CN103547625B - 包含基于哌嗪的金属盐混合物的阻燃聚烯烃树脂 - Google Patents
包含基于哌嗪的金属盐混合物的阻燃聚烯烃树脂 Download PDFInfo
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- CN103547625B CN103547625B CN201180067852.7A CN201180067852A CN103547625B CN 103547625 B CN103547625 B CN 103547625B CN 201180067852 A CN201180067852 A CN 201180067852A CN 103547625 B CN103547625 B CN 103547625B
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- polyolefin resin
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- 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 54
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 17
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title abstract description 38
- 229910052751 metal Inorganic materials 0.000 title abstract description 14
- 239000002184 metal Substances 0.000 title abstract description 14
- 150000003839 salts Chemical class 0.000 title abstract description 11
- -1 piperazine bis phosphoric acid aluminium salt Chemical class 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 18
- 229920001155 polypropylene Polymers 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 229920000388 Polyphosphate Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 239000001205 polyphosphate Substances 0.000 claims description 12
- 235000011176 polyphosphates Nutrition 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical group 0.000 claims description 7
- DNVIGFDFKWXCCP-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.OP(O)(O)=O.C1CNCCN1 DNVIGFDFKWXCCP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- FBMRTJHSEUTGEY-UHFFFAOYSA-H [Mg+2].P([O-])([O-])([O-])=O.P([O-])([O-])([O-])=O.N1CCNCC1.[Mg+2].[Mg+2] Chemical class [Mg+2].P([O-])([O-])([O-])=O.P([O-])([O-])([O-])=O.N1CCNCC1.[Mg+2].[Mg+2] FBMRTJHSEUTGEY-UHFFFAOYSA-H 0.000 claims description 3
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 2
- 239000011707 mineral Substances 0.000 claims 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 229960005141 piperazine Drugs 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- GHDAPYJTGWHWEK-UHFFFAOYSA-N P(=O)(O)OP(=O)O.N1CCNCC1 Chemical compound P(=O)(O)OP(=O)O.N1CCNCC1 GHDAPYJTGWHWEK-UHFFFAOYSA-N 0.000 description 11
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000011833 salt mixture Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000206 moulding compound Substances 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012747 synergistic agent Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NCVSERRNBKFENW-UHFFFAOYSA-K Cl.N1CCNCC1.P(=O)([O-])([O-])[O-].[Na+].[Na+].[Na+] Chemical compound Cl.N1CCNCC1.P(=O)([O-])([O-])[O-].[Na+].[Na+].[Na+] NCVSERRNBKFENW-UHFFFAOYSA-K 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- QHEGDQFQWZXPST-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.ClNC#N Chemical class OP(O)(=O)OP(=O)(O)O.ClNC#N QHEGDQFQWZXPST-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229960000890 hydrocortisone Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 150000007974 melamines Chemical class 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 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
- 235000021317 phosphate Nutrition 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical class NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical class OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
- C08K5/529—Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
-
- 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
- C08K5/5205—Salts of P-acids with N-bases
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- 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
- C09K21/10—Organic materials containing nitrogen
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及一种阻燃聚烯烃树脂,其包含的混合物含有:0.1至80wt%的哌嗪金属盐或其聚合物,10至80.0wt%的含氮增效剂或磷/氮阻燃剂,1-50wt%的无机化合物物,其中所述混合物组分的总和为100wt%。
Description
技术领域
本发明涉及一种阻燃混合物和其制备方法,更具体的涉及了一种聚烯烃树脂,其具有优秀的阻燃性且包含基于哌嗪的金属盐混合物。
发明背景
热塑性树脂具有优秀耐化学性、机械强度、电绝缘性,在电气、电子、汽车配件的外壳、连接器等中被广泛使用。在热塑性树脂于电器和电子装置领域中使用的情况下,为确保消防安全而赋予其阻燃性是十分必要的。
在制备过程中其处于熔化状态时,阻燃剂对热塑性塑料的安全性产生影响。根据国际标准应当使用大量阻燃剂以实现塑料合适的阻燃性。此外,需要高温下的化学反应以实现阻燃性,因而阻燃剂可能损害塑料的加工稳定性。例如,聚合物降解,交联反应,气体释放或退色可能会增加。另外,在以上描述的过程中,加热分解生成基于卤素的气体,从而由于如模塑装置、冲模等装置的腐蚀和有毒气体,导致工作环境的恶化。
尤其是,据发现在聚乙烯和聚丙烯中使用含磷的阻燃剂不能充分减少加工引发的问题,例如树脂的降解和退色。
以下专利,例如PCT/EP97/01664和出版号为No.19734437和19737727的德国公开专利,公开了,经过与单独使用一种主阻燃剂的情况对比,通过将一种主阻燃剂与其他的作为阻燃剂增效剂的阻燃剂混合可能可以增强阻燃性。另外公开了增效剂的实例,其可能包含三聚氰胺和三聚氰胺化合物(三聚氰胺氰尿酸盐和三聚氰胺磷酸盐),其可能独立的赋予任意一种热塑性塑料某种程度的阻燃性的且显著的改善了通过混合磷酸等获得的效果。
最近,一种哌嗪焦磷酸盐化合物由于它作为阻燃组合物的一个组分加入合成树脂产生卓越的效果而引起了关注。制造哌嗪焦磷酸盐的方法已被大量报道。例如,出版号为No.Sho 47-88791的日本公开专利公开了一种哌嗪焦磷酸盐作为可溶于水沉淀物,其通过将哌嗪盐酸盐与焦磷酸钠在水溶液中反应获得。另外,出版号为Nos.3810850和4599375的美国专利公开了一种制备哌嗪焦磷酸盐的方法,通过将哌嗪(无水)与焦磷酸钠(无水)在水溶液中反应,随后盐酸处理,以沉淀的形式获得。然而,关于哌嗪酸金属盐化合物研究尚未被发现。特别是,可理解为是哌嗪双磷酸盐以中介物的形式存在,是水溶性的且具有优秀的阻燃性,但难以处理,因而哌嗪双磷酸盐以金属盐化合物的形式制备从而作为具有结构安全性和优秀品质的阻燃剂使用。
另外,众所周知氯化钠等是作为以上描述的制备中生成的杂质被生产的,在应用到半导体,电子装置等时,造成负面效果。进一步,根据以上描述的制备,这样制备的产物收率低,未加工材料昂贵且需要处理废弃物的花费。另外,最大的困难之一是由于具有良好的阻燃性的哌嗪双磷酸盐是水溶性的,难于应用与树脂和处理。
在哌嗪双磷酸盐或哌嗪焦磷酸盐被当做阻燃组合物中的一个组分使用的情况下,不计杂质作用为显示V-0等级的阻燃性,应当在其中使用大量,至少大约30wt%或更多的量。因此,从经济角度看,大量昂贵的哌嗪焦磷酸盐并非显著有效。
发明内容
技术问题
本发明的一个目的是为了提供一种具有十分优秀的阻燃性的热塑性聚烯烃树脂,其中基于哌嗪的化合物和基于三聚氰胺的化合物以合适的比例使用于聚烯烃树脂,选择性的往其中加入填充剂,从而具备优秀的阻燃性,同时没有机械性质的退化,且因卤素不包含其中,以至于不会生成卤代毒性气体,以及提供一种制备所述聚烯烃树脂的方法。
技术方案
在一个方面,本发明提供了一种阻燃聚烯烃树脂,在聚烯烃聚合物组合物中包含基于哌嗪的金属盐混合物,通过使用含有缩合产物的阻燃混合物,可具有优秀的工艺加工性质,优秀的阻燃性和色彩属性,所述阻燃混合物中有1至80.0wt%哌嗪酸盐或聚合物,10至80.0wt%的三聚氰胺多聚磷酸盐(其为磷/氮阻燃剂),以及0.1至30wt%的在其中作为稳定剂的基本化合物、两性化合物和无机物,其中各组分的总量为100wt%。
有益效果
根据本发明具有优秀阻燃性的聚烯烃树脂组合物可能包含10至60wt%的阻燃混合物,所述混合物在热塑型聚烯烃形成的树脂为100重量份的基础上,包含1至80wt%的哌嗪盐化合物,10至80wt%的三聚氰胺基化合物,以及填料。其中哌嗪盐化合物是哌嗪双磷酸盐或哌嗪焦磷酸盐。尤其是,当制备在合适比例下具有优秀均一性和分散性的混合物时,可能会使用可以提供合适热量的搅拌器等。且由于应用的热量和自身潜在的热量,制备的阻燃剂的剂型为小丸剂等。
附图说明
图1是哌嗪酸双磷酸盐化合物的FT-IR分析获得的结果示意图;和
图2是使用阻燃混合物得到热分解结果示意图。
最佳实施方式
本发明人致力于研究非卤系阻燃剂,其结果是,研究集中于含磷量高的以盐形式存在的哌嗪酸盐化合物,并发现包含有作为有效组分的化合物中无机阻燃剂和三聚氰胺盐的阻燃剂,可以提供优秀的阻燃性同时不引起任意种类树脂相关机械性质的恶化,从而使本发明完整。也就是说,本发明的目的是提供一种非卤系的阻燃组合物,其可以提供优秀的阻燃性同时不引发机械性质的恶化、烟和不良气味的生成,通过包含以以下化学式1为代表的哌嗪酸盐金属化合物,与聚烯烃树脂相关,然后得到具有优秀阻燃性的树脂。
化学式1
哌嗪双磷酸金属盐
在熔化状态下制备本发明混合物的过程中,塑料的退色减少,塑料的降解受抑制,那么就完全保持了阻燃性。另外,令人惊讶的是本发明的添加剂在挤压和注射塑模的过程中完全阻止了挥发性异物生产。哌嗪酸金属盐化合物所包含的的众所周知的金属的实例,可能最好包括铝、钙、镁和锌。
磷酸与哌嗪在水溶液中互相反应,盐酸处理以重结晶,从而得到哌嗪焦磷酸盐的中间体,哌嗪双磷酸盐沉淀物。另外,进行脱水缩合反应以获得可溶于水的哌嗪焦磷酸盐(化学式2)。哌嗪双磷酸盐与哌嗪焦磷酸盐作为阻燃剂都具有优秀的性质,但哌嗪双磷酸盐具有水溶性因而其应用的局限性。以下化学式3表示了哌嗪酸金属盐,作为中间体由哌嗪双磷酸盐与金属反应获得。
化学式2
哌嗪焦磷酸盐
化学式3
哌嗪金属盐
在本发明阻燃混合物中使用的哌嗪双磷酸盐化合物中的金属(M)最好可能是铝、钙、镁、锌等。一分子的哌嗪双磷酸盐可能结合4(n=4)个金属,且即使在哌嗪双磷酸盐与一个金属结合(n=1)的情况下,所述可溶于水的化合物可制备且可作为阻燃剂起效。
图1为哌嗪酸双磷酸盐化合物FT-IR分析结果示意图,其为合成的哌嗪酸双磷酸盐成金属盐反应前后的光谱图。从图1可理解,反应后羟基(OH基团)成盐后完全消失于2400-3400(cm-1).因此,可以确定的是,可溶于水的哌嗪双磷酸金属盐已成功制备。
另外,在本发明中使用的磷/氮阻燃剂可能为双三聚氰胺磷酸盐,双三聚氰胺焦磷酸盐,三聚氰胺磷酸盐,三氯氰胺焦磷酸盐,三聚氰胺多聚磷酸盐,密白胺多聚磷酸盐,melon多聚磷酸盐和蜜勒胺多聚磷酸盐以及混合聚合盐。最好是三聚氰胺多聚磷酸盐。
众所周知,多种金属氧化物被当做填料和稳定剂使用。尤其是,金属氧化物最好可能是氧化镁,氧化锌,氧化锰和/或氧化锡。氢氧化物可能最好是氢氧化镁、铝碳酸镁、水铝钙石、氢氧化钙、氢氧化锌、锡氧化物水合物和/或氢氧化锰。
阻燃混合物的构成比可能依据于具有实际预期目的的应用领域,可在大范围内变化。根据应用领域提供组分,本发明的阻燃混合物可能包含1至80wt%的哌嗪双磷酸盐和10至80wt%的三聚氰胺多聚磷酸盐。图2是使用阻燃混合物获得的热分解结果示意图。从图2可理解,混合物在约320℃下被加热分解时,具有良好性质。
尤其是,本专利中塑料模塑组合物中的阻燃混合物,可能基于塑料模塑组合物被使用2至50wt%。聚烯烃形成的塑料的实例,最好可能包含烯烃聚合物,如聚丙烯、高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯、聚丁烯-1、聚3-甲基戊烯,或聚烯烃,例如乙烯-醋酸乙烯酯共聚物和乙烯丙烯共聚物,和其共聚物。尤其指出,最好是聚丙烯树脂。
下文中,本专利的实施实例将被详细描述,但以下实例仅为了帮助所述领域的技术人员明确理解本发明,本发明的范围并不由实例进行限定。
所用组合物
聚丙烯(PP):商业可获得标准聚合物(颗粒)
阻燃组分(粉末):
哌嗪双磷酸金属盐:本发明中合成的组分
三聚氰胺多聚磷酸盐(MPP):NONPLA-601(DOOBON INC.)
铝碳酸镁:PolyLizer-120(DOOBON INC.)
例1
阻燃剂,(本发明中包含树脂的组分总量为100wt%)其包含10wt%的哌嗪双磷酸铝盐,10wt%的三聚氰胺多聚磷酸盐,和1wt%作为无机金属氢氧化物铝碳酸镁化合物,使用搅拌器使其互相混合。混合物充分干燥后,干燥混合物经聚丙烯(PP)树脂处理成为模塑组合物,布拉班德粘度计与压力机(a Brabender anda press)用于在150-190(PP)的温度下制备测试样品,且根据UL94测试(保险商试验所)进行阻燃性测试。为了均一混合物,每个样品的测试都在同样条件下进行。
例2
除哌嗪双磷酸铝盐不加入其中外,但20wt%的三聚氰胺多聚磷酸盐随其混合外,例2中阻燃混合物的制备方法与例1相同。阻燃性测试方法与例1相同。
例3
除随其混入5wt%的哌嗪磷酸铝盐和25wt%的三聚氰胺多聚磷酸盐外,例3的阻燃混合物的制备方法与例1相同。阻燃性的测试方法与例1相同。
例4
除了随其混入20wt%的哌嗪双磷酸铝盐和5wt%的三聚氰胺多聚磷酸盐外,例4的阻燃混合物的制备方法与例1相同。阻燃性的测试方法与例1相同。
例5
除混合物经由PBT树脂处理成为模塑组合物,且在190的温度下使用布拉班德粘度计和压力机以制备测试样品外,例5的阻燃混合物的制备方法与例1相同,阻燃性的测试方法与例1相同。
例6
除使用哌嗪双磷酸镁盐外,例6的阻燃混合物的制备方法与例1相同。阻燃性的测试方法与例1相同。
根据本发明使用阻燃组合物获得的测试结果如表1所示。组合物使用的每个含量都基于含有阻燃混合物添加剂的塑料模塑组合物以wt%的形式表示。
经本发明的实例证实,根据本发明使用哌嗪基和磷基的添加剂,阻燃性略有增加,聚合物的加工型充分改善。另外,应当理解的是,通过将哌嗪双磷酸铝(镁)盐,三聚氰胺多聚磷酸盐和铝碳酸镁与聚丙烯(PP)合并获得的阻燃混合物,作为UL-94防火等级显示V-0等级的的阻燃剂,然而,根据未包含哌嗪双磷酸铝盐的例2,阻燃性不能完全显示且聚合物降解至含有浅棕色。
哌啶双磷酸铝盐作为阻燃剂的树脂,聚丙烯(PP)与聚酯(PBT)之间的区别可理解为实例1与实例5的比较。在五个测试样本总计十个数据中,使用聚丙烯(PP)的阻燃剂由总燃烧时间判定,在UL-94防火等级中显示V-0等级。然而,使用聚酯(PBT)树脂的阻燃剂,其应用到树脂上有问题,阻燃性并未完全显示。
表1
实例 | 树脂 | DPPAl | MPP | HT | 燃烧时间1)(秒) | UL.94等级 | 颜色 |
1 | PP | 10 | 10 | 1 | 11 | V-O | 白 |
2 | PP | 0 | 20 | 1 | - | - | 浅棕色 |
3 | PP | 5 | 25 | 1 | 25 | V-O | 白 |
4 | PP | 20 | 5 | 1 | 10 | V-O | 白 |
5 | PBT | 10 | 10 | 1 | - | - | 白 |
6 | PP | 10(DPPMg) | 10 | 1 | 17 | V-O | 白 |
(1)5个样本每个两次测试总燃烧时间
DPPA1:哌嗪双磷酸铝盐,MPP:三聚氰胺多聚磷酸盐,HT:铝碳酸镁
DPPMg:哌嗪双磷酸镁盐
Claims (7)
1.一种包含阻燃混合物的聚烯烃树脂,包含:
选自由哌嗪双磷酸金属盐、三聚氰胺多聚磷酸盐和无机化合物组成的组中的至少一种缩合物混合物,作为阻燃混合物;
其中,所述哌嗪双磷酸金属盐选自哌嗪双磷酸铝盐和哌嗪双磷酸镁盐,所述无机化合物为铝碳酸镁。
2.权利要求1的阻燃聚烯烃树脂,其中所述阻燃混合物基于塑料模塑组合物而被包含的量为10至60wt%。
3.权利要求1的阻燃聚烯烃树脂,其中所述哌嗪双磷酸金属盐基于聚烯烃树脂,在阻燃混合物中被包含的量为0.1至50wt%。
4.一种阻燃母料,其通过混合通过使用聚烯烃树脂和权利要求1的阻燃混合物获得的混合物和/或小丸剂而生产。
5.权利要求2的聚烯烃树脂,其中所述聚烯烃树脂包含至少一种选自由烯烃聚合物或者热塑性聚烯烃树脂组成的组中的聚合物。
6.权利要求5的聚烯烃树脂,所述烯烃聚合物为聚丙烯、高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯、聚丁烯-1或聚3-甲基戊烯。
7.权利要求5的聚烯烃树脂,所述热塑性聚烯烃树脂为乙烯-醋酸乙烯酯共聚物或乙烯丙烯共聚物。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1662629A (zh) * | 2002-06-24 | 2005-08-31 | 旭电化工业株式会社 | 阻燃剂组合物以及含有该组合物的阻燃性树脂组合物 |
CN101827885A (zh) * | 2007-11-14 | 2010-09-08 | 株式会社艾迪科 | 加工性得以改善的阻燃剂组合物、阻燃性合成树脂组合物及其成形品 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3810850A (en) | 1973-01-08 | 1974-05-14 | Jefferson Chem Co Inc | Piperazine phosphates as fire retardants for organic polymers |
IT1201097B (it) | 1983-05-18 | 1989-01-27 | Montedison Spa | Composizioni polimeriche resistenti alla fiamma |
DE19734437A1 (de) | 1997-08-08 | 1999-02-11 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19737727A1 (de) | 1997-08-29 | 1999-07-08 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Kunststoffe |
JP2001011462A (ja) * | 1999-06-30 | 2001-01-16 | Tosoh Corp | ピペラジン骨格を含むアミン含有リン酸亜鉛からなる難燃剤、及びそれを配合してなる難燃性樹脂組成物 |
JP2001348490A (ja) | 2000-06-08 | 2001-12-18 | Toyo Ink Mfg Co Ltd | 難燃性樹脂組成物およびその成形品 |
US6756430B2 (en) | 2000-06-13 | 2004-06-29 | Mitsui Chemicals, Inc. | Flame-retarding thermoplastic resin composition |
JP4753498B2 (ja) | 2001-07-17 | 2011-08-24 | 株式会社Adeka | 難燃性合成樹脂組成物 |
JP4526255B2 (ja) * | 2003-10-16 | 2010-08-18 | 株式会社Adeka | 高純度ピロリン酸ピペラジンの製造方法 |
CN1922260B (zh) * | 2004-02-24 | 2011-05-25 | 株式会社艾迪科 | 改善了流动性的阻燃剂组合物、阻燃性树脂组合物及其成形品 |
DE102007015083A1 (de) * | 2007-03-29 | 2008-10-02 | Clariant International Limited | Flammgeschützte Klebe- und Dichtmassen |
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---|
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US20130296467A1 (en) | 2013-11-07 |
EP2662404A2 (en) | 2013-11-13 |
EP2662404A4 (en) | 2015-04-08 |
KR101267465B1 (ko) | 2013-05-31 |
US9221961B2 (en) | 2015-12-29 |
CN103547625A (zh) | 2014-01-29 |
WO2012093781A2 (ko) | 2012-07-12 |
EP2662404B1 (en) | 2017-02-15 |
KR20120080001A (ko) | 2012-07-16 |
WO2012093781A3 (ko) | 2012-11-29 |
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