WO2024056417A1 - Flame retardant thermoplastic polyurethane composition - Google Patents
Flame retardant thermoplastic polyurethane composition Download PDFInfo
- Publication number
- WO2024056417A1 WO2024056417A1 PCT/EP2023/074111 EP2023074111W WO2024056417A1 WO 2024056417 A1 WO2024056417 A1 WO 2024056417A1 EP 2023074111 W EP2023074111 W EP 2023074111W WO 2024056417 A1 WO2024056417 A1 WO 2024056417A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic polyurethane
- polyurethane composition
- composition according
- ionic liquid
- phosphorus
- Prior art date
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 84
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002608 ionic liquid Substances 0.000 claims abstract description 34
- 150000002148 esters Chemical class 0.000 claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 25
- 239000011574 phosphorus Substances 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- ASONQZPECNCPCA-UHFFFAOYSA-N P(=O)(OC1(C(C=CC=C1)C)C)(OC1(C(C=CC=C1)C)C)OC1=CC(O)=CC=C1 Chemical compound P(=O)(OC1(C(C=CC=C1)C)C)(OC1(C(C=CC=C1)C)C)OC1=CC(O)=CC=C1 ASONQZPECNCPCA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- 125000006714 (C3-C10) heterocyclyl group Chemical group 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000013016 damping Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 claims 1
- 229920005862 polyol Polymers 0.000 description 17
- 150000003077 polyols Chemical class 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- -1 1-ethyl-3-methylimidazolium hexafluorophosphate Chemical compound 0.000 description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920005906 polyester polyol Polymers 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920006347 Elastollan Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical group OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
Definitions
- thermoplastic polyurethane composition Flame retardant thermoplastic polyurethane composition
- the present disclosure relates to a flame retardant thermoplastic polyurethane composition, an article produced from the same, and the use of the article.
- Thermoplastic polyurethane is suitable for many applications, for example wires, cables, pipelines, etc. As TPU per se is combustible, flame retardant TPU is highly desired in scenarios, such as those in aircrafts, electric vehicles, appliances, buildings, and constructions.
- Traditional flame retardant TPUs usually incorporate nitrogen or phosphorus-based flame retardants, such as, melamine cyanurate, ammonium polyphosphate, aluminum hypophosphite, cresyl diphenyl phosphate.
- nitrogen or phosphorus-based flame retardants such as, melamine cyanurate, ammonium polyphosphate, aluminum hypophosphite, cresyl diphenyl phosphate.
- One of the issues with these flame retardants is the poor improvement of flame retardancy.
- a dosage of about 20-30 wt.% of the flame retardants is needed. Such high dosage will impact the compatibility and mechanical strength of the TPU composition. Additionally, high usage of flame retardants also increases the production costs.
- Ionic liquids as flame retardants have been reported. However, they also deteriorate the mechanical properties of the TPU matrix.
- CN111909503A describes a thermoplastic polyurethane composition containing 3 wt.% of tributylmethylammonium tributyl phosphate. Tensile strength decreases by 20% and 30% for polyether and polyester polyurethanes, respectively.
- US20150353832A1 teaches use of phosphinate ionic liquids as flame retardants and as a melt viscosity reduction agent for polymer processing at the same time.
- CN105440652A discloses a flame-retardant thermoplastic polyurehtnae elastomer with an intumescent flame retardant and an ionic liquid.
- the ionic liquid is preferably a dialkylimidazolium ionic liquid, such as 1-ethyl-3-methylimidazolium hexafluorophosphate.
- the intumescent flame retardant includes aluminum hypophosphite, ammonium polyphosphate, aluminum diethylphosphinate, etc.
- thermoplastic polyurethane compositions with low dosage of flame retardants and good mechanical strength are desired.
- thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition, 84-97 wt.% of a thermoplastic polyurethane, and 3-16 wt.% of a flame retardant, wherein the flame retardant comprises an ionic liquid and a phosphorus-containing ester.
- thermoplastic polyurethane composition According to another aspect of the present disclosure, provided is an article produced from the thermoplastic polyurethane composition.
- a further aspect of the present disclosure provides a use of the article.
- the polyurethane composition shows good flame retardancy, and, at the same time, good mechanical properties.
- the articles “a” and “an” refer to one or to more than one (i.e. , to at least one) of the grammatical object of the article.
- an element means one element or more than one element.
- phosphorus-containing esters refer to a class of organophosphorus compounds including organophosphate, organophosphonate, or organophosphinate.
- organophosphates include triethyl phosphate, triphenyl phosphate.
- Organophosphonates are organophosphorus compounds containing C — PO(OH)2, C — PO(OH)(OR) or C — PO(OR)2 groups, wherein R is an alkyl or aryl group.
- Organophosphinates are organophosphorus compounds containing the following group: wherein R is an alkyl or aryl group. Unless otherwise identified, the temperature refers to room temperature and the pressure refers to ambient pressure.
- ionic liquid refers to a salt whose melting point is below 100 °C.
- thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition,
- thermoplastic polyurethane 84-97 wt.% of a thermoplastic polyurethane
- a flame retardant comprises an ionic liquid and a phosphorus-containing ester.
- a sheet of a thickness of 2mm prepared from the thermoplastic polyurethane composition achieves a UL94 VO rating, following procedures of Underwriter's Laboratory Bulletin 94 entitled “Tests for Flammability of Plastic Materials, UL94".
- the flame retardant according to the present disclosure include an ionic liquid and a phosphorus-containing ester. It has been discovered that the simultaneous use of the ionic liquid and the phosphorus-containing ester can enhance the flame retardancy and thus reduce the total dosage of the flame retardants needed. As a result of reduction in dosage of flame retardants, the deterioration of mechanical properties of thermoplastic polyurethane composition could be mitigated.
- the ionic liquid is a phosphorus-based ionic liquid. More preferably, the ionic liquid has a formula of: wherein M + represents a monovalent cation selected from the group consisting of an ammonium, a quaternary ammonium, an imidazolium, a guanidinium, a pyridinium, a pyridazinium, 1 ,2,4-triazolium, a triazine, a sulfonium, a phosphazenium and a phosphonium cation.
- M + represents a phosphonium cation. More preferably, M + represents a quaternary alkylphosphonium or a quaternary arylphosphonium.
- the ionic liquid has a weight percentage of 0.2-2.8 wt.%, preferably 0.3-1.5 wt.%, more preferably 0.5-1.0 wt.%, based on a total weight of the thermoplastic polyurethane composition.
- the phosphorus-containing ester includes one or more organophosphate, organophosphonate, organophosphinate.
- Phosphorus-containing ester preferably includes one or more selected from trialkyl phosphates, triaryl phosphates, halogenated phosphates, and organophosphonates.
- phosphorus-containing ester includes one or more selected from resorcinol bis(diphenylphosphate) (shortened as “RDP”), bisphenol A bis(diphenyl phosphate) (shortened as “BDP”), cresyl diphenyl phosphate (shortened as “CDP”), monomeric resorcinol dixylenyl phosphate, polymeric resorcinol dixylenyl phosphate, trixylenyl phosphate, triethyl phosphate (TEP), tricresyl phosphate, triphenyl phosphate, tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP), dimethyl methylphosphonate (DMMP), and dimethyl propane phosphonate (DMPP).
- RDP resorcinol bis(diphenylphosphate)
- BDP bisphenol A bis(diphenyl phosphate)
- the phosphorus-containing ester has a weight percentage of 1-18 wt.%, more preferably 2-15 wt.%, still more preferably 3-10 wt.%, based on a total weight of the thermoplastic polyurethane composition.
- the ionic liquid and the phosphorus-containing ester preferably are in a weight ratio of 1 : 100- 1 :0.7, preferably 1 :50-1 :2, more preferably 1 :20-1 :5. Under the preferred weight ratio, the overall dosage of the two kinds of flame retardants can be reduced, while the mechanical strength and other properties can be maintained or even enhanced.
- halogenated compounds for example, halogenated polyols, as well as solids, such as diethyl aluminum hypophosphite, aluminum hypophosphite, aluminum trihydroxide, ammonium polyphosphate (APP), red phosphorus, expanded graphite and melamine are suitable as an auxiliary flame retardant.
- the flame retardant may be added into the thermoplastic polyurethane during or after the synthesis in liquid state, masterbatch pellets, or powders if any powdery flame retardant is used as auxiliary flame retardant, via an extruder, a mixer, a miller, or the like.
- the ionic liquid and the phosphorus-containing ester may be added into thermoplastic polyurethane composition simultaneously or separately.
- the ionic liquid may be pre-mixed with the phosphorus-containing ester to form a mixture of flame retardants.
- thermoplastic polyurethane a thermoplastic polyurethane is needed, which may be prepared beforehand, as in form of pellets, or in-situ synthesized.
- the polyurethane may be synthesized by reacting a polyol component and an isocyanate component.
- the polyol component comprises, a polyether polyol, a polyester polyol or a mixture thereof; and one or more chain extenders.
- the isocyanate component may include one or more selected from monomeric, oligomeric, or polymeric isocyanates, prepolymers of isocyanates with active hydrogen containing compounds which are end-capped with isocyanate groups, or polymerized alkyl or aryl isocyanates.
- thermoplastic polyurethane has a weight average molecular weight in the range from 50,000 to 500,000 Da.
- thermoplastic polyurethane composition has a hardness of Shore 40 A to Shore 80 D, preferably Shore 50 A to Shore 98 A, as determined in accordance with DIN ISO 48- 4.
- the polyol component includes a polyether polyol, a polyester polyol or a mixture thereof and one or more chain extender.
- Polyether polyols and polyester polyols are collectively known as polyols.
- Polyol refers to a polyhydroxy compound.
- polyhydroxy compounds having a functionality of 1.9 to 2.1 , and a hydroxyl number of 30 to 200 mg KOH/g are examples of higher molecular weight compounds having at least two reactive hydrogen atoms.
- Suitable polyester polyols can be produced, for example, from organic dicarboxylic acids with 2 to 12 carbons, preferably aliphatic dicarboxylic acids with 4 to 6 carbons, and multivalent alcohols, preferably diols, with 2 to 12 carbons, preferably 2 to 6 carbons.
- dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
- the dicarboxylic acids can be used individually or in mixtures.
- dicarboxylic acid derivatives may also be used such as dicarboxylic acid mono- or di-esters of alcohols with 1 to 4 carbons, or dicarboxylic acid anhydrides.
- Dicarboxylic acid mixtures of succinic acid, glutaric acid and adipic acid in quantity ratios of 20-35:35-50:20-32 parts by weight are preferred, especially adipic acid.
- divalent and multivalent alcohols especially diols
- diols examples include ethanediol, diethylene glycol, 1 ,2- and 1 ,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10- decanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, glycerin, and trimethylolpropane.
- Glycol diethylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, or mixtures of at least two of these diols are preferred, especially ethanediol, 1 ,4-butanediol, and 1 ,6-hexanediol.
- the polyester polyols can be produced by polycondensation of organic polycarboxylic acids, e.g., aromatic or preferably aliphatic polycarboxylic acids and/or derivatives thereof and multivalent alcohols in the presence of catalysts or preferably in the presence of esterification catalysts, preferably in an atmosphere of inert gases, e.g., nitrogen, carbon dioxide, helium, argon, etc., in the melt at temperatures of 150°C to 250°C, preferably 180°C to 220°C, optionally under reduced pressure, up to the desired polymerization degree, which is preferably less than 20, especially less than 15.
- organic polycarboxylic acids e.g., aromatic or preferably aliphatic polycarboxylic acids and/or derivatives thereof and multivalent alcohols
- catalysts or preferably in the presence of esterification catalysts preferably in an atmosphere of inert gases, e.g., nitrogen, carbon dioxide, helium, argon, etc., in the melt at temperatures of 150
- the esterification mixture is subjected to polycondensation at the temperatures mentioned above up to an acid value of less than 1 mg KOH/g, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar.
- suitable esterification catalysts include iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin catalysts in the form of metals, metal oxides or metal salts.
- the polycondensation may also be per formed in liquid phase in the presence of diluents and/or entraining agents such as benzene, toluene, xylene, or chlorobenzene for azeotropic distillation of the water of condensation.
- the organic polycarboxylic acids and/or derivatives thereof and multi valent alcohols are preferably polycondensed in a mole ratio of 1 :1-1.8, preferably 1 :1.05-1.2.
- the resulting polyester polyols preferably have a functionality of 1.9 to 2.1 , and a hydroxyl number of 30 to 200 mg KOH/g.
- Polyether polyols which can be obtained by known methods, may also be used as the polyhydroxy compounds.
- polyether polyols can be produced by anionic polymerization with alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one initiator molecule containing 2 to 8, preferably 3 to 8, reactive hydrogens or by cationic polymerization with Lewis acids such as antimony pentachloride, boron trifluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides with 2 to 4 carbons in the alkylene radical.
- alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate
- Lewis acids such as antimony pentachloride, boro
- Suitable cyclic ethers and alkylene oxides include, for example, tetra hydrofuran, 1 ,3- propylene oxide, 1 ,2- and 2,3-butylene oxide, styrene oxide, and preferably ethylene oxide and
- alkylene cyclic ethers and oxides may be used individually, in alternation, one after the other or as a mixture.
- suitable initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N-, and N,N'-dialkyl substituted diamines with 1 to 4 carbons in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1 ,3-propylenediamine, 1 ,3- and 1 ,4-butylenediamine,
- Suitable initiator molecules also include alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl ethanolamine, N-methyl- and N-ethyl diethanolamine and triethanolamine plus ammonia.
- Divalent alcohols are preferred such as ethanediol, 1 ,2-propanediol and 1 ,3-propanediol, diethylene glycol, dipropylene glycol, 1 ,4-butanediol, and 1 ,6-hexanediol.
- the polyether polyols have a functionality of preferably 1.9 to 2.1 and have a hydroxyl number of 30 to 200 mg KOH/g.
- the polyether polyols may be used either individually or in the form of mixtures. Furthermore, they can be mixed with the polyester polyols as well as the polycarbonates, and/or polycaprolactone.
- Suitable hydroxyl group-containing polycarbonates include those of the known type such as those obtained by reaction of diols, e.g., 1 ,3-propanediol, 1 ,4-butanediol, and/or 1 ,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol and diaryl carbonates, e.g., diphenyl carbonate, or phosgene.
- the thermoplastic polyurethane is prepared using chain extenders.
- Suitable chain extenders include preferably diols. Typical examples are aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 14, more preferably 4 to 10 carbon atoms such as ethylene glycol, 1 ,3-propanediol, 1 ,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, and preferably 1 ,4-butanediol, 1 ,6-hexanediol, and bis(2-hydroxyethyl)hydroquinone.
- thermoplastic polyurethane composition examples include antioxidants, UV stabilizers, lubricants, matting agents, nucleating agents, plasticizers, catalysts, crosslinkers, fillers, dyes, pigments, hydrolysis preventing agents, fungistatic and bacteriostatic agents.
- antioxidants UV stabilizers
- lubricants matting agents
- nucleating agents nucleating agents
- plasticizers plasticizers
- catalysts crosslinkers
- fillers dyes, pigments
- dyes pigments
- hydrolysis preventing agents fungistatic and bacteriostatic agents
- fungistatic and bacteriostatic agents examples include antioxidants, UV stabilizers, lubricants, matting agents, nucleating agents, plasticizers, catalysts, crosslinkers, fillers, dyes, pigments, hydrolysis preventing agents, fungistatic and bacteriostatic agents.
- the kinds and/or dosage of the additives and auxiliaries may be determined according to the specific application where the thermoplastic polyurethane composition is used.
- the isocyanate component in the present disclosure comprises one or more selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates.
- the isocyanate component may include alkylene diisocyanates with 4 to 12 carbons in the alkylene radical such as 1 ,12-dodecane diisocyanate, 2-ethyl-1 ,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1 ,4-tetramethylene diisocyanate and preferably 1 ,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates such as 1 ,3- and 1 ,4- cyclohexane diisocyanate as well as any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate), 2,4- and
- thermoplastic polyurethane Preparation of thermoplastic polyurethane has been described elsewhere, but basically involves reaction of polyol and a chain extender with an isocyanate optionally in the presence of a catalyst.
- thermoplastic polyurethane can be carried out by known methods, either batchwise or continuously, for example using reaction extruders or by the belt process by the one-shot process or the prepolymer process, preferably by the one-shot process.
- thermoplastic polyurethane composition may be processed by conventional ways including injection molding, compression molding, extrusion, co-extrusion, thermoforming cast, sintering, vacuum molding, extrusion, co-extrusion, fused deposition modelling, fused filament fabrication, selective laser sintering, selective laser melting, powder bed fusion, sheet lamination, material extrusion, etc.
- thermoplastic polyurethane composition may be powder, flakes, rods, sheets, or blocks, or alternatively in the form of pellets or granules through e.g., strand cutting or underwater cutting.
- thermoplastic polyurethane composition Various articles may be produced from the thermoplastic polyurethane composition according to the present disclosure.
- the articles include, inter alia, artificial leathers, films, sheets, moldings, fibers, trim in automobiles, tubes, hoses, profiles, pipelines, cable connectors, towing cables, cable sheathing, wires, optical components, electronic components, electrical components, seals, nonwovens, belts or damping elements.
- These articles may find applications in an electric vehicle, or a charging device for electric vehicles, a home appliance, house or office furniture, a construction, an optical device, an electronic device, an electrical device, etc.
- Elastollan® 1190A a polyether based aromatic TPU from BASF Polyurethanes GmbH, tensile strength, 50 MPa; tear strength (angle), 89 kN/m; abrasion loss, 40 mm 3 .
- CDP and RDP from Zhejiang Wansheng Co., Ltd.
- IL 1 an ionic liquid based on quaternary phosphonium cation and organophosphate anion, used as flame retardant.
- Butanediol from BASF, used as chain extender for synthesizing thermoplastic polyurethane of examples in Table 3.
- Lupranate® MS mainly 4,4’-MDI, from BASF, used as isocyanate for synthesizing thermoplastic polyurethane of examples in Table 3.
- Polystyrene-based matting agent Polystyrene-based matting agent.
- Antioxidant Irganox® 1010 a sterically hindered phenol from BASF.
- thermoplastic polyurethane composition To prepare flame-retardant thermoplastic polyurethane composition, the two flame retardants were added into the thermoplastic polyurethane. The ionic liquid and the phosphorus-containing ester were added into the thermoplastic polyurethane separately, then they were dispersed evenly. The mixture was heated under 80 °C for several hours until the liquids were evenly dissolved into the matrix of thermoplastic polyurethane.
- the resultant flame-retardant thermoplastic polyurethane composition was shaped into testing sheets with a thickness of 2 mm via injection molding for mechanical performance and flame-retardancy testing.
- Table 2 shows examples with a UL94 V0 level of flame retardancy, while Table 3 shows examples with a UL94 V2 level.
- TPU compositions with both ionic liquid and phosphorus- containing ester as co-flame retardant can achieve the same level of flame-retardancy under a much lower dosage.
- the TPU composition with both ionic liquid and phosphorus-containing ester exhibits improvements with regards to mechanical performances especially tear strength and abrasion loss. Abrasion loss and tear strength important for products such as cable sheathing, wire, hose, pipeline, belt, etc.
- the weight percentage of ionic liquid is preferably 0.2-2.8 wt.%, 0.3-1.5 wt.%, more preferably 0.5-1.0 wt.%, based on the total weight of the thermoplastic polyurethane composition.
- the flame-retardant thermoplastic polyurethane with ionic liquid and phosphorus- containing ester deteriorates less in tensile strength, tear strength and abrasion loss.
- TPUs in Table 3 were synthesized via an extruder.
- the isocyanate index calculated as the ratio of the number of isocyanate groups in polyisocyanate to the total number of hydroxyl groups in chain extender and polyol was about 1.
- the flame retardants, matting agent, and antioxidant were added to the thermoplastic polyurethane during its synthesis.
- thermoplastic polyurethane sample with ionic liquid and phosphorus-containing ester outperforms those samples containing only phosphorus-containing ester as flame-retardant in terms of mechanical strength, elongation at break, and abrasion loss.
Abstract
Disclosed is a thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition, 84-97 wt.% of a thermoplastic polyurethane, and 3-16 wt.% of a flame retardant, wherein the flame retardant comprises an ionic liquid and a phosphorus-containing ester. Also provided are an article produced from the thermoplastic polyurethane composition, and its use.
Description
Flame retardant thermoplastic polyurethane composition
Technical Field
The present disclosure relates to a flame retardant thermoplastic polyurethane composition, an article produced from the same, and the use of the article.
Background
Thermoplastic polyurethane (TPU) is suitable for many applications, for example wires, cables, pipelines, etc. As TPU per se is combustible, flame retardant TPU is highly desired in scenarios, such as those in aircrafts, electric vehicles, appliances, buildings, and constructions.
Traditional flame retardant TPUs usually incorporate nitrogen or phosphorus-based flame retardants, such as, melamine cyanurate, ammonium polyphosphate, aluminum hypophosphite, cresyl diphenyl phosphate. One of the issues with these flame retardants is the poor improvement of flame retardancy. To reach UL 94 VO rating, a dosage of about 20-30 wt.% of the flame retardants is needed. Such high dosage will impact the compatibility and mechanical strength of the TPU composition. Additionally, high usage of flame retardants also increases the production costs.
Ionic liquids as flame retardants have been reported. However, they also deteriorate the mechanical properties of the TPU matrix.
CN111909503A describes a thermoplastic polyurethane composition containing 3 wt.% of tributylmethylammonium tributyl phosphate. Tensile strength decreases by 20% and 30% for polyether and polyester polyurethanes, respectively.
US20150353832A1 teaches use of phosphinate ionic liquids as flame retardants and as a melt viscosity reduction agent for polymer processing at the same time.
CN105440652A discloses a flame-retardant thermoplastic polyurehtnae elastomer with an intumescent flame retardant and an ionic liquid. The ionic liquid is preferably a dialkylimidazolium ionic liquid, such as 1-ethyl-3-methylimidazolium hexafluorophosphate. The intumescent flame retardant includes aluminum hypophosphite, ammonium polyphosphate, aluminum diethylphosphinate, etc.
Still, flame-retardant thermoplastic polyurethane compositions with low dosage of flame retardants and good mechanical strength are desired.
Summary
An objective of the present disclosure is to overcome the problems of the prior art discussed above and to provide a flame-retardant thermoplastic polyurethane composition that requires low addition of flame retardants while maintaining physical properties such as tensile strength, abrasion loss, elongation at break, etc.
Surprisingly, it has been found by the inventors that the above object can be achieved by a thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition, 84-97 wt.% of a thermoplastic polyurethane, and 3-16 wt.% of a flame retardant, wherein the flame retardant comprises an ionic liquid and a phosphorus-containing ester.
According to another aspect of the present disclosure, provided is an article produced from the thermoplastic polyurethane composition.
A further aspect of the present disclosure provides a use of the article.
It has been surprisingly found in this application that, by incorporating the phosphorus- containing ester and the ionic liquid in the thermoplastic polyurethane composition, the polyurethane composition shows good flame retardancy, and, at the same time, good mechanical properties.
Detailed description
Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which the present disclosure belongs. As used herein, the following terms have the meanings ascribed to them below, unless specified otherwise.
As used herein, the articles "a" and "an" refer to one or to more than one (i.e. , to at least one) of the grammatical object of the article. By way of example, "an element" means one element or more than one element.
Unless otherwise identified, all percentages (%) are “percent by weight".
Here, phosphorus-containing esters refer to a class of organophosphorus compounds including organophosphate, organophosphonate, or organophosphinate.
Organophosphates are a class of organophosphorus compounds with the general structure O=P(OH)2(OR), O=P(OH)(OR)2, O=P(OR)S, wherein R is an alkyl or aryl group, a central phosphate molecule with alkyl or aromatic substituents. Exemplary organophosphates include triethyl phosphate, triphenyl phosphate.
Organophosphonates are organophosphorus compounds containing C — PO(OH)2, C — PO(OH)(OR) or C — PO(OR)2 groups, wherein R is an alkyl or aryl group.
Organophosphinates are organophosphorus compounds containing the following group:
wherein R is an alkyl or aryl group.
Unless otherwise identified, the temperature refers to room temperature and the pressure refers to ambient pressure.
Unless otherwise identified, the term ionic liquid refers to a salt whose melting point is below 100 °C.
According to the present disclosure, provided is a thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition,
84-97 wt.% of a thermoplastic polyurethane, and
3-16 wt.% of a flame retardant, wherein the flame retardant comprises an ionic liquid and a phosphorus-containing ester.
Preferably, a sheet of a thickness of 2mm prepared from the thermoplastic polyurethane composition achieves a UL94 VO rating, following procedures of Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL94".
Flame retardants
The flame retardant according to the present disclosure include an ionic liquid and a phosphorus-containing ester. It has been discovered that the simultaneous use of the ionic liquid and the phosphorus-containing ester can enhance the flame retardancy and thus reduce the total dosage of the flame retardants needed. As a result of reduction in dosage of flame retardants, the deterioration of mechanical properties of thermoplastic polyurethane composition could be mitigated.
Preferably, the ionic liquid is a phosphorus-based ionic liquid. More preferably, the ionic liquid has a formula of:
wherein M+ represents a monovalent cation selected from the group consisting of an ammonium, a quaternary ammonium, an imidazolium, a guanidinium, a pyridinium, a pyridazinium, 1 ,2,4-triazolium, a triazine, a sulfonium, a phosphazenium and a phosphonium cation. Preferably, M+ represents a phosphonium cation. More preferably, M+ represents a quaternary alkylphosphonium or a quaternary arylphosphonium.
R1 and R2 are each independently selected from hydrogen, hydroxy, C1-C18 alkyl, aryl, CICIS alkoxyl, aryl, (C3-C10) heterocyclyl, (C3-C10)cycloalkyl, (C3-C10)heterocyclyl (C1-C8)alkyl, aryl (C1-C8)alkyl, heteroaryl and heteroaryl (C1-C8)alkyl group, each of which is unsubstituted or substituted with one or two halogen atoms, — NO2, — CF3, — OCF3, — OCH3, — CO2H, — NH2, — OH, — SH, — NHCH3, — N(CH3)2, — CN, — SCH3, — SO3H, — CH=CH— CH2— CH=CH2, — P((C1- C5) alkyl)2, and — P(O)(OEt)2, or mixtures of the substituents.
Preferably, the ionic liquid has a weight percentage of 0.2-2.8 wt.%, preferably 0.3-1.5 wt.%, more preferably 0.5-1.0 wt.%, based on a total weight of the thermoplastic polyurethane composition.
The phosphorus-containing ester includes one or more organophosphate, organophosphonate, organophosphinate. Phosphorus-containing ester preferably includes one or more selected from trialkyl phosphates, triaryl phosphates, halogenated phosphates, and organophosphonates. More preferably, phosphorus-containing ester includes one or more selected from resorcinol bis(diphenylphosphate) (shortened as “RDP”), bisphenol A bis(diphenyl phosphate) (shortened as “BDP”), cresyl diphenyl phosphate (shortened as “CDP”), monomeric resorcinol dixylenyl phosphate, polymeric resorcinol dixylenyl phosphate, trixylenyl phosphate, triethyl phosphate (TEP), tricresyl phosphate, triphenyl phosphate, tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP), dimethyl methylphosphonate (DMMP), and dimethyl propane phosphonate (DMPP).
Preferably, the phosphorus-containing ester has a weight percentage of 1-18 wt.%, more preferably 2-15 wt.%, still more preferably 3-10 wt.%, based on a total weight of the thermoplastic polyurethane composition.
The ionic liquid and the phosphorus-containing ester preferably are in a weight ratio of 1 : 100- 1 :0.7, preferably 1 :50-1 :2, more preferably 1 :20-1 :5. Under the preferred weight ratio, the overall dosage of the two kinds of flame retardants can be reduced, while the mechanical strength and other properties can be maintained or even enhanced.
Besides the ionic liquid and the phosphorus-containing ester, halogenated compounds, for example, halogenated polyols, as well as solids, such as diethyl aluminum hypophosphite, aluminum hypophosphite, aluminum trihydroxide, ammonium polyphosphate (APP), red phosphorus, expanded graphite and melamine are suitable as an auxiliary flame retardant.
The flame retardant may be added into the thermoplastic polyurethane during or after the synthesis in liquid state, masterbatch pellets, or powders if any powdery flame retardant is used as auxiliary flame retardant, via an extruder, a mixer, a miller, or the like.
The ionic liquid and the phosphorus-containing ester may be added into thermoplastic polyurethane composition simultaneously or separately. The ionic liquid may be pre-mixed with the phosphorus-containing ester to form a mixture of flame retardants.
Thermoplastic polyurethane
To prepare the thermoplastic polyurethane composition, a thermoplastic polyurethane is needed, which may be prepared beforehand, as in form of pellets, or in-situ synthesized. For example, the polyurethane may be synthesized by reacting a polyol component and an isocyanate component. In various embodiments, the polyol component comprises, a polyether polyol, a polyester polyol or a mixture thereof; and one or more chain extenders.
The isocyanate component may include one or more selected from monomeric, oligomeric, or polymeric isocyanates, prepolymers of isocyanates with active hydrogen containing compounds which are end-capped with isocyanate groups, or polymerized alkyl or aryl isocyanates.
Preferably, the thermoplastic polyurethane has a weight average molecular weight in the range from 50,000 to 500,000 Da.
Preferably, the thermoplastic polyurethane composition has a hardness of Shore 40 A to Shore 80 D, preferably Shore 50 A to Shore 98 A, as determined in accordance with DIN ISO 48- 4.
Polyol component
The polyol component includes a polyether polyol, a polyester polyol or a mixture thereof and one or more chain extender.
Polyether polyols and polyester polyols are collectively known as polyols. Polyol refers to a polyhydroxy compound. Preferably, polyhydroxy compounds having a functionality of 1.9 to 2.1 , and a hydroxyl number of 30 to 200 mg KOH/g are examples of higher molecular weight compounds having at least two reactive hydrogen atoms.
Suitable polyester polyols can be produced, for example, from organic dicarboxylic acids with 2 to 12 carbons, preferably aliphatic dicarboxylic acids with 4 to 6 carbons, and multivalent alcohols, preferably diols, with 2 to 12 carbons, preferably 2 to 6 carbons. Examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. The dicarboxylic acids can be used individually or in mixtures. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives may also be used such as dicarboxylic acid mono- or di-esters of alcohols with 1 to 4 carbons, or dicarboxylic acid anhydrides. Dicarboxylic acid mixtures of succinic acid, glutaric acid and adipic acid in quantity ratios of 20-35:35-50:20-32 parts by weight are preferred, especially adipic acid. Examples of divalent and multivalent alcohols, especially diols, include ethanediol, diethylene glycol, 1 ,2- and 1 ,3-propanediol, dipropylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10- decanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, glycerin, and trimethylolpropane. Glycol, diethylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, or mixtures of at least two of these diols are preferred, especially ethanediol, 1 ,4-butanediol, and 1 ,6-hexanediol.
The polyester polyols can be produced by polycondensation of organic polycarboxylic acids, e.g., aromatic or preferably aliphatic polycarboxylic acids and/or derivatives thereof and multivalent alcohols in the presence of catalysts or preferably in the presence of esterification catalysts, preferably in an atmosphere of inert gases, e.g., nitrogen, carbon dioxide, helium, argon, etc., in the melt at temperatures of 150°C to 250°C, preferably 180°C to 220°C, optionally under reduced pressure, up to the desired polymerization degree, which is preferably less than 20,
especially less than 15. In a preferred embodiment, the esterification mixture is subjected to polycondensation at the temperatures mentioned above up to an acid value of less than 1 mg KOH/g, under normal pressure and then under a pressure of less than 500 mbar, preferably 50 to 150 mbar. Examples of suitable esterification catalysts include iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation may also be per formed in liquid phase in the presence of diluents and/or entraining agents such as benzene, toluene, xylene, or chlorobenzene for azeotropic distillation of the water of condensation.
To produce the polyester polyols, the organic polycarboxylic acids and/or derivatives thereof and multi valent alcohols are preferably polycondensed in a mole ratio of 1 :1-1.8, preferably 1 :1.05-1.2.
The resulting polyester polyols preferably have a functionality of 1.9 to 2.1 , and a hydroxyl number of 30 to 200 mg KOH/g.
Polyether polyols, which can be obtained by known methods, may also be used as the polyhydroxy compounds. For example, polyether polyols can be produced by anionic polymerization with alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one initiator molecule containing 2 to 8, preferably 3 to 8, reactive hydrogens or by cationic polymerization with Lewis acids such as antimony pentachloride, boron trifluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides with 2 to 4 carbons in the alkylene radical.
Suitable cyclic ethers and alkylene oxides include, for example, tetra hydrofuran, 1 ,3- propylene oxide, 1 ,2- and 2,3-butylene oxide, styrene oxide, and preferably ethylene oxide and
1.2-propylene oxide. The alkylene cyclic ethers and oxides may be used individually, in alternation, one after the other or as a mixture. Examples of suitable initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N-, and N,N'-dialkyl substituted diamines with 1 to 4 carbons in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1 ,3-propylenediamine, 1 ,3- and 1 ,4-butylenediamine,
1.2-, 1 ,3-, 1 ,4-, 1 ,5-, and 1 ,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6- toluenediamine and 4,4'-, 2,4'-, and 2,2'-diaminodiphenylmethane.
Suitable initiator molecules also include alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl ethanolamine, N-methyl- and N-ethyl diethanolamine and triethanolamine plus ammonia.
Divalent alcohols are preferred such as ethanediol, 1 ,2-propanediol and 1 ,3-propanediol, diethylene glycol, dipropylene glycol, 1 ,4-butanediol, and 1 ,6-hexanediol.
The polyether polyols have a functionality of preferably 1.9 to 2.1 and have a hydroxyl number of 30 to 200 mg KOH/g.
Like the polyester polyols, the polyether polyols may be used either individually or in the form of mixtures. Furthermore, they can be mixed with the polyester polyols as well as the polycarbonates, and/or polycaprolactone.
Suitable hydroxyl group-containing polycarbonates include those of the known type such as those obtained by reaction of diols, e.g., 1 ,3-propanediol, 1 ,4-butanediol, and/or 1 ,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol and diaryl carbonates, e.g., diphenyl carbonate, or phosgene.
Chain extenders
The thermoplastic polyurethane is prepared using chain extenders. Suitable chain extenders include preferably diols. Typical examples are aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 14, more preferably 4 to 10 carbon atoms such as ethylene glycol, 1 ,3-propanediol, 1 ,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol, and preferably 1 ,4-butanediol, 1 ,6-hexanediol, and bis(2-hydroxyethyl)hydroquinone.
Other additives and auxiliaries
Optionally other additives and/or auxiliaries may be incorporated into the thermoplastic polyurethane composition. Examples include antioxidants, UV stabilizers, lubricants, matting agents, nucleating agents, plasticizers, catalysts, crosslinkers, fillers, dyes, pigments, hydrolysis preventing agents, fungistatic and bacteriostatic agents. The kinds and/or dosage of the additives and auxiliaries may be determined according to the specific application where the thermoplastic polyurethane composition is used.
Isocyanate component
The isocyanate component in the present disclosure comprises one or more selected from the group consisting of aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. For example, the isocyanate component may include alkylene diisocyanates with 4 to 12 carbons in the alkylene radical such as 1 ,12-dodecane diisocyanate, 2-ethyl-1 ,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1 ,4-tetramethylene diisocyanate and preferably 1 ,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates such as 1 ,3- and 1 ,4- cyclohexane diisocyanate as well as any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate), 2,4- and 2,6-hexahydrotoluene diisocyanate as well as the corresponding isomeric mixtures, 4,4', 2,2'-, and 2,4'- dicyclohexylmethane diisocyanate as well as the corresponding isomeric mixtures and preferably aromatic diisocyanates and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomeric mixtures 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate and the corresponding isomeric mixtures, mixtures of 4,4'- and 2,4'-diphenylmethane diisocyanates, as
well as mixtures of polymeric M DI and toluene diisocyanates. The organic di- and polyisocyanates can be used individually or in the form of mixtures.
Preparation
Preparation of thermoplastic polyurethane has been described elsewhere, but basically involves reaction of polyol and a chain extender with an isocyanate optionally in the presence of a catalyst.
The preparation of the thermoplastic polyurethane can be carried out by known methods, either batchwise or continuously, for example using reaction extruders or by the belt process by the one-shot process or the prepolymer process, preferably by the one-shot process.
Processing
The thermoplastic polyurethane composition may be processed by conventional ways including injection molding, compression molding, extrusion, co-extrusion, thermoforming cast, sintering, vacuum molding, extrusion, co-extrusion, fused deposition modelling, fused filament fabrication, selective laser sintering, selective laser melting, powder bed fusion, sheet lamination, material extrusion, etc.
The thermoplastic polyurethane composition may be powder, flakes, rods, sheets, or blocks, or alternatively in the form of pellets or granules through e.g., strand cutting or underwater cutting.
Applications
Various articles may be produced from the thermoplastic polyurethane composition according to the present disclosure. The articles include, inter alia, artificial leathers, films, sheets, moldings, fibers, trim in automobiles, tubes, hoses, profiles, pipelines, cable connectors, towing cables, cable sheathing, wires, optical components, electronic components, electrical components, seals, nonwovens, belts or damping elements.
These articles may find applications in an electric vehicle, or a charging device for electric vehicles, a home appliance, house or office furniture, a construction, an optical device, an electronic device, an electrical device, etc.
Examples
Measuring and test methods
Materials
The following materials were used in the examples shown in Tables 2 and 3.
Elastollan® 1190A, a polyether based aromatic TPU from BASF Polyurethanes GmbH, tensile strength, 50 MPa; tear strength (angle), 89 kN/m; abrasion loss, 40 mm3.
CDP and RDP, from Zhejiang Wansheng Co., Ltd.
IL 1 , an ionic liquid based on quaternary phosphonium cation and organophosphate anion, used as flame retardant.
Butanediol, from BASF, used as chain extender for synthesizing thermoplastic polyurethane of examples in Table 3.
Poly(tetrahydrofuran ether), functionality 2, hydroxyl value 112.2 mgKOH/g, from BASF, used as polyol for synthesizing thermoplastic polyurethane of examples in Table 3.
Lupranate® MS, mainly 4,4’-MDI, from BASF, used as isocyanate for synthesizing thermoplastic polyurethane of examples in Table 3.
Polystyrene-based matting agent.
Antioxidant Irganox® 1010, a sterically hindered phenol from BASF.
To prepare flame-retardant thermoplastic polyurethane composition, the two flame retardants were added into the thermoplastic polyurethane. The ionic liquid and the phosphorus-containing ester were added into the thermoplastic polyurethane separately, then they were dispersed evenly. The mixture was heated under 80 °C for several hours until the liquids were evenly dissolved into the matrix of thermoplastic polyurethane.
The resultant flame-retardant thermoplastic polyurethane composition was shaped into testing sheets with a thickness of 2 mm via injection molding for mechanical performance and flame-retardancy testing.
Table 2 shows examples with a UL94 V0 level of flame retardancy, while Table 3 shows examples with a UL94 V2 level.
Table 2 Properties of thermoplastic polyurethane compositions
From Table 2, it is indicated that compared with TPU compositions with only phosphorus- containing ester as flame retardant, TPU compositions with both ionic liquid and phosphorus- containing ester as co-flame retardant can achieve the same level of flame-retardancy under a much lower dosage. To achieve the roughly same level of flame retardancy, the TPU composition with both ionic liquid and phosphorus-containing ester exhibits improvements with regards to mechanical performances especially tear strength and abrasion loss. Abrasion loss and tear strength important for products such as cable sheathing, wire, hose, pipeline, belt, etc. To achieve good mechanical performances, the weight percentage of ionic liquid is preferably 0.2-2.8 wt.%, 0.3-1.5 wt.%, more preferably 0.5-1.0 wt.%, based on the total weight of the thermoplastic polyurethane composition. Compared with the original thermoplastic polyurethane Elastollan® 1190A, the flame-retardant thermoplastic polyurethane with ionic liquid and phosphorus- containing ester deteriorates less in tensile strength, tear strength and abrasion loss.
Table 3 Properties of thermoplastic polyurethane compositions
TPUs in Table 3 were synthesized via an extruder. The isocyanate index calculated as the ratio of the number of isocyanate groups in polyisocyanate to the total number of hydroxyl groups in chain extender and polyol was about 1. The flame retardants, matting agent, and antioxidant were added to the thermoplastic polyurethane during its synthesis.
From Table 3, it can be found that TPU compositions with both ionic liquid and phosphorus- containing ester as co-flame retardant can achieve the same level of flame-retardancy with a much lower dosage and under the presence of other additives. The thermoplastic polyurethane sample with ionic liquid and phosphorus-containing ester outperforms those samples containing only phosphorus-containing ester as flame-retardant in terms of mechanical strength, elongation at break, and abrasion loss.
Claims
1. A thermoplastic polyurethane composition comprising, based on a total weight of the thermoplastic polyurethane composition,
84-97 wt.% of a thermoplastic polyurethane, and
3-16 wt.% of a flame retardant, wherein the flame retardant comprises an ionic liquid and a phosphorus-containing ester.
2. The thermoplastic polyurethane composition according to claim 1 , wherein the ionic liquid is a phosphorus-based ionic liquid.
3. The thermoplastic polyurethane composition according to claim 2, wherein the ionic liquid has a formula of:
M+ represents a monovalent cation selected from the group consisting of an ammonium, a quaternary ammonium, an imidazolium, a guanidinium, a pyridinium, a pyridazinium, 1 ,2,4- triazolium, a triazine, a sulfonium, a phosphazenium and a phosphonium cation; and
Ri and R2 are each independently selected from hydrogen, hydroxyl, C1-C18 alkyl, aryl, CICIS alkoxyl, aryl, (C3-C10) heterocyclyl, (C3-C10)cycloalkyl, (C3-C10)heterocyclyl (C1-C8)alkyl, aryl (C1-C8)alkyl, heteroaryl and heteroaryl (C1-C8)alkyl group, each of which is unsubstituted or substituted with one or two halogen atoms, — NO2, — CF3, — OCF3, — OCH3, — CO2H, — NH2, — OH, — SH, — NHCH3, — N(CH3)2, — CN, — SCH3, — SO3H, — CH=CH— CH— CH=CH2, — P((C1- C5) alkyl)2, and — P(0)(0Et)2, or mixtures of the substituents.
4. The thermoplastic polyurethane composition according to claim 3, wherein M+ represents a phosphonium cation.
5. The thermoplastic polyurethane composition according to claim 1 , wherein the ionic liquid has a weight percentage of 0.2-2.8 wt.%, preferably 0.3-1.5 wt.%, more preferably 0.5-1.0 wt.%, based on a total weight of the thermoplastic polyurethane composition.
6. The thermoplastic polyurethane composition according to claim 1 , wherein the phosphorus-containing ester includes one or more selected from resorcinol bis(diphenylphosphate), bisphenol A bis(diphenyl phosphate), cresyl diphenyl phosphate,
monomeric resorcinol dixylenyl phosphate, polymeric resorcinol dixylenyl phosphate, trixylenyl phosphate, triethyl phosphate, tricresyl phosphate, and triphenyl phosphate.
7. The thermoplastic polyurethane composition according to claim 1 , wherein the phosphorus-containing ester has a weight percentage of 1-18 wt.%, preferably 2-15 wt.%, more preferably 3-10 wt.%, based on a total weight of the thermoplastic polyurethane composition.
8. The thermoplastic polyurethane composition according to claim 1 , wherein the ionic liquid and the phosphorus-containing ester are in a weight ratio of 1 :100-1 :0.7, preferably 1 :50-1 :2, more preferably 1 :20-1 :5.
9. The thermoplastic polyurethane composition according to any of claims 1 through 8, wherein the thermoplastic polyurethane has a weight average molecular weight in the range from 50,000 to 500,000 Da.
10. The thermoplastic polyurethane composition according to any of claims 1 through 8, wherein the thermoplastic polyurethane composition has a hardness of Shore 40 A to Shore 80 D, preferably Shore 50 A to Shore 98 A, as determined in accordance with DIN ISO 48-4.
11. The thermoplastic polyurethane composition according to any of claims 1 through 8, wherein a sheet of a thickness of 2mm prepared from the thermoplastic polyurethane composition achieves a LIL94 V0 rating, following procedures of Underwriter's Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic Materials, UL94".
12. An article produced from the thermoplastic polyurethane composition according to any of claims 1 through 11.
13. The article according to claim 12, wherein the article is an artificial leather, a film, a sheet, a molding, a fiber, a trim in automobiles, a tube, a hose, a profile, a pipeline, a cable connector, a towing cable, a cable sheathing, a wire, an optical component, an electronic component, an electrical component, a seal, a nonwoven, a belt, or a damping element.
14. Use of the article according to claim 12 or 13 in an electric vehicle, or a charging device for electric vehicles, a home appliance, house or office furniture, a construction, an optical device, an electronic device, or an electrical device.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0617079A2 (en) * | 1993-03-22 | 1994-09-28 | Elastogran GmbH | Self extinguishing thermoplastic polyurethanes and process for their preparation |
US20150353832A1 (en) | 2013-01-30 | 2015-12-10 | H & C Scientific Resources International, LLC | Phosphinate ionic liquid compositions and methods of use |
CN105440652A (en) | 2015-12-25 | 2016-03-30 | 青岛科技大学 | Flame retardant thermoplastic polyurethane elastomer (TPU) and preparation method thereof |
CN111117205A (en) * | 2019-08-27 | 2020-05-08 | 张媛婷 | Silica aerogel heat insulation sealing material |
CN111909503A (en) | 2019-05-07 | 2020-11-10 | 南通诺为新材料科技有限公司 | Flame-retardant thermoplastic polyurethane plastic, flame retardant and application |
-
2023
- 2023-09-04 WO PCT/EP2023/074111 patent/WO2024056417A1/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0617079A2 (en) * | 1993-03-22 | 1994-09-28 | Elastogran GmbH | Self extinguishing thermoplastic polyurethanes and process for their preparation |
US20150353832A1 (en) | 2013-01-30 | 2015-12-10 | H & C Scientific Resources International, LLC | Phosphinate ionic liquid compositions and methods of use |
CN105440652A (en) | 2015-12-25 | 2016-03-30 | 青岛科技大学 | Flame retardant thermoplastic polyurethane elastomer (TPU) and preparation method thereof |
CN111909503A (en) | 2019-05-07 | 2020-11-10 | 南通诺为新材料科技有限公司 | Flame-retardant thermoplastic polyurethane plastic, flame retardant and application |
CN111117205A (en) * | 2019-08-27 | 2020-05-08 | 张媛婷 | Silica aerogel heat insulation sealing material |
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