid ethylene glycol ester with a multifunctional monomer selected from alcohols, esters, alkanes, carboxylic acids and anhydrides. Foaming properties of this material are said to be improved relative to PEF, but no information on the foaming process is provided.
- PEF 2,5-furandicarboxylic-acid-based polyesters
- US 2020/0308363 and US 2020/0308396 each disclose the production of amorphous polyester copolymers that comprise starting with a recycled polyester, of which only PET is exemplified, as the main component and then proceeding through a series of processing steps to achieve an amorphous co-polymer, that is, as copolymer having no crystallinity.
- These publications indicate that it is not possible to readily form low density polyester foams from crystalline or semi-crystalline polymers and indicates that this problem can be solved by forming amorphous copolyester polymer material and using such amorphous material to form the foam.
- polyethylene furanoate (PEF) using ethylene glycol and 2,5-furandicarboxylic acid is mentioned but is not exemplified.
- amorphous i.e., no crystallinity as per 0 J/G AH before foaming
- ternary copolymers formed from PET, polytrimethylene furanoate and polycarbonate are said to have been foamed using CO2 as the blowing agent. No foam properties are disclosed.
- a wide variety of different classes of blowing agent are mentioned for use with amorphous polymers generally, including CO2, HFO-1233zd, cyclopentane, acetone and methanol.
- US 9790342 discloses foams formed from the polyphenolic tannin, which may be combined with a large number of possible monomers, and among the list of monomers is 2,5- furandicarboxylic acid.
- the foams are said to be partially open cell and partially closed cell, with open cell content being less than 50%.
- Numerous potential blowing agents are disclosed, including the halogenated olefin HFO-1336mmz.
- blowing agents With respect to blowing agents, the use generally of halogenated olefin blowing agents, including hydrofluoroolefins (HFOs) and hydrochlorofluorolefins (HCFOs), for several specific thermoplastic foams is known, as disclosed for example in US 2009/0305876, which is assigned to the assignee of the present invention and which is incorporated herein by reference. While the '876 application discloses the use of HFO and HFCO blowing agents with various thermoplastic materials to form foams, including PET, there is no disclosure or suggestion to use any of such blowing agents with any other type of polyester resin.
- HFOs hydrofluoroolefins
- HCFOs hydrochlorofluorolefins
- thermoplastic foams and in particular extruded thermoplastic foams, using a polyester resin as disclosed herein in combination with a blowing agent comprising one of more hydrohaloolefin as disclosed herein.
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% of said cells are closed cells;
- Foam 1A1 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1A1.
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% of said cells are closed cells;
- Foam 1A2 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1A2.
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% of said cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 1A3.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- (b) 1224yd is contained in the closed cells.
- Foam 1B1 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1B1.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- Foam 1B2 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1B2.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- Foam 1B3 For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 1B3.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- Foam 1C foams in accordance with this paragraph are referred to herein as Foam 1C.
- the present invention includes low-density, thermoplastic foam comprising: (a) thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer; and
- gas in the closed cell comprising at least about 25% by weight of 1224yd, preferably 1224yd(Z).
- Foam 1D foams in accordance with this paragraph are referred to herein as Foam 1D.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of said cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- gas in the closed cell comprising at least about 50% by weight of 1224yd, preferably 1224yd(Z).
- Foam 1E foams in accordance with this paragraph are referred to herein as Foam 1E.
- a numbered foam e.g., Foam 1
- group of numbered foams that have been defined herein
- such reference means each of such numbered systems, including each system having a number within the group, including any suffixed numbered system.
- reference to Foam 1 includes a separate reference to each of Foams 1A, 1 B, 1C, 1 D and 1 E
- reference to Foams 1 - 2 is understood to include a separate reference to each of Foams 1A, 1 B, 1C, 1 D, 1 E, 2A, 2B, 2C, 2D, 2E and 2F.
- this convention is used throughout the present specification for other defined materials, including Blowing Agents.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate wherein at least 25% of said cells are closed cells;
- Foam 2A foams in accordance with this paragraph are referred to herein as Foam 2A.
- thermoplastic foam comprising: (a) thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% of said cells are closed cells and wherein said thermoplastic polymer contains no tannin moieties or tannin moieties in an amount of less than 20% by weight; and
- Foam 2B For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 2B.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least 50% of said cells are closed cells;
- Foam 2C foams in accordance with this paragraph are referred to herein as Foam 2C.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least 50% of said cells are closed cells;
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least 50% of said cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 2E.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least 50% of said cells are closed cells;
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15% wherein at least about 50% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer;
- Foam 3A foams in accordance with this paragraph are referred to herein as Foam 3A.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has a crystallinity of at least 15% and a molecular weight of from about 25,000 to about 170,000, wherein at least about 25% by volume of the cells are closed cells;
- Foam 3B For the purposes of convenience, foams in accordance with this paragraph are referred to herein as Foam 3B.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15% and a molecular weight of from about 80,000 to about 170,000, wherein at least about 25% by volume of the cells are closed cells;
- Foam 3C foams in accordance with this paragraph are referred to herein as Foam 3C.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 25% and a molecular weight of from about 80,000 to about 170,000, wherein from about 35% by volume to about 90% by volume of the cells are closed cells;
- Foam 3D foams in accordance with this paragraph are referred to herein as Foam 3D.
- the present invention includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate having a crystallinity of from about 35% to about 65% and a molecular weight of from about 80,000 to about 170,000, wherein from about 35% by volume to about 90% by volume of the cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 3E.
- the present invention includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls comprising polyethylene furanoate ;
- foams in accordance with this paragraph are referred to herein as Foam 4A.
- the present invention includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- foams in accordance with this paragraph are referred to herein as Foam 4B.
- the present invention includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic comprises polyethylene furanoate-based polymer having a crystallinity of at least about 15% and a molecular weight of greater than 25,000;
- blowing agent contained in said closed cells said blowing agent comprises 1224yd, preferably 1224yd(Z),.
- foams in accordance with this paragraph are referred to herein as Foam 5A.
- the present invention includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein said thermoplastic comprises polyethylene furanoate-based polymer having a crystallinity of at least about 25% and a molecular weight of from about 25,000 to about 170,000;
- blowing agents contained in said closed cells said blowing agent comprising 1224yd.
- foams in accordance with this paragraph are referred to herein as Foam 5B.
- the present invention includes low-density, closed-cell thermoplastic foam comprising:
- the present invention includes closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate wherein at least about 50% by volume of the cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 6B.
- the present invention includes closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate wherein at least about 75% by volume of the cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 6C.
- the present invention includes closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate wherein at least about 90% by volume of the cells are closed cells;
- foams in accordance with this paragraph are referred to herein as Foam 6D.
- the present invention also provides the foamable compositions, foaming methods and additional foams as described hereinafter.
- Figure 1 is a schematic representation of an extrusion system and process according to one embodiment of the invention and according to the examples herein.
- Trans 1234ze and 1234ze(E) each means trans1 ,3,3,3-tetrafluoropropene.
- Cis1234ze and 1234ze(Z) each means cis1,3,3,3-tetrafluoropropene.
- 1234yf means 2,3,3,3-tetrafluoropropene.
- 1233zd means 1-chloro-3,3,3-trifluoropropene, without limitation as to isomeric form.
- Trans1233zd and 1233zd(E) each means trans1-chloro-3,3,3-trifluoropropene.
- 1224yd means 1-chloro-2,3,3,3-tetrafluoropropane, without limitation as to isomeric form.
- cis1224yd and 1224yd(Z) means cis1-chloro-2,3,3,3-tetrafluoropropane.
- trans1224yd and 1224yd(E) means trans1-chloro-2, 3,3, 3-tetrafluoropropane.
- 1336mzz means 1,1,1 ,4,4,4-hexafluorobutene, without limitation as to isomeric form.
- Trans1336mzz and 1336mzz(E) each means transl ,1 ,1,4,4, 4-hexafluorobutene.
- Cis1336mzz and 1336mzz(Z) each means cis1 , 1 ,1, 4, 4, 4-hexafluorobutene.
- Closed cell foam means that a substantial volume percentage of the cells in the foam are closed, for example, about 20% by volume or more.
- Crystallinity means the degree of crystallinity of a polymer measured by differential scanning calorimetry (DSC) according to ASTM D3418 and ASTM E1356.
- Ethylene furanoate moiety means the following structure:
- FDCA means 2,5-furandicarboxylic acid and has the following structure:
- FDME dimethyl 2,5-furandicarboxylate and has the following structure:
- MEG means monoethylene glycol and has the following structure:
- Moiety as used herein means a distinct repeating unit in a polymer.
- a copolymer having two repeating units A and B present in a 1:1 ratio would have 50 molar % A moieties and 50 molar % of B moieties.
- Moiety as used herein means a moiety that is not ethylene furanoate and not formed from tannin.
- Methylal means dimethoxymethane ((CH3O)2CH2).
- PEF homopolymer means a polymer consisting of ethylene furanoate moieties.
- the PEF homopolymer may include impurity levels of materials that may be present.
- PEF copolymer means a polymer having at least 50% by weight of ethylene furanoate moieties and some amount a moiety other than ethylene furanoate moieties.
- PEF means poly (ethylene furanoate) and encompasses and is intended to reflect a description of PEF homopolymer and PEF coploymer.
- SSP means solid-state polymerization.
- PM DA means pyromellitic dianhydride having the following structure:
- Tannin moiety as used herein means a polymeric repeating unit corresponding to the tannin used to form the polymer, including as disclosed in US Patent No. 9,890,342.
- the present invention relates to foams and foam articles that comprise cell walls that comprise PEF.
- the PEF which forms the cells walls of the foams and foam articles of the present invention can be PEF homopolymer or PEF copolymer.
- PEF homopolymer is a known material that is known to be formed by either:(a) esterification and polycondensation of FDCA with MEG; or (b) transesterification and polycondensation of FDME with MEG as illustrated below for example:
- the foams of the present invention are formed from either PEF homopolymers, PEF copolymers, or a combination/mixture of these.
- the foams may be formed in preferred embodiments from PEF homopolymer in which the polymer has at least 99.5% by weight, or at least 99.9% of by weight, of ethylene furanoate moieties.
- the foams may be formed in preferred embodiments from PEF copolymer in which the polymer, including PEF copolymer that has from about 60% to about 99% by weight of ethylene furanoate moieties, or from about 70% to about 99% by weight of ethylene furanoate moieties, or from about 85% to about 99% by weight of ethylene furanoate moieties, or from about 90% to about 99% by weight of ethylene furanoate moieties or from about 95% to about 99.5% by weight of ethylene furanoate moieties.
- the polymer including PEF copolymer that has from about 60% to about 99% by weight of ethylene furanoate moieties, or from about 70% to about 99% by weight of ethylene furanoate moieties, or from about 85% to about 99% by weight of ethylene furanoate moieties, or from about 90% to about 99% by weight of ethylene furanoate moieties or from about 95% to about 99.5% by weight of ethylene furanoate
- the present invention also includes foams formed from PEF having less than 20% by weight of tannin moieties, or less than 15% by weight of tannin moieties, or less than 10% by weight of tannin moieties, or less than 5% by weght of tannin moieties, or is essentially free of tannin moieties.
- PEF polyethylene glycol
- the foams including each of Foams 1 - 6, are formed from PEF having the ranges of characteristics identified in Table 1 below, which are measured as described in the Examples hereof:
- PEF in general and PEF homopolymer in particular having these properties is achieved using one or more of the synthesis methods described above, in combination with a variety of known supplemental processing techniques, including by treatment with chain extenders, such as PMDA, and/or SSP processing. It is believed that in view of the disclosures contained herein, including the polymer synthesis described in the Examples below, a person skilled in the art will be able to produce PEF polymers within the range of characteristics described in the table above and elsewhere herein.
- chain extenders generally are typically compounds that are at least di-functional with respect to reactive groups which can react with end groups or functional groups in the polyester to extend the length of the polymer chains.
- such a treatment can advantageously increases the average molecular weight of the polyester to improve its melt strength and/or other important properties.
- the degree of chain extension achieved is related, at least in part, to the structure and functionalities of the compounds used.
- Various compounds are useful as chain extenders.
- Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, haloformyl derivatives thereof, or compounds containing multi-functional epoxy (e.g., glycidyl), or oxazoline functional groups.
- Nanocomposite material such as finely dispersed nanoclay may optionally be used for controlling viscosity.
- chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema.
- the amount of chain extender can vary depending on the type and molecular weight of the polyester components.
- the amount of chain extender used to treat the polymer can vary widely, and in preferred embodiments ranges from about 0.1 to about 5 wt. %, or preferably from about 0.1 to about 1.5 wt. %. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.
- Nejib Kasmi Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which is incorporated herein by reference.
- thermoplastic polymers which are especially advantageous for making foamable compositions and foams of the present invention are identified in the following Thermoplastic Polymer Table (Table 2), wherein all numerical values in the table are understood to be preceded by the word “about.”
- thermoplastic polymers identified in the first column in each of rows in the TPP table above and reference to each of these numbers is a reference to a thermoplastic polymer as defined in the corresponding columns of that row.
- Reference to a group of TPPs that have been defined in the table above by reference to a TPP number means separately and individually each such numbered TPP, including each TPP having the indicated number, including any such number that has a suffix. So for example, reference to TPP1 is a separate and independent reference to TPP1A, TPP1 B, TPP1C, TPP1 D and TPP1 E.
- TPP1 - TPP2 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1 D, TTP1 E, TPP2A, TPP2B, TPP2C, TPP1 D and TTP1 E.
- This use convention is used for the Foamable Composition Table and the Foam Table below as well.
- the present invention includes, but is not limited to, applicant’s discovery that a select group of blowing agents are capable of providing foamable PEF foamable compositions and PEF foams having a difficult to achieve a surprising combination of physical properties, including low density as well as good mechanical strength properties.
- blowing agent used in accordance with of the present invention preferably comprises one or more hydrohaloolefins having three or four carbon atoms.
- Blowing Agent 1 a blowing agent in accordance with this paragraph is sometimes referred to herein as Blowing Agent 1.
- the blowing agent used in accordance with of the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz(Z), 1336mzz(E),1233zd and 1224yd (referred to hereinafter for convenience as Blowing Agent 2); or comprises one or more of trans1234ze, 1336mzz(Z), 1336mzz(E), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 3) ; or comprises one or more of trans1234ze, 1336mzz(Z), 1336mzz(E), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 4); or comprises one or more of trans1234ze and 1224yd (referred to hereinafter for convenience as Blowing Agent 5); or comprises 1224yd(Z) (referred to hereinafter for convenience as Blowing Agent 6); ; or comprises 1234yf( referred to hereinafter for convenience as Blowing Agent 7); or comprises 1224yd (
- blowing agent of the present invention including each of Blowing Agents 1 - 9, can include, in addition to each of the above-identified blowing agent(s), co-blowing agent including in one or more of the optional potential co-blowing agents as described below.
- the present foamable compositions, foams, and foaming methods include a blowing agent as described according described herein, wherein the indicated blowing agent (including the compound or group of compound(s) specifically identified in each of Blowing Agent 1 - 9) is present in an amount, based upon the total weight of all blowing agent present, of at least about 50% by weight, or preferably at least about 60% by weight, preferably at least about 70% by weight, or preferably at least about 80% by weight, or preferably at least about 90% by weight, or preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total of all blowing agent components.
- blowing agent used in accordance with of the present invention also preferably consists essentially of one or more of 1234ze, 1234yf, 1336mzz(Z), 1233zd and 1224yd (referred to hereinafter for convenience as Blowing Agent 10); or consists essentially of one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 11); or consists essentially of one or more of trans 1234ze, 1336mzz(Z), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 12); or consists essentially of one or more of trans1234ze and 1224yd (referred to hereinafter for convenience as Blowing Agent 13); or consists essentially of trans1234ze (referred to hereinafter for convenience as Blowing Agent 14); or consists essentially of 1336mzz(Z) (referred to hereinafter for convenience as Blowing Agent 15); or consists essentially of 1336m
- blowing agent of the present invention can include one or more co-blowing agents which are not included in the indicated selection, provided that such co-blowing agent in the amount used does not interfere with or negate the ability to achieve relatively low-density foams as described herein, including each of Foams 1 - 6, and preferably further does not interfere with or negate the ability to achieve foam with mechanical strengths properties as described herein.
- HFCs saturated hydrocarbons or hydrofluorocarbons
- HFC co-blowing agents include, but are not limited to, one or a combination of difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC- 125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC- 227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356) and all isomers of all such HFC's.
- HFC-32 difluoromethane
- HFC-161 fluoroethane
- HFC-152 difluoroethane
- HFC-143 trifluoroethane
- HFC-134
- the present blowing agent compositions also may include in certain preferred embodiments, for example, iso, normal and/or cyclopentane and butane and/or isobutane.
- Other materials such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs such as dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as, for example, ethanol and/or propanol and/or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxy methane and diethoxy methane)), and methyl formate, organic acids (such as
- the blowing agent used in accordance with of the present invention also preferably consists of one or more of 1234ze, 1234yf, 1336mzz(Z) , 1233zd and 1224yd (referred to hereinafter for convenience as Blowing Agent 20); or consists of one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 21); or consists of one or more of trans1234ze, trans1336mzz(Z), trans1233zd and cis1224yd (referred to hereinafter for convenience as Blowing Agent 22); or consists of one or more of trans1234ze and 1224yd (referred to hereinafter for convenience as Blowing Agent 23); or consists of 1224yd(Z) (referred to hereinafter for convenience as Blowing Agent 24); or consists of t1224yd(E) (referred to hereinafter for convenience as Blowing Agent 25).
- the foams of the present invention may generally be formed from a foamable composition of the present invention.
- the foamable compositions of the present invention may be formed by combining a PEF polymer with a blowing agent of the present invention, including each of Blowing Agents 1 - 25.
- Foamable compositions that are included within the present invention, and which provide particular advantage in connection with forming the foams of the present invention, are described in the following Foamable Composition Table (Table 3), in which all numerical values in the table are understood to be preceded by the word “about” and in which the following terms used in the table have the following meanings:
- CBAG1 means co-blowing agent selected from the group consisting of 1234ze(E),1336mzz(E), 1336mzzm(Z), 1233zd(E), 1234yf and combinations of two or more of these.
- CBAG2 means co-blowing agent selected from the group consisting of water, CO2, 01 - C6 hydrocarbons (HCs) HCFCs, 01 - C5 HFCs, C2 - C4 hydrohaloolefins, C1-C5 alcohols, 01- 04 aldehydes, C1-C4 ketones, C1-C4 ethers, C1 - 04 esters, organic acids and combinations of two or more of these.
- HCs hydrocarbons
- C2 - C4 hydrohaloolefins C1-C5 alcohols
- 01- 04 aldehydes 01- 04 aldehydes
- C1-C4 ketones C1-C4 ethers
- C1 - 04 esters organic acids and combinations of two or more of these.
- CCBAG3 means co-blowing agent selected from the group consisting of water, C02, isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-dichloroethylene, ethanol, propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxy methane, diethoxy methane, methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1 ,1- difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1 ,1 ,1 ,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (H
- thermoplastic foam any one or more of a variety of known techniques for forming a thermoplastic foam can be used in view of the disclosures contained herein to form a foam of the present invention, including each of Foams 1 - 6 and each of foams F1 - F6, and all such techniques and all foams formed thereby or within the broad scope of the present invention.
- definition of the foams in the Table below all begin with only the letter F, in contrast to the foams defined by the paragraphs in the summary above, which begin with the capitalized word Foam.
- the forming step involves first introducing into a PEF polymer of the present invention, including each of TPP1 - TPP6, a blowing agent of the present invention, including each of Blowing Agents 1 - 31 , to form a foamable PEF composition comprising PEF and blowing agent.
- a preferred method for forming a foamable PEF composition of the present invention is to plasticize the PEF, preferably comprising heating the PEF to its melt temperature, preferably above its melt temperature, and thereafter exposing the PEF melt to the blowing agent under conditions effective to incorporate (preferably by solubilizing) the desired amount of blowing agent into the polymer melt.
- the foaming methods of the present invention comprising providing a foamable composition of the present invention, including each of FC1 - FC6 and foaming the provided foamable composition.
- the foaming methods of the present invention comprising providing a foamable composition of the present invention, including each of FC1 - FC6, and extruding the provided foamable composition to form a foam of the present invention, including each of Foams 1 - 6 and each of foams F1 - F6.
- Foaming processes of the present invention can include batch, semi-batch, continuous processes, and combinations of two or more of these.
- Batch processes generally involve preparation of at least one portion of the foamable polymer composition, including each of FC1 - FC6, in a storable state and then using that portion of foamable polymer composition at some future point in time to prepare a foam.
- Semi-batch process involves preparing at least a portion of a foamable polymer composition, including each of FC1 - FC6, and intermittently expanding that foamable polymer composition into a foam including each of Foams 1 - 6 and each of foams F1 - F6, all in a single process.
- thermoplastic foams via an accumulating extrusion process.
- the present invention thus includes processes that comprises: 1 ) mixing PEF thermoplastic polymer, including each of TPP1 - TPP6, and a blowing agent of the present invention, including each of Blowing Agents 1 - 31 , under conditions to form a foamable PEF composition; 2) extruding the foamable PEF composition, including each of FC1 - FC6, into a holding zone maintained at a temperature and pressure which does not allow the foamable composition to foam, where the holding zone preferably comprises a die defining an orifice opening into a zone of lower pressure at which the foamable polymer composition, including each of FC1 - FC6, foams and an openable gate closing the die orifice; 3) periodically opening the gate while substantially concurrently applying mechanical pressure by means of a movable ram on the foamable polymer composition, including each of FC1 - FC6, to eject it from the holding zone through the die orifice
- the present invention also can use continuous processes for forming the foam.
- a continuous process involves forming a foamable PEF composition, including each of FC1 - FC6, and then expanding that foamable PEF composition without substantial interruption.
- a foamable PEF composition, including each of FC1 - FC6 may be prepared in an extruder by heating the selected PEF polymer resin, including each of TPP1 - TPP6, to form a PEF melt, incorporating into the PEF melt a blowing agent of the present invention, including each of Blowing Agents 1 - 31 , preferably by solubilizing the blowing agent into the PEF melt, at an initial pressure to form a foamable PEF composition comprising a substantially homogeneous combination of PEF and blowing agent, including each of FC1 - FC6, and then extruding that foamable PEF composition through a die into a zone at a selected foaming pressure and allowing the foamable PEF composition to expand into a foam, including each of Foams 1 - 6 and each
- the foamable PEF composition which comprises the PEF polymer, including each of FC1 - FC6, and the incorporated blowing agent, including each of Blowing Agents 1 - 31 , may be cooled prior to extruding the composition through the die to enhance certain desired properties of the resulting foam, including each of Foams 1 - 6 and each of foams F1 - F6.
- the extrusion apparatus can include a raw material feed hopper 10 for holding the PEF polymer 15 of the present invention, including each of TPP1 - TPP6, and one or more optional components (which may be added with the PEF in the hopper or optionally elsewhere in the process depending on the particular needs of the user).
- the feed materials 15, excluding the blowing agent, can be charged to the hopper and delivered to the screw extruder 10.
- the extruder 20 can include thermocouples (not shown) located at three points along the length thereof and a pressure sensor (not shown) at the discharge end 20A of the extruder.
- a mixer section 30 can be located at the discharge end 20A of the extruder for receiving blowing agent components of the present invention, including each of Blowing Agents 1 - 31 , via one or more metering pumps 40A and 40B and mixing those blowing agents into the PEF melt in the mixer section. Sensors (not shown) can be included for monitoring the temperature and pressure of the mixer section 30.
- the mixer section 30 can then discharge the foamable composition melt of the present invention, including each of FC1 - FC6, into a pair of melt coolers 50 oriented in series, with temperature sensors (not shown) located in each cooler to monitor the melt temperature.
- the melt is then extruded through a die 60, which also had temperature and pressure sensors (not shown) for monitoring the pressure and temperature at the die.
- the die pressure and temperature can be varied, according to the needs of each particular extrusion application to produce a foam 70 of the present invention, including each of including each of Foams 1 - 6 (defined above) and each of foams F1 - F6(defined below).
- the foam can then be carried away from the extrusion equipment by a conveyor belt 80.
- the foamable polymer compositions of the present invention may optionally contain additional additives such as nucleating agents, cellcontrolling agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizing agents, antistatic agents, fire retardants, IR attenuating agents and thermally insulating additives.
- Nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such azodicarbonamide or sodium bicarbonate and citric acid.
- IR attenuating agents and thermally insulating additives can include carbon black, graphite, silicon dioxide, metal flake or powder, among others.
- Flame retardants can include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
- brominated materials such as hexabromocyclodecane and polybrominated biphenyl ether.
- additional optional additives can be introduced into the foam at various times and that various locations in the process according to known techniques, and all such additives and methods of addition or within the broad scope of the present invention.
- the foams of the present invention are formed in a commercial extrusion apparatus and have the properties as indicated in the following Table 4, with the values being measured as described in the Examples hereof:
- the foams of the present invention have wide utility.
- the present foams, including each of Foams 1 - 6 and foams F1 - F6, have unexpected advantage in applications requiring low density and/or good compression and/or tensile and/or shear properties, and/or long-term stability, and/or sustainable sourcing, and/or being made from recycled material and being recyclable.
- the present foams including each of Foams 1 - 6 and each of foams F1 - F6, have unexpected advantage in: wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles); marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors); industrial low weight applications; automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft).
- wind energy applications wind turbine blades (shear webs, shells, cores, and nacelles)
- marine applications hulls, decks, superstructures, bulkheads, stringers, and interiors
- industrial low weight applications automotive and transport applications (interior and exterior of cars, trucks, trains, aircraft, and spacecraft).
- a bio-based polyethylene furanoate homopolymer was prepared by esterification and polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol according to known methods to produce PEF homopolymer, which is then treated according to techniques corresponding to the techniques described in detail in Examples 47, 49 and 51 below, with the chain extender PMDA at 0.6% by weight and then subject to solid state polymerization according to known techniques to produce a PEF homopolymer.
- the PEF polymer was tested and found to have the following characteristics 1 : Molecular Weight - 114,000 Density (g/cc) - 1.43
- the PEF polymer so produced is referred to in these Examples as PEX1.
- Example 1B CLOSED CELL PEF FOAMS FROM PEX1 OVER A RANGE OF RELATIVE DENSITIES AND BLOWING AGENTS
- the present invention includes the advantages formation of PEF foams having a high volume percentage of closed cells over a range of relative foam densities (RFDs) and using a range of blowing agents.
- RFDs relative foam densities
- Molecular weight as determined and referenced herein refers to molecular weight determination by diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR) as per the description contained in "Application of 1H DOSY NMR in Measurement of Polystyrene Molecular Weights/' VNU Journal of Science: Natural Sciences and Technology, Vol. 35, No.
- DOSY NMR diffusion ordered nuclear magnetic resonance spectroscopy
- the polymer/COz blowing agent was maintained in this melt state for about 1 hour and the temperature and pressure of the melt/blowing agent was then reduced over a period of about 5 - 15 minutes to about 190°C and 610 psig (hereinafter referred to for convenience as pre-foaming temperature and pre-foaming pressure, respectively), and then maintained at about this temperature and pressure for a period of about 30 minutes to allow the amount of blowing agent incorporated into the melt under such conditions to reach equilibrium.
- the temperature and pressure in the autoclave were then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water)) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
- the foam thus produced was tested to determine the following properties:
- CM compressive modulus
- TS tensile strength
- TM tensile modulus
- RFD is the density of the foam produced divided by the density of the starting polymer. Density is measured in these Examples using a method which corresponds generally to ASTM D71, except that hexane is used for displacement instead of water.
- the foam made using CO2 under the reported conditions had an RFD of 0.25, that is, a density that was only 25% of the density of the starting polymer. This is a foam density that is too high for many important applications.
- Comparative Example 1 was repeated, except the CO2 blowing agent was replaced in the process with cis1224yd and the process conditions were modified in a manner to produce a foam having an RFD that was within about 15 relative percent of the RFD produced using CO2 in Comparative Example 1 .
- the foam produced was tested to determine various properties, including strength and modulus properties compared to CO2, and was found to be dramatically superior in each of the measured properties, as reported in Table E2 below:
- the foam made using cis1224yd was surprisingly superior to the foam made using CO2 based on each of the physical strength and modulus properties tested.
- the foam made with cis1224yd produced a foam with both tensile and compressive modulus that is twice the value produced using CO2, while at the same time having compressive and tensile strengths that are more than 60% better than CO2. This result is unexpected.
- the polymer/isopentane blowing agent was maintained in this melt state for about 1 hour and the temperature and pressure of the melt/blowing agent was then reduced over a period of about 5 - 15 minutes to about 190°C and 320 psig (hereinafter referred to for convenience as pre-foaming temperature and pre-foaming pressure, respectively), and then maintained at about this temperature and pressure for a period of about 30 minutes to allow the amount of blowing agent incorporated into the melt under such conditions to reach equilibrium.
- the temperature and pressure in the autoclave was then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water) ) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
- the foam thus produced had a relatively acceptable foam structure and was tested to determine relative foam density (RFD) and strength and modulus properties.
- the RFD of the foam was 0.2.
- Comparative Example 2 was repeated, except: (i) the cylcopentane blowing agent was replaced in the process with cis1224yd; and (ii) the process conditions were modified in a manner to produce a foam having an RFD value that was within about 15% of the RFD produced using cyclopentane in Comparative Example 2.
- the foam produced was tested to determine various properties, including strength and modulus properties, and was found to be dramatically superior in each of the measured property, as reported in Table E3 below:
- the foams made using cis1224yd were surprisingly and dramatically superior to the foam made using cyclopentane in terms of all of the physical strength and modulus properties tested.
- the foam made with cis1224yd produced a foam with both tensile and compressive moduli and strength that were more than 2 times better than the values achieved using cyclopentane. This result shows that dramatic and unexpected improvement in physical properties of the foam can be achieved according to the present invention.
- Comparative Example 1 is repeated, except that the conditions and materials are altered as indicted below in Table E5 through Table E9, using blowing agents shown in the table on a molar equivalent (i.e. , within 15%) basis (with all values understood to be “about” the indicated value).
- thermoplastic polymer used to make the foam had characteristics (measured in accordance with same procedures as identified above in Comparative Example 1) within the ranges indicated below: Glass Transition Temperature - 75 - 95°C
- Example 11 The foams made with 1224yd(Z) in Example 11 having a volume of closed cells being 90% or greater are repeated, except that instead of using a blowing agent consisting of 1224yd(Z), a co-blowing as indicated the following table is used to replace portions of the 1224yd(Z) ranging from 5% to 45% on a molar basis, as indicated below in Table E9 - 20(with all values understood to be “about” the indicated value).
- SSP A bio-based polyethylene furanoate homopolymer was prepared by esterification and polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol according to known methods to produce PEF homopolymer, which is then treated according to techniques generally corresponding to the techniques described in detail in Example 1, with the chain extender PM DA at 0.7% by weight and then subject to solid state polymerization according to known techniques to produce a PEF homopolymer having a molecular weight of about 43,500.
- the PEF polymer was tested and found to have the following characteristics: Molecular Weight - 43,500 Density (g/cc) - 1.43 Glass Transition Temperature - 90.4°C Melt Temperature - 219°C Decomposition Temperature - 344°C Crystallinity - 41.9%
- the PEF polymer so produced is referred to in these Examples as PEX20.
- a foam was formed by placing 1 gram of PEX20 in a glass container, which was loaded into a 60 cc autoclave and then dried for under vacuum for six (6) hours at 130°C. The dried polymer was then cooled to room temperature and placed in a glass container inside an autoclave. 38 grams of the 1224yd(Z) blowing agent were then pumped into the autoclave containing the dried polymer, and then the autoclave was heated to bring the polymer to a melt state at a temperature of about 240°C and a pressure above the pre-foaming pressure.
- the polymer/1224yd(Z) blowing agent was maintained in this melt state for about 1 hour and the temperature and pressure of the melt/blowing agent was then reduced over a period of about 5 - 15 minutes to about 190°C and 573 psig (hereinafter referred to for convenience as prefoaming temperature and pre-foaming pressure, respectively), and then maintained at about this temperature and pressure for a period of about 30 minutes to allow the amount of blowing agent incorporated into the melt under such conditions to reach equilibrium.
- the temperature and pressure in the autoclave were then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water)) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
- the foams thus produced were tested and found to have the properties as reported in Table E21 below: TABLE E21
- a bio-based polyethylene furanoate homopolymer was prepared by esterification and polycondensation of 2,5-furandicarboxylic acid with mono ethylene glycol according to known methods to produce PEF homopolymer, which is then treated according to techniques generally corresponding to the techniques described in detail in Example 1, with the chain extender PMDA at 0.7% by weight and then subject to solid state polymerization according to known techniques to produce a PEF homopolymer having a molecular weight of about 160,000.
- the PEF polymer was tested and found to have the following characteristics: Molecular Weight - 160,500 Density (g/cc) - 1.43
- the PEF polymer so produced is referred to in these Examples as PEX22.
- Example 23 PEF FOAM PREPARATION USING PEX22 and cis1224yd as BLOWING AGENT Using a procedure corresponding generally to that described in Comparative Example 1 , a foam was formed by placing 1 gram of PEX22 in a glass container, which was loaded into a 60 cc autoclave and then dried for under vacuum for six (6) hours at 130°C. The dried polymer was then cooled to room temperature and placed in a glass container inside an autoclave.
- the polymer/1224yd(Z) blowing agent was maintained in this melt state for about 1 hour and the temperature and pressure of the melt/blowing agent was then reduced over a period of about 5 - 15 minutes to about 190°C and 573 psig (hereinafter referred to for convenience as prefoaming temperature and pre-foaming pressure, respectively), and then maintained at about this temperature and pressure for a period of about 30 minutes to allow the amount of blowing agent incorporated into the melt under such conditions to reach equilibrium.
- the temperature and pressure in the autoclave were then reduced rapidly (over a period of about 10 seconds for the pressure reduction and about 1 - 10 minutes for the temperature reduction using chilled water)) to ambient conditions (approximately 22°C and 1 atmosphere) and foaming occurred.
- the foams thus produced were tested and found to have the properties as reported in Table E23 below:
- the use of 1224yd(Z) blowing agent with a PEF polymer according to the present invention produced a foam that had a dramatically and unexpectedly improved density compared to the foam made with C020f Comparative Example 1 , even though that foam was made from a polymer with a much higher molecular weight.
- the density of the foam produced with 1224yd(Z) of this example resulted in density value that is, on average, about 3.0 times less than the density of the CO2 blown foam of Comparative Example 1, and at the same time achieve tensile strength and modulus values that are better than the foam blown with CO2.
- thermoplastic foam comprising: (a) thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer; and
- Clause 3 The foam of clause 1 wherein said cell walls consist essentially of polyethylene furanoate having a molecular weight of greater than 25,000.
- Clause 7 The foam of clause 1 wherein said foam has a foam density of less than 0.4 g/cc.
- Clause 8 The foam of clause 1 wherein said foam has a foam density of less than 0.2 g/cc.
- Clause 10 The foam of clause 9 wherein said cell walls consist essentially of polyethylene furanoate having a molecular weight of greater than 100,000.
- Clause 16 The foam of clause 15 wherein said cell walls consist essentially of polyethylene furanoate having a molecular weight of greater than 100,000 and wherein said foam has a relative foam density (RFD) of about 0.2 or less.
- RFD relative foam density
- a wind energy turbine blade and/or nacelle comprising a foam according to anyone of clauses 1 - 16.
- a low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer
- a low-density, thermoplastic foam comprising:
- closed thermoplastic cells comprising cell walls forming closed cells, said cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000;
- a low-density, thermoplastic foam comprising:
- thermoplastic cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein ethylene furanoate moieties are at least 70% by weight of the thermoplastic polymer;
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein ethylene furanoate moieties are at least 90% of the thermoplastic contains ethylene furanoate moieties;
- A includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls wherein at least about 50% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer;
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein ethylene furanoate moieties are at least 50% of the thermoplastic and wherein at least about 50% by volume of the cells are closed cells;
- A includes low-density, thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein ethylene furanoate moieties are at least 50% of the thermoplastic and wherein at least about 75% by volume of the cells are closed cells;
- thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein ethylene furanoate moieties are at least 50% of the thermoplastic and wherein at least about 90% by volume of the cells are closed cells;
- A includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 50,000, wherein ethylene furanoate moieties are at least 50% of the thermoplastic and wherein at least about 50% by volume of the cells are closed cells;
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 50,000, wherein ethylene furanoate moieties are at least 50% of the thermoplastic and wherein at least about 75% by volume of the cells are closed cells;
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 100,000;
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- blowing agent contained in said closed cells and comprising one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms, wherein said foam has a density of less than 0.3 g/cc.
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate that has been treated with a chain extender
- a blowing agent contained said closed cells and comprising one or more HFOs having three or four carbon atoms and/or one or more HFCOs having three or four carbon atoms, wherein said foam has a density of less than 0.25 g/cc.
- a low-density, closed-cell thermoplastic foam comprising: (a) thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer and wherein said thermoplastic comprises polyethylene furanoate-based polymer that has been treated with a chain extender and that has a molecular weight of greater than 25,000; and
- blowing agent contained in said closed cells, said blowing agent comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and 1336mzz(Z).
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 70% by weight of the thermoplastic polymer and wherein said thermoplastic comprises polyethylene furanoate-based polymer that has been treated with a chain extender and that has a molecular weight of greater than 100,000;
- blowing agent contained in said closed cells, said blowing agent comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and 1336mzz(Z).
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein said thermoplastic comprises polyethylene furanoate-based polymer that has been treated with a chain extender and that has having a molecular weight of greater than 100,000;
- blowing agent contained in said closed cells, said blowing agent comprising one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E) and 1336mzz(Z).
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein said thermoplastic comprises has a molecular weight of greater than 100,000; and (b) one or more blowing agents contained in said closed cells, said blowing agent comprising one or more of 1234ze(E), 1336mzz(E) and 1336mzz(Z).
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein said thermoplastic comprises has a molecular weight of greater than 100,000;
- blowing agent contained in said closed cells, said blowing agent consisting essentially of 1234ze(E).
- A includes low-density, closed-cell thermoplastic foam comprising:
- thermoplastic polymer cells comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein said thermoplastic comprises has a molecular weight of greater than 100,000;
- blowing agent contained in said closed cells, said blowing agent consisting essentially of 1336mzz(E).
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cell walls consisting essentially of polyethylene furanoate
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate
- a low-density, closed-cell thermoplastic foam comprising:
- thermoplastic cells comprising cells walls consisting essentially of polyethylene furanoate
- a foamable thermoplastic compositions comprising:
- thermoplastic material consisting essentially of polyethylene furanoate that has been treated with a chain extender and that has a molecular weight of greater than 25,000, wherein at least 50% of the thermoplastic contains ethylene furanoate moieties;
- a foamable thermoplastic compositions comprising:
- thermoplastic material consisting essentially of polyethylene furanoate having a molecular weight of greater than 100,000, wherein at least 50% of the thermoplastic contains ethylene furanoate moieties;
- a foamable thermoplastic compositions comprising:
- thermoplastic material consisting essentially of chain-extended polyethylene furanoate having a molecular weight of greater than 100,000, wherein at least 90% of the thermoplastic contains ethylene furanoate moieties;
- Clause 45 Methods for forming thermoplastic foam comprising foaming a foamable composition of the present invention, including each of Clauses 42 - 44.
- Clause 46 Methods for forming extruded thermoplastic foam comprising extruding a foamable composition of the present invention, including each of Clauses 42 - 44..
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2402636.1A GB2624573A (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
EP22859063.4A EP4388042A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
CN202280060997.2A CN117916296A (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic composition, thermoplastic foam and method of making the same |
CA3228701A CA3228701A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
KR1020247008084A KR20240046757A (en) | 2021-08-16 | 2022-08-16 | Expandable thermoplastic composition, thermoplastic foam and method for producing the same |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US202163233720P | 2021-08-16 | 2021-08-16 | |
US63/233,720 | 2021-08-16 | ||
US202163252110P | 2021-10-04 | 2021-10-04 | |
US63/252,110 | 2021-10-04 | ||
US202163278497P | 2021-11-12 | 2021-11-12 | |
US63/278,497 | 2021-11-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023023088A1 true WO2023023088A1 (en) | 2023-02-23 |
Family
ID=85239689
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2022/040507 WO2023023088A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
PCT/US2022/040504 WO2023023085A1 (en) | 2021-07-20 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
PCT/US2022/040506 WO2023023087A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
PCT/US2022/040505 WO2023023086A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2022/040504 WO2023023085A1 (en) | 2021-07-20 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
PCT/US2022/040506 WO2023023087A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
PCT/US2022/040505 WO2023023086A1 (en) | 2021-08-16 | 2022-08-16 | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
Country Status (5)
Country | Link |
---|---|
EP (4) | EP4388040A1 (en) |
KR (4) | KR20240046755A (en) |
CA (4) | CA3228703A1 (en) |
GB (4) | GB2624573A (en) |
WO (4) | WO2023023088A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023225372A1 (en) * | 2022-05-19 | 2023-11-23 | Honeywell International Inc. | Thermoplastic foams and uses in applications requiring strength and lightweight |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017178500A1 (en) * | 2016-04-13 | 2017-10-19 | Autoneum Management Ag | Process for producing an open cell thermoplastic foam |
WO2017192550A1 (en) * | 2016-05-06 | 2017-11-09 | The Chemours Company Fc, Llc | Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC POLYMER COMPRISING POLYSTYRENE |
WO2019088035A1 (en) * | 2017-11-01 | 2019-05-09 | Agc株式会社 | Method for producing hard synthetic resin foam |
US20200172661A1 (en) * | 2017-06-07 | 2020-06-04 | Sabic Global Technologies B.V. | Foamable thermoplastic polyester copolymer |
WO2021151900A1 (en) * | 2020-01-27 | 2021-08-05 | Kingspan Holdings (Irl) Limited | Phenolic foam and method of manufacture thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9499729B2 (en) * | 2006-06-26 | 2016-11-22 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
US20110144216A1 (en) * | 2009-12-16 | 2011-06-16 | Honeywell International Inc. | Compositions and uses of cis-1,1,1,4,4,4-hexafluoro-2-butene |
CN104619758A (en) * | 2012-07-19 | 2015-05-13 | 霍尼韦尔国际公司 | Blowing agents for extruded polystyrene foam and extruded polystyrene foam and methods of foaming |
US20180327565A1 (en) * | 2017-05-10 | 2018-11-15 | The Chemours Company Fc, Llc | Z-hfo-1336mzz blowing agent blends for foaming thermoplastic polymer comprising polystyrene |
-
2022
- 2022-08-16 GB GB2402636.1A patent/GB2624573A/en active Pending
- 2022-08-16 GB GB2402635.3A patent/GB2624572A/en active Pending
- 2022-08-16 EP EP22859061.8A patent/EP4388040A1/en active Pending
- 2022-08-16 CA CA3228703A patent/CA3228703A1/en active Pending
- 2022-08-16 WO PCT/US2022/040507 patent/WO2023023088A1/en active Application Filing
- 2022-08-16 KR KR1020247008082A patent/KR20240046755A/en unknown
- 2022-08-16 WO PCT/US2022/040504 patent/WO2023023085A1/en active Application Filing
- 2022-08-16 EP EP22859062.6A patent/EP4388041A1/en active Pending
- 2022-08-16 CA CA3228701A patent/CA3228701A1/en active Pending
- 2022-08-16 CA CA3228700A patent/CA3228700A1/en active Pending
- 2022-08-16 EP EP22859063.4A patent/EP4388042A1/en active Pending
- 2022-08-16 WO PCT/US2022/040506 patent/WO2023023087A1/en active Application Filing
- 2022-08-16 WO PCT/US2022/040505 patent/WO2023023086A1/en active Application Filing
- 2022-08-16 KR KR1020247008081A patent/KR20240046754A/en unknown
- 2022-08-16 GB GB2402492.9A patent/GB2624991A/en active Pending
- 2022-08-16 CA CA3228702A patent/CA3228702A1/en active Pending
- 2022-08-16 KR KR1020247008083A patent/KR20240046756A/en unknown
- 2022-08-16 EP EP22859060.0A patent/EP4388039A1/en active Pending
- 2022-08-16 GB GB2402411.9A patent/GB2624565A/en active Pending
- 2022-08-16 KR KR1020247008084A patent/KR20240046757A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017178500A1 (en) * | 2016-04-13 | 2017-10-19 | Autoneum Management Ag | Process for producing an open cell thermoplastic foam |
WO2017192550A1 (en) * | 2016-05-06 | 2017-11-09 | The Chemours Company Fc, Llc | Z-HFO-1336mzz BLOWING AGENT FOR FOAMING THERMOPLASTIC POLYMER COMPRISING POLYSTYRENE |
US20200172661A1 (en) * | 2017-06-07 | 2020-06-04 | Sabic Global Technologies B.V. | Foamable thermoplastic polyester copolymer |
WO2019088035A1 (en) * | 2017-11-01 | 2019-05-09 | Agc株式会社 | Method for producing hard synthetic resin foam |
WO2021151900A1 (en) * | 2020-01-27 | 2021-08-05 | Kingspan Holdings (Irl) Limited | Phenolic foam and method of manufacture thereof |
Also Published As
Publication number | Publication date |
---|---|
GB202402492D0 (en) | 2024-04-10 |
CA3228702A1 (en) | 2023-02-23 |
KR20240046757A (en) | 2024-04-09 |
WO2023023087A1 (en) | 2023-02-23 |
CA3228701A1 (en) | 2023-02-23 |
EP4388041A1 (en) | 2024-06-26 |
KR20240046754A (en) | 2024-04-09 |
GB2624573A (en) | 2024-05-22 |
WO2023023085A1 (en) | 2023-02-23 |
EP4388040A1 (en) | 2024-06-26 |
EP4388042A1 (en) | 2024-06-26 |
EP4388039A1 (en) | 2024-06-26 |
GB2624991A (en) | 2024-06-05 |
GB202402635D0 (en) | 2024-04-10 |
WO2023023086A1 (en) | 2023-02-23 |
GB2624565A (en) | 2024-05-22 |
CA3228703A1 (en) | 2023-02-23 |
KR20240046755A (en) | 2024-04-09 |
KR20240046756A (en) | 2024-04-09 |
GB2624572A (en) | 2024-05-22 |
CA3228700A1 (en) | 2023-02-23 |
GB202402636D0 (en) | 2024-04-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6049810B2 (en) | Process for producing foamable polylactic acid-containing granules | |
US8026291B2 (en) | Expanded and extruded polyolefin foams made with methyl formate-based blowing agents | |
US10138345B2 (en) | Process for the production of expanded polyester foam beads | |
EP2089460B1 (en) | Expanded and extruded biodegradable and reduced emission foams made with methyl formate-based blowing agents | |
JP5684730B2 (en) | Tetrafluoropropene-based blowing agent composition | |
JP2017071780A (en) | Hydrochlorofluoroolefin foaming product | |
WO2023023088A1 (en) | Foamable thermoplastic compositions, thermoplastic foams and methods of making same | |
WO2023164085A1 (en) | Foamable thermoplastic compositions, thermoplastic foams and methods of making same | |
CN117940499A (en) | Foamable thermoplastic composition, thermoplastic foam and method of making the same | |
US20230365774A1 (en) | Foamable thermoplastic compositions, thermoplastic foams and methods of making same | |
JP5110615B2 (en) | Polylactic acid resin foam molding | |
US20230374243A1 (en) | Thermoplastic foams and uses in applications requiring strength and lightweight | |
JP2002293977A (en) | Method for producing preliminarily foamed particle of thermoplastic polyester-based resin | |
WO2023225372A1 (en) | Thermoplastic foams and uses in applications requiring strength and lightweight |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22859063 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2024508370 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 3228701 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 202402636 Country of ref document: GB Kind code of ref document: A Free format text: PCT FILING DATE = 20220816 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280060997.2 Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 20247008084 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022859063 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022859063 Country of ref document: EP Effective date: 20240318 |