WO2015142613A1 - Composition d'argile modifiée par un ester de phosphate, procédé de production de celle-ci et nanocomposite à base de pvc ignifugé, contenant celle-ci - Google Patents
Composition d'argile modifiée par un ester de phosphate, procédé de production de celle-ci et nanocomposite à base de pvc ignifugé, contenant celle-ci Download PDFInfo
- Publication number
- WO2015142613A1 WO2015142613A1 PCT/US2015/020156 US2015020156W WO2015142613A1 WO 2015142613 A1 WO2015142613 A1 WO 2015142613A1 US 2015020156 W US2015020156 W US 2015020156W WO 2015142613 A1 WO2015142613 A1 WO 2015142613A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphate ester
- clay
- pvc
- phosphate
- modified clay
- Prior art date
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- 239000004927 clay Substances 0.000 title claims abstract description 109
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 108
- 239000010452 phosphate Substances 0.000 title claims abstract description 108
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 49
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 22
- -1 phosphate ester Chemical class 0.000 claims abstract description 74
- 239000003063 flame retardant Substances 0.000 claims description 32
- 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 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000004014 plasticizer Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000275 saponite Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 9
- 229910000278 bentonite Inorganic materials 0.000 claims description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 5
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 5
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 235000021317 phosphate Nutrition 0.000 description 83
- 239000004800 polyvinyl chloride Substances 0.000 description 81
- 229920000915 polyvinyl chloride Polymers 0.000 description 78
- 230000008569 process Effects 0.000 description 13
- 229910052787 antimony Inorganic materials 0.000 description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000001412 amines Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012767 functional filler Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 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 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 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 description 2
- WOURXYYHORRGQO-UHFFFAOYSA-N Tri(3-chloropropyl) phosphate Chemical compound ClCCCOP(=O)(OCCCCl)OCCCCl WOURXYYHORRGQO-UHFFFAOYSA-N 0.000 description 2
- 229920006266 Vinyl film Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000011363 dried mixture Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- UNYASDZTYUOWNJ-UHFFFAOYSA-N (2,3-dimethyl-4-phenylphenyl) dihydrogen phosphate Chemical class C1=C(OP(O)(O)=O)C(C)=C(C)C(C=2C=CC=CC=2)=C1 UNYASDZTYUOWNJ-UHFFFAOYSA-N 0.000 description 1
- UIYDTXYIPKRDPD-UHFFFAOYSA-N (2-phenyl-3-propan-2-ylphenyl) dihydrogen phosphate Chemical class CC(C)C1=CC=CC(OP(O)(O)=O)=C1C1=CC=CC=C1 UIYDTXYIPKRDPD-UHFFFAOYSA-N 0.000 description 1
- SDASIJIURWSHIC-UHFFFAOYSA-N (3-butyl-2-phenylphenyl) dihydrogen phosphate Chemical class CCCCC1=CC=CC(OP(O)(O)=O)=C1C1=CC=CC=C1 SDASIJIURWSHIC-UHFFFAOYSA-N 0.000 description 1
- MVDVRXOWIPONFY-UHFFFAOYSA-N 1-diethoxyphosphoryloctane Chemical compound CCCCCCCCP(=O)(OCC)OCC MVDVRXOWIPONFY-UHFFFAOYSA-N 0.000 description 1
- IUZXGJKDSGEWCQ-UHFFFAOYSA-N 1-dimethoxyphosphorylhexane Chemical compound CCCCCCP(=O)(OC)OC IUZXGJKDSGEWCQ-UHFFFAOYSA-N 0.000 description 1
- AYIYGMYWHVTKNV-UHFFFAOYSA-N 1-dimethoxyphosphoryloctane Chemical compound CCCCCCCCP(=O)(OC)OC AYIYGMYWHVTKNV-UHFFFAOYSA-N 0.000 description 1
- IUYYVMKHUXDWEU-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,1-diol Chemical compound CC(C)CC(C)(C)C(O)O IUYYVMKHUXDWEU-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- KPCIOPODVHBMQR-UHFFFAOYSA-N CC1=CC=C(OP(O)(O)=O)C(C=2C=CC=CC=2)=C1 Chemical class CC1=CC=C(OP(O)(O)=O)C(C=2C=CC=CC=2)=C1 KPCIOPODVHBMQR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 244000147568 Laurus nobilis Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
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- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- FRQDZJMEHSJOPU-UHFFFAOYSA-N Triethylene glycol bis(2-ethylhexanoate) Chemical compound CCCCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CCCC FRQDZJMEHSJOPU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZHTFEVGYQCBSFQ-UHFFFAOYSA-N [2-(2-methylpropyl)phenyl] dihydrogen phosphate Chemical class C(C(C)C)C1=C(C=CC=C1)OP(O)(O)=O ZHTFEVGYQCBSFQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
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- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- XBJJRSFLZVLCSE-UHFFFAOYSA-N barium(2+);diborate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]B([O-])[O-].[O-]B([O-])[O-] XBJJRSFLZVLCSE-UHFFFAOYSA-N 0.000 description 1
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- IPZUQRLCNOKXGP-UHFFFAOYSA-N bis(11-methyldodecyl) 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CC(C)CCCCCCCCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCCCCCCCCCC(C)C IPZUQRLCNOKXGP-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- UAKCGUNFFZWDIS-UHFFFAOYSA-N bis(6,6-dimethylheptyl) 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound BrC=1C(=C(C(=C(C=1C(=O)OCCCCCC(C)(C)C)C(=O)OCCCCCC(C)(C)C)Br)Br)Br UAKCGUNFFZWDIS-UHFFFAOYSA-N 0.000 description 1
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- YICSVBJRVMLQNS-UHFFFAOYSA-N dibutyl phenyl phosphate Chemical group CCCCOP(=O)(OCCCC)OC1=CC=CC=C1 YICSVBJRVMLQNS-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- QRBLPTJJQNRVAJ-UHFFFAOYSA-N dioctyl 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCCCCCCCC QRBLPTJJQNRVAJ-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000515 huntite Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- GCTMVWJHICUMRV-UHFFFAOYSA-N octan-3-yl diphenyl phosphate Chemical group C=1C=CC=CC=1OP(=O)(OC(CC)CCCCC)OC1=CC=CC=C1 GCTMVWJHICUMRV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- UYQARBPRMDXMLB-UHFFFAOYSA-N phenyl (2-propylphenyl) hydrogen phosphate Chemical class CCCC1=CC=CC=C1OP(=O)(O)OC2=CC=CC=C2 UYQARBPRMDXMLB-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000001557 phthalyl group Chemical group C(=O)(O)C1=C(C(=O)*)C=CC=C1 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- YQKGJRGUAQVYNL-UHFFFAOYSA-N tris(1,2-dichloropropan-2-yl) phosphate Chemical compound ClCC(Cl)(C)OP(=O)(OC(C)(Cl)CCl)OC(C)(Cl)CCl YQKGJRGUAQVYNL-UHFFFAOYSA-N 0.000 description 1
- AMHVNVKLDLHXTM-UHFFFAOYSA-N tris(2-butylphenyl) phosphate Chemical compound CCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCC)OC1=CC=CC=C1CCCC AMHVNVKLDLHXTM-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- FPIUEVPELBLXGL-UHFFFAOYSA-N tris(2-propylphenyl) phosphate Chemical compound CCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCC)OC1=CC=CC=C1CCC FPIUEVPELBLXGL-UHFFFAOYSA-N 0.000 description 1
- ZZFANQIKAIAQMV-UHFFFAOYSA-N tris(8-methylnonyl) phosphate Chemical compound CC(C)CCCCCCCOP(=O)(OCCCCCCCC(C)C)OCCCCCCCC(C)C ZZFANQIKAIAQMV-UHFFFAOYSA-N 0.000 description 1
- LWYPBQJBRGDLOI-UHFFFAOYSA-N tris[4-(2-methylpropyl)phenyl] phosphate Chemical compound C1=CC(CC(C)C)=CC=C1OP(=O)(OC=1C=CC(CC(C)C)=CC=1)OC1=CC=C(CC(C)C)C=C1 LWYPBQJBRGDLOI-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the present invention relates to the field of flame-retarded PVC nanocompo sites and more particularly to a flame-retarded PVC composition(s) and articles containing the same, e.g., a flame-retarded cable jacket, vinyl films/sheet goods, PVC tubing or automotive component(s).
- Polyvinyl chloride is often employed to achieve a pass of high standardized levels of flammability and also to obtain improved light, oxidative stability as well as high resistance to abrasion all at low cost.
- PVC has problems with process stability which can lead to discoloration, or in more severe cases, to the lost of physical properties.
- Thermal decomposition of PVC has been well studied and is attributed to a mechanism known as "autocatalytic dehydrohalogenation" or an "unzipping" reaction; i.e., the PVC may degrade before melting or during compounding.
- the oxygen index (01) of PVC is 45.0 to 49.0, but when PVC is forced to burn, it can generate high levels of black smoke.
- the plasticizer(s) has flame resistance.
- the oxygen indices of piasiicized PVC in general obey a simple two-parameter equation wherein the plasticizer is often more flammable than the PVC itself. In order to meet flammability specifications such as oxygen index, heat release, smoke evolution, or cable tests, fiame- retardants and smoke-suppressants are often incorporated into plasticized PVC.
- nanometer-sized particles dispersed in a polymer matrix helps to improve, not only the physical properties of the polymer matrix, but also, the polymer's resistance to fire.
- Most common nanocomposite materials comprise a polymeric matrix in which particles of clay of a nanometric size are dispersed therein, e.g., so- called organoclays, e.g. organophilically treated clays.
- Good dispersion has been shown to provide for a consistent improvement of the physical properties and resistance against fire. It is believed that the latter feature is due to the formation of a ceramic-carbonaceous protective layer (char) on the surface of the burning polymer, which impedes the evolution of combustible gases and therefore reduces the speed of fire propagation.
- char ceramic-carbonaceous protective layer
- Nanocomposites are commercially available in various polymers such as polyamides, polyesters, polypropylene, poly(ethylvinyl acetate) and similar polymers, but nanocomposites are not available in PVC, because, commercially available organoclays have not been shown to be compatible with PVC.
- the nanocomposite comprising PVC resin and phosphate ester-modified clay has the same or improved light, oxidative stability and resistance to abrasion as compared to
- the PVC nanocomposite of the present invention provides for flame retardant efficiency in PVC compounds while avoiding the aforementioned problems.
- Figure 1 is an XRD scan of original clay (PGN) and clay treated with Phosflex 418 (418-PGN) as described in Example 1.
- Figure 2 is a photograph of the process stability test at 185°C/55rpm/variable times as described in Examples 2-5.
- the present invention is directed to a phosphate ester-modified clay composition, along with the process of making a phosphate ester-modified clay, as well as a PVC nanocomposite comprising PVC resin and the phosphate ester-modified clay composition, which has improved flame retardant properties.
- the phosphate ester clay is made by reacting a clay, e.g., a smectite- type clay with a phosphate ester, wherein the phosphate ester doesn't destabilize PVC, e.g.
- Such flame-retarded PVC nanocomposite can be used in cable jacketing in production of PVC tubing or in production of automotive parts or a like while providing flame retardancy and maintaining good physical properties.
- a phosphate ester-modified clay composition comprising a clay and a phosphate ester.
- the phosphate ester modifier is a phosphate ester containing from one to three long aliphatic chains, more specifically one, two or three linear or branched alkyl, cycloalkyl, linear or branched alkyl-substituted cycloalkyl, linear or branched alkenyl, and linear or branched alkynyl groups containing up to about 30 carbon atoms, more specifically up to about 20 carbon atoms, even more specifically up to about 12 carbon atoms, yet even more specifically up to about 8 carbon atoms, wherein said ranges are understood in one embodiment to contain a lower endpoint of one, three or six carbon atoms, as can any of the other ranges of R 1 , R 2 or R 3 defined herein.
- the phosphate ester may have the following structure formula (I):
- the phosphate ester is alkyl diphenyl phosphate of the general formula (II)
- R 3 is a linear or branched or saturated or unsaturated alkyl containing up to 22 carbon atoms, more specifically from 6 to 22 carbon atoms.
- Examples of commercial phosphate esters specifically useful in this invention are those selected from the group consisting of triphenyl phosphate, tricresylphosphate, mixed phenyl- cresyl phosphates, trixylyl phosphate, mixed phenyl-xylyl phosphates, tris(propylphenyl) phosphate, mixed propylphenyl phenyl phosphates, tris(isopropylphenyl) phosphate, mixed isopropylphenyl-phenyl phosphates, tris(butylphenyl) phosphate, mixed butylphenyl-phenyl phosphates, tris(isobutylphenyl) phosphate, mixed isobutyl-phenyl phosphates, tri(ehylhexyi) phosphate, tri(isodecyl) phosphate, dimethyl hexylphosphonate, dimethyl octylphosphonate,
- the most specific phosphate esters useful in this invention are selected from the group consisting of 2-ethylhehyl diphenyl phosphate available from ICL-IP as Phosflex 362, isodecyl diphenyl phosphate available from ICL-IP as Phosflex 390, a linear alkyl Cn-Ci3 diphenyl phosphate available from ICL-IP as Phosflex 418 and combinations thereof.
- the phosphate ester-modified clay composition will contain from 5 to 40% by weight phosphate ester, specifically from 15 to 40% by weight of phosphate ester, more specifically from 25 to 40 % by weight of phosphate ester, based on the total weight of the phosphate ester- modified clay composition used to make the flame-retardant PVC nanocomposite.
- the clay is obtained from a smectitic-type clay selected from the group consisting of montmorillonite, hectorite, saponite and combinations thereof.
- the clays useful for making the nanocomposites herein can be layered clay materials comprising an agglomeration of individual platelet particles that are closely stacked together in domains called tactoids. Individual platelet particles of the clays specifically can have tliickness of less than 2 nm.
- the clay material can be selected from the group of natural or synthetic phyllosilicates, or combinations thereof.
- suitable natural clays include smectite clays such as montmorillonite, saponite, hectorite, mica, vermiculite, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, and the like. Natural clays can be further refined or purified to remove undesirable impurities.
- Some suitable synthetic clays can include synthetic mica, synthetic saponite, synthetic hectorite, and the like.
- a bentonite or montmorillonite with mineral content large than 50% is appropriate for the composition/nanocomposite and applications described herein.
- the higher purity can be achieved via selective mining, purification or synthetic processes.
- the most specific clays useful in this invention are purified montmorillonite clays available from Nanocor LLC, Hoffman Estates, IL 60192, USA. Typical products include PGN, PGW and PGV.
- the clay can be previously purified of impurities embedded therein, thus, obtaining a purified clay, in particular, the purification process lowers the impurities to less than 2% by weight, preferably less than 1% by weight.
- the selected natural or synthetic clay (purified or not) can be further treated to increase spacing between the platelets to facilitate separation of the platelet agglomerates to individual platelet particles to form smaller-sized tactoids.
- Such treatment prior to incorporation into the polymer also improves the polymer/platelet interface. Any method of treatment that achieves the above goals can be used. Many clay treatments used to modify the clay for the purpose of improving dispersion of clay materials are known and can be used.
- organocations exchange with the natural interlayer cations of the clay to generate organophilic surfaces while maintaining a lamellar structure similar to the natural clay.
- the organocations are not quaternary ammonium compounds, in that, as stated above, quaternary ammonium compounds are damaging to PVC because they catalyze dechlorination and unzipping of the resin.
- organoclay or "phosphate ester-modified clay” herein is prepared by the reaction of a swellable layered clay with a phosphate ester. This is not the above noted cation exchange reaction, but rather, an absorption reaction which proceeds by coordination of dipolar phosphate group with the charged clay platelets. Similar to the organocation exchange reaction the absorption reaction results in production of the organophilic clay. If desired, two or more phosphate esters can be used to treat the clay.
- the clay become hydrophobic and can be dispersed into the PVC polymer resin system to form polymer-clay nanocomposite materials.
- 10% phosphate ester is needed to convert the clay to a hydrophobic state. The more specific ratios are 30%-40% of phosphate ester in the final phosphate ester-modified clay.
- the phosphate ester is chemically intercalated between the layers of the clay.
- Water is the more specific media for delivering phosphate ester in contact with interlayer cations in the clay.
- the formation of the phosphate ester-modified clay can be carried out in dilute clay suspension/slurry form and followed by drying using means such as the non-limiting embodiments of natural sun-dry, heated drum drying or high efficiency spray drying.
- the reaction can also occur in a solid-like environment via an extrusion process with the assistance of water.
- the process to prepare the phosphate ester-modified clays can be conducted in a batch, semi-batch, or continuous manner.
- a non-limiting method for the production of a phosphate ester-modified clay comprising the steps of: blending a clay, e.g, a smectite-type clay, water and a phosphate ester in a mixture; and, drying the mixture to produce the phosphate ester -modified clay.
- a flame retarded PVC nanocomposite comprising a PVC resin and a flame retardant effective amount of phosphate ester-modified clay as described herein.
- the clay is dispersed in the PVC resin so as to provide a mixture of nanoclay platelets dispersed among the PVC molecules. This feature avoids the production of HC1 and therefore the decomposition of polyvinylchloride.
- the phosphate ester-modified clay, or the flame retarded PVC nanocomposite further comprises an inorganic additive (filler).
- the inorganic additive can be selected from the group comprised of aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, antimony oxide, zinc borate, glass powder and combinations thereof.
- the combination of a clay with an inorganic additive has a synergistic effect and provides a product with surprising flame retardant properties, e.g., in the flame retarded nanocomposite described herein.
- the nanocomposite is obtained by mixing from 1 to 60 parts by weight of a phosphate ester-modified clay per one hundred (100) parts of resin (phr), i.e., the polymeric PVC matrix.
- the nanocomposite comprises between 0 to 50 phr of inorganic additive.
- PVC resins suitable for use in the present invention include, but are not limited to, polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), and other PVC resins, alloys/blends.
- the preferred resin for the present invention is polyvinyl chloride (PVC).
- PVC polyvinyl chloride
- the present invention may be applied to both rigid and flexible PVC formulations.
- a "rigid" formulation is a formulation having a plasticizer in a concentration of zero to less than about 5 parts per hundred of resin (phr).
- a "flexible” formulation typically has a plasticizer in a concentration from greater than about 5 to as much as about 150 parts per hundred of resin (phr).
- PVC resins may be selected for optimum physical properties and process performance.
- suspension PVC resins have better thermal stability than PVC resins produced by mass or emulsion polymerization.
- Other properties such as average particle size, particle size distribution, porosity, and the like may greatly affect the performance of PVC resin in the same formulation.
- PVC nanocomposite in the context of this invention is the combination of the phosphate ester-modified clay in a PVC matrix.
- the flame-retardant effective amount can vary greatly depending on the particular PVC resin being employed, the desired article and/or application to which the PVC nanocomposite directed and processing limitations.
- the flame-retardant effective amount is the amount of phosphate ester-modifed clay described above, i.e., 1 to 60 parts by weight of an phosphate ester-modified clay per one hundred (100) parts of resin (phr), i.e., the polymeric PVC matrix, more specifically from 5 to about 45 parts by weight and most specifically from about 10 to about 40 parts by weight.
- the components e.g., the phosphate ester-modifed clay and the PVC resin, and any others, can be mixed by any known methods.
- a premixing step the dry ingredients are mixed together.
- the premixing is typically performed using a tumbler mixer or ribbon blender.
- the premix can be manufactured using a high shear mixer such as a Henschel mixer or similar high intensity device.
- the process is typically followed by melt mixing in which the premix is melted and mixed again as a melt- blended composite.
- the premixing can be omitted, and raw materials can be added directly into the feed section of a melt mixing device, preferably via multiple feeding systems.
- melt mixing the ingredients are typically melt kneaded in a single screw or twin screw extruder, a Banbury mixer, a two roll mill, a batch mixer or similar device.
- the examples are batch mixed using a Brabender type bowl mixer with a temperature regime of 160° to 180° C.
- phosphate ester-modified clay of the present invention can be added to PVC resin in the form of a masterbatch (or concentrate) and further melt mixed with PVC and other ingredients.
- a masterbatch is a concentrated form of the additive blended into a compatible resin base to benefit dispersion and provide the clay in an exfoliated form for improved properties in the finished compound.
- PVC nanocomposites offer flame-retardancy properties because such nanocomposite formulations burn at a noticeably reduced rate and form a hard char at the surface. They also exhibit minimum dripping and fire sparkling. In order to pass more stringent flame retardant tests (for example for the cable industry) the use of antimony based flame retardants may also required in the phosphate ester-modified clay composition, as well as the resultant PVC nanocomposite thereof.
- the phosphate ester-modified clay composition, as well as the resultant PVC nanocomposite thereof may further comprise at least one of an antimony -based flame retardant (e.g., an antimony trioxide flame retardant), a flame retardant filler, an inert filler and a functional filler.
- an antimony -based flame retardant e.g., an antimony trioxide flame retardant
- a flame retardant filler e.g., an inert filler and a functional filler.
- the phosphate ester-modified clay composition, as well as the resultant PVC nanocomposite thereof may still further comprise, optionally in addition to any of the above noted components, at least one plasticizer.
- the antimony based flame retardant is antimony trioxide.
- the typical particle size of antimony based flame retardants is from 0.5 ⁇ to 5 ⁇ .
- Antimony based flame retardants may be surface-treated with an epoxy compound, silane compound, isocyanate compound, titanate compound, or the like as required.
- other examples of antimony based flame retardants can be antimony pentaoxide or sodium antimonate and combinations of any of the noted antimony synergists.
- the antimony the antimony can be present in an amount from 0.5 to 10 parts per one hundred parts of PVC resin (p.h.r.), more preferably from 2 to 7 p.h.r.
- the PVC nanocomposite can contain other flame retardant fillers for example aluminium trihydroxide (ATH) or inert fillers such as chalk or talc or glass powder.
- ATH is particularly preferred because of its FR efficacy and low costs.
- Other known inert fillers or flame retardant fillers could be used instead of or in addition to those listed above and still produce a synergistic effect.
- magnesium carbonate examples include: magnesium carbonate, magnesium hydroxide (which could be added as either the refined compound or the ore brucite), hydromagnesite, huntite, boehmite, bauxite.
- Other functional filler which are typically used for smoke suppression are borates (e.g., zinc borates, calcium borates or barium borate) and molybdates (e.g., ammonium molybdates, ammonium octamolybdates). It is to be understood that these inorganic fillers may be added to PVC nanocomposites either individually or in combinations of two or more.
- the flame retardant filler (or any of the fillers described herein) can be present in an amount from 20 to 100 parts per one hundred parts of PVC resin (p.h.r.), more preferably from 20 to 70 phr.
- additional phosphate ester plasticizer can be added to the phosphate ester-modified composition and flame-retarded PVC nanocomposite as the primary plasticizer or in combination with other types of plasticizers.
- the phosphate ester herein can be the same phosphate ester employed in the clay or different.
- the phosphate ester employed herein can be halogenated or non-halo genated.
- halogenated compounds used herein with generally good results include tris(chloropropyl)phosphate (TCPP), tris(dichloroisopropyl)phosphate (TDCP) and 2,2- bis(chloromethyl)trimethylene bis[bis(2-chloroethyl)phosphate] (chlorinated diphosphate or V6 type product) and their mixtures.
- TCPP tris(chloropropyl)phosphate
- TDCP tris(dichloroisopropyl)phosphate
- 2,2- bis(chloromethyl)trimethylene bis[bis(2-chloroethyl)phosphate] chlorinated diphosphate or V6 type product
- Mixtures of different phosphate ester compounds are also contemplated, e.g., mixtures of halogenated and non-halogenated.
- the phosphate ester can be any phosphate ester than contains at least one aryl moiety, wherein the aryl moiety can be alkyl substituted or non-substituted.
- the aryl moiety can comprise substitution by an alkyl of from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, most preferably, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like, wherein such alkyl substitution can occur in any one or more of the available carbon atoms of the aryl moiety.
- the aryl phosphate ester is selected from the group consisting of butylated aryl phosphate, a propylated aryl phosphate, or a methylated aryl phosphate.
- a butylated aryl phosphate could be t-butyl substituted.
- a propylated aryl phosphate could be isopropyl-substituted.
- the aryl phosphate ester is selected from the group consisting of dibutyl phenyl phosphate, butyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, butylated or isopropylated triphenyl phosphate and combinations thereof.
- the aryl phosphate ester herein is available as Phosflex 7 IB or Phosflex 31L, both available from ICL-IP.
- the phosphate ester is selected from the group consisting of ethylhexyl diphenyl phosphate, such as Phosflex 362, isodecyl diphenyl phosphate ester, such as Phosflex 390 and, C )2 -Ci4 linear alkyl ester of diphenyl phosphate, such as Phosflex 418 all available from ICL-IP.
- the flame retarded P V C nanocomposite can contain non flame retardant plasticizers.
- non flame retardant plasticizers are adipates, citrates; non-halogenated phthalates (e.g., di-2-ethyl-hexyl, di-n-octyl, dioctyl, diisooctyl, diisodecyl, dibutyl, dihexyl, or diheptylnonyl); bisphthalates; benzoates; trimellitates;
- pyromellitates azelates; polymeric plasticizers based on adipic, azelaic, or sebacic acids and glycols such as ethylene, propylene, and butylene, with either alcohol or monobasic acid termination (e.g., benzoate diester of 2,2,4 trimethyl pentanediol or triethylene glycol di-2- ethylhexanoate); epoxies; esters of dibasic acids (e.g., aliphatic ester adipates such as dioctyl adipate, aliphatic ester sebacates such as dioctyl sebacate); alkyl sulfonate esters; aliphatic hydrocarbons; aromatic hydrocarbons; alkylated aromatic hydrocarbons; butyl phthalyl butyl glycollate, isobutyrate; dipentaerythritol esters; and combinations thereof.
- alcohol or monobasic acid termination e.g.
- phosphate ester plasticizers and non flame retardant plasticizers can be employed in the flame-retarded PVC nanocomposite composition as a mixture thereof. Specific proportion of each plasticizer depends on the final application and the flammability test.
- halogenated non phosphate ester based plasticizers can be employed in the flame retardant PVC nanocomposite composition.
- Dialkyl or dialkenyl tetracholophthalates and tetrabromophthalates represent one common class of halogenated phthalate plasticizers. More specifically the dialkyl or dialkenyl tetrahalophthalate is a C5-C15 alkyl or alkenyl tetrahalophthalate.
- dialkyl tetrahalophthalate is bis-2-ethylhexyl tetrachlorophthalate, bis-2- ethylhexyl tetrabromophthalate, bis-trimethylhexyl tetrabromophthalate, bis-isodecyl
- halogenated non phosphate based plasticizers Another class of halogenated non phosphate based plasticizers is halogenated paraffins.
- Halogenated paraffins can provide secondary plasticizing effects and also flame retardant properties.
- the halogenated paraffin can be brominated paraffin, chlorinated paraffin, bromochlorinated paraffin, and mixtures thereof, produced from a straight chain C 10 to Q20 paraffins.
- PVC is a shear-sensitive, heat-sensitive, and ultraviolet light sensitive polymer.
- Most applications for PVC require a well-balanced formulation with all ingredients carefully selected. Therefore the phosphate ester-modifed clay composition and the PVC nanocompo sites thereof of present invention can be stabilized and mixed with other formulating ingredients, including, but not limited to, thermal stabilizers, plasticizers, lubricants, processing aids, impact modifiers, other inert and functional fillers, antioxidants, ultraviolet light stabilizers, hindered amine light stabilizers, pigments, anti-static agents; foaming agents;
- the phosphate ester-modified clay composition and the PVC nanocomposites thereof of present invention are useful for producing flame-retarded cable jacket, a film, a sheet, PVC tubing or automotive component(s).
- Purified bentonite clay PGN produced by Nanocor was used. It is a Na+ rich bentonite.
- Phosflex 418 from ICL-IP is the selection of phosphate ester.
- Phosflex 418/water/PGN (weight ratio: 30/30/100) were fed into the main feed of a continuous mixer. The mixture was mixed under high shear at 120°C temperature. The compounded mixture was placed on a dryer to remove water. The dryer was set at 150°C heating temperature. The dried mixture had less than 5% moisture. The dried mixture was milled to fine powder with a mean particle size in the range of 10-20 microns. As Figure 1 shows, X-ray diffraction was used to investigate the structural change of the clay after the Phosflex reaction.
- the line of original PGN has a dOOl interlayer spacing (7 degree, 2 theta) at 12- 13 A, which is typical for hydrated bentonite clay.
- the peak at 4.5 A (19.5 degree, 2 theta) belongs to the clay d020 silicate structure.
- the line for the clay reacted with Phosphlex 418 marked as 418-PGN has a dOOl interlayer spacing (2.45 degree, 2 theta) at 36-37A.
- the original dOOl of PGN did not exist in the mixture. Therefore, the
- Phosflex 418 had entered the clay interlayer region to form a complex with Na + .
- the d020 silicate structure of the mixture was identical to the original PGN clay since tliere was no change in the clay silicate layer structure after the Phospflex interaction with the clay.
- Comparative example 3 with the quaternary amine treated clay exhibited significant discoloration after ten minutes of processing and within the next five minutes developed a deep brown hue with obvious polymer degradation agglomerates (black specks).
- the trial containing Nanomer I.44P amine treated clay was terminated at this point (fifteen minutes).
- Both phosphate ester treated organoclays showed no color development after thirty minutes of this aggressive process regime similar to untreated clay.
- Table 1 Compositions of PVC compounds used in process stability study
- compositions were mixed in the Brabender bowl mixer at 165° C, at 55 rpm rotation speed for 5 minutes. All materials were pre-blended prior to Brabender mixing. Compositions are shown in Table 2.
- Shore A hardness - physical property ASTM D2240, Shore A Durometer. Two numbers were measured; the initial (value when the probe is first plunged into the composite) and
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Abstract
L'invention concerne une composition d'argile modifiée par un ester de phosphate comprenant une argile et un ester de phosphate, un procédé de préparation de la composition d'argile modifiée par un ester de phosphate et un nanocomposite à base de PVC comprenant celle-ci.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108948596A (zh) * | 2018-08-11 | 2018-12-07 | 华北科技学院 | 一种复合阻燃软质pvc树脂的制备方法 |
CN115073816A (zh) * | 2022-08-17 | 2022-09-20 | 江苏港虹纤维有限公司 | 一种无机-有机杂化纳米材料及其制备方法和应用 |
CN117301677A (zh) * | 2023-11-27 | 2023-12-29 | 宁波市嘉化新材料科技有限公司 | 一种聚氨酯层状材料的隔热阻燃车衣及制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4546134A (en) * | 1983-03-25 | 1985-10-08 | Day Star Concepts | Coated, heat shrinkable expanded polystyrene |
WO2003039228A2 (fr) * | 2001-10-15 | 2003-05-15 | Cryovac, Inc. | Composition et feuil de chlorure de polyvinylidene constituant une barriere efficace |
CN101343387A (zh) * | 2007-07-12 | 2009-01-14 | 上海化工研究院 | 一种聚烯烃用无卤耐水性膨胀型磷氮阻燃剂及其制备方法 |
WO2012067685A1 (fr) * | 2010-11-16 | 2012-05-24 | Lubrizol Advanced Materials, Inc. | Polyuréthane thermoplastique retardateur de flamme non halogéné |
-
2015
- 2015-03-12 WO PCT/US2015/020156 patent/WO2015142613A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4546134A (en) * | 1983-03-25 | 1985-10-08 | Day Star Concepts | Coated, heat shrinkable expanded polystyrene |
WO2003039228A2 (fr) * | 2001-10-15 | 2003-05-15 | Cryovac, Inc. | Composition et feuil de chlorure de polyvinylidene constituant une barriere efficace |
CN101343387A (zh) * | 2007-07-12 | 2009-01-14 | 上海化工研究院 | 一种聚烯烃用无卤耐水性膨胀型磷氮阻燃剂及其制备方法 |
WO2012067685A1 (fr) * | 2010-11-16 | 2012-05-24 | Lubrizol Advanced Materials, Inc. | Polyuréthane thermoplastique retardateur de flamme non halogéné |
Non-Patent Citations (2)
Title |
---|
CHIGWADA G ET AL: "Synergy between conventional phosphorus fire retardants and organically-modified clays can lead to fire retardancy of styrenics", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 81, no. 3, 1 January 2003 (2003-01-01), pages 551 - 557, XP004438399, ISSN: 0141-3910, DOI: 10.1016/S0141-3910(03)00156-3 * |
JITKA ZÝKOVÁ ET AL: "INFLUENCE OF INTERCALATION AGENTS ON THE THERMAL STABILITZY OF PVC/CLAY NANOCOMPOSITES", 2009 NANOCON, 1 January 2009 (2009-01-01), XP055191087, Retrieved from the Internet <URL:http://konsys-t.tanger.cz/files/proceedings/nanocon_09/Lists/Papers/145.pdf> [retrieved on 20150522] * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108948596A (zh) * | 2018-08-11 | 2018-12-07 | 华北科技学院 | 一种复合阻燃软质pvc树脂的制备方法 |
CN115073816A (zh) * | 2022-08-17 | 2022-09-20 | 江苏港虹纤维有限公司 | 一种无机-有机杂化纳米材料及其制备方法和应用 |
CN117301677A (zh) * | 2023-11-27 | 2023-12-29 | 宁波市嘉化新材料科技有限公司 | 一种聚氨酯层状材料的隔热阻燃车衣及制备方法 |
CN117301677B (zh) * | 2023-11-27 | 2024-02-27 | 宁波市嘉化新材料科技有限公司 | 一种聚氨酯层状材料的隔热阻燃车衣及制备方法 |
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