WO2012011519A1 - Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition - Google Patents
Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition Download PDFInfo
- Publication number
- WO2012011519A1 WO2012011519A1 PCT/JP2011/066534 JP2011066534W WO2012011519A1 WO 2012011519 A1 WO2012011519 A1 WO 2012011519A1 JP 2011066534 W JP2011066534 W JP 2011066534W WO 2012011519 A1 WO2012011519 A1 WO 2012011519A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame retardant
- cyclic amine
- resin
- component
- amine salt
- Prior art date
Links
- -1 cyclic amine salt Chemical class 0.000 title claims abstract description 212
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 title claims description 133
- 239000003340 retarding agent Substances 0.000 title abstract 4
- 229920005989 resin Polymers 0.000 claims abstract description 82
- 239000011347 resin Substances 0.000 claims abstract description 82
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 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 124
- 150000001875 compounds Chemical class 0.000 claims description 72
- 229910019142 PO4 Inorganic materials 0.000 claims description 62
- 235000021317 phosphate Nutrition 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 55
- 239000010452 phosphate Substances 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 45
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 150000005690 diesters Chemical class 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 16
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 229920005672 polyolefin resin Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 150000002500 ions Chemical group 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 239000000126 substance Substances 0.000 abstract description 10
- 230000000979 retarding effect Effects 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 40
- 238000003786 synthesis reaction Methods 0.000 description 40
- 238000005481 NMR spectroscopy Methods 0.000 description 38
- 239000007795 chemical reaction product Substances 0.000 description 36
- 238000005160 1H NMR spectroscopy Methods 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 33
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 32
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 27
- 229920001276 ammonium polyphosphate Polymers 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 239000004114 Ammonium polyphosphate Substances 0.000 description 23
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 150000002430 hydrocarbons Chemical group 0.000 description 22
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- 229920003002 synthetic resin Polymers 0.000 description 22
- 239000000057 synthetic resin Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 20
- 238000000921 elemental analysis Methods 0.000 description 18
- 238000005259 measurement Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 150000001793 charged compounds Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 235000011176 polyphosphates Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- GDWXPDZDYKOTPH-RYUDHWBXSA-N 4-[(3r,4r)-4-(3,4-dihydroxyphenyl)pyrrolidin-3-yl]benzene-1,2-diol Chemical compound C1=C(O)C(O)=CC=C1[C@H]1[C@H](C=2C=C(O)C(O)=CC=2)CNC1 GDWXPDZDYKOTPH-RYUDHWBXSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 5
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- XPPBXZUEFPKJOH-UHFFFAOYSA-N C1CNCCN1.OP(O)(=O)OC1=CC=CC=C1 Chemical compound C1CNCCN1.OP(O)(=O)OC1=CC=CC=C1 XPPBXZUEFPKJOH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 4
- 150000004885 piperazines Chemical class 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 150000003918 triazines Chemical class 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- JBXOEKAMFYVLNP-UHFFFAOYSA-N diphenyl hydrogen phosphate;piperazine Chemical compound C1CNCCN1.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 JBXOEKAMFYVLNP-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 150000005691 triesters Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 description 2
- JNUCNIFVQZYOCP-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C=C1 JNUCNIFVQZYOCP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WXCXJSOCIOHPLT-UHFFFAOYSA-N 2-[chloro-(2,6-dimethylphenoxy)phosphoryl]oxy-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1OP(Cl)(=O)OC1=C(C)C=CC=C1C WXCXJSOCIOHPLT-UHFFFAOYSA-N 0.000 description 2
- GJXLXCBGGOAWDI-UHFFFAOYSA-N 2-dichlorophosphoryloxy-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1OP(Cl)(Cl)=O GJXLXCBGGOAWDI-UHFFFAOYSA-N 0.000 description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HWWKEEKUMAZJLL-UHFFFAOYSA-N 4-bromo-2,5-dichlorophenol Chemical compound OC1=CC(Cl)=C(Br)C=C1Cl HWWKEEKUMAZJLL-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 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
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 2
- PLUDEAUQZKPAIN-UHFFFAOYSA-N bis(4-methylphenyl) hydrogen phosphate Chemical compound C1=CC(C)=CC=C1OP(O)(=O)OC1=CC=C(C)C=C1 PLUDEAUQZKPAIN-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- GUSFEBGYPWJUSS-UHFFFAOYSA-N pentaazanium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O GUSFEBGYPWJUSS-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FCQGJGLSOWZZON-UHFFFAOYSA-N (2-amino-4-hydroxy-7,8-dihydropteridin-6-yl)methyl trihydrogen diphosphate Chemical compound N1=C(COP(O)(=O)OP(O)(O)=O)CNC2=NC(N)=NC(O)=C21 FCQGJGLSOWZZON-UHFFFAOYSA-N 0.000 description 1
- IDIHGZAZUJGAEB-VMXMFDLUSA-N (9r,10r,13s,17r)-17-acetyl-17-hydroxy-10,13-dimethyl-2,9,11,12,15,16-hexahydro-1h-cyclopenta[a]phenanthren-3-one Chemical compound C1=CC2=CC(=O)CC[C@]2(C)[C@@H]2C1=C1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2 IDIHGZAZUJGAEB-VMXMFDLUSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- RVJABZUDCPZPPM-UHFFFAOYSA-N 1,4,7,10,13,16-hexazacyclooctadecane Chemical compound C1CNCCNCCNCCNCCNCCN1 RVJABZUDCPZPPM-UHFFFAOYSA-N 0.000 description 1
- KDCBVVQAMMXRFB-UHFFFAOYSA-N 1,4,7,10,13-pentazacyclopentadecane Chemical compound C1CNCCNCCNCCNCCN1 KDCBVVQAMMXRFB-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BNDUYVNXBZYPMZ-UHFFFAOYSA-N 1-[chloro-(4-methylphenoxy)phosphoryl]oxy-4-methylbenzene Chemical compound C1=CC(C)=CC=C1OP(Cl)(=O)OC1=CC=C(C)C=C1 BNDUYVNXBZYPMZ-UHFFFAOYSA-N 0.000 description 1
- OSDCKQFKYUESEG-UHFFFAOYSA-N 1-dichlorophosphoryloxy-4-methylbenzene Chemical compound CC1=CC=C(OP(Cl)(Cl)=O)C=C1 OSDCKQFKYUESEG-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SDSUSOOLEPDQPJ-UHFFFAOYSA-N 6-morpholin-4-yl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(N2CCOCC2)=N1 SDSUSOOLEPDQPJ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- BMPDHVMKZMFDRH-UHFFFAOYSA-N 6-thiomorpholin-4-yl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(N2CCSCC2)=N1 BMPDHVMKZMFDRH-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PZLKLYOQJLMJMU-UHFFFAOYSA-N Cc(cc1)ccc1OP(Oc1ccc(C)cc1)(O[N+2](CC1)CCN1[O](C)P(Oc1ccc(C)cc1)(Oc1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1OP(Oc1ccc(C)cc1)(O[N+2](CC1)CCN1[O](C)P(Oc1ccc(C)cc1)(Oc1ccc(C)cc1)=O)=O PZLKLYOQJLMJMU-UHFFFAOYSA-N 0.000 description 1
- SXICDRWHMMQPKV-UHFFFAOYSA-N Cc(cccc1C)c1OP(Oc1c(C)cccc1C)(/[O]=[N+](\CC1)/CC/[N+]1=[O]/P(Oc1c(C)cccc1C)(Oc1c(C)cccc1C)=O)=O Chemical compound Cc(cccc1C)c1OP(Oc1c(C)cccc1C)(/[O]=[N+](\CC1)/CC/[N+]1=[O]/P(Oc1c(C)cccc1C)(Oc1c(C)cccc1C)=O)=O SXICDRWHMMQPKV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- VJEIIJANCJRLFJ-UHFFFAOYSA-N azecane Chemical compound C1CCCCNCCCC1 VJEIIJANCJRLFJ-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- QXNDZONIWRINJR-UHFFFAOYSA-N azocane Chemical compound C1CCCNCCC1 QXNDZONIWRINJR-UHFFFAOYSA-N 0.000 description 1
- NRHDCQLCSOWVTF-UHFFFAOYSA-N azonane Chemical compound C1CCCCNCCC1 NRHDCQLCSOWVTF-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- YRTMEEURRDTMST-UHFFFAOYSA-N diazetidine Chemical compound C1CNN1 YRTMEEURRDTMST-UHFFFAOYSA-N 0.000 description 1
- DJMIKAGANCZWLL-UHFFFAOYSA-N dihydroxy hydrogen phosphate Chemical compound OOP(O)(=O)OO DJMIKAGANCZWLL-UHFFFAOYSA-N 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000026731 phosphorylation Effects 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- 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
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
-
- 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
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Definitions
- the present invention relates to a novel flame retardant and a flame retardant resin composition.
- the present invention relates to a flame retardant containing a cyclic amine salt, a flame retardant resin composition containing the flame retardant, and a molded product thereof. More specifically, it is useful for molding injection-molded articles and extrusion-molded articles. For example, it is suitable for home appliances, OA equipment, automobile parts, wire coating materials, etc. It relates to molded products.
- Polyolefin resins polystyrene resins, polyacrylic resins, polyamide resins, polyester resins, polyether resins, thermoplastic resins such as polycarbonate resins, thermosetting resins such as phenol resins and epoxy resins, or these Resin alloys by combination, for example, various materials in addition to building materials, electrical equipment materials, vehicle parts, automobile interior parts, household goods, etc., depending on the characteristics such as specific mechanical characteristics, thermal characteristics, moldability, etc. Widely used in industrial products.
- halogen-based organic compounds include tetrabromobisphenol A, hexabromocyclododecane, bisdibromopropyl ether of tetrabromobisphenol A, bisdibromopropyl ether of tetrabromobisphenol S, tris 2,3-dibromopropyl isocyanurate, bistribromophenoxy
- halogen-based organic compounds that easily generate harmful gases (hydrogen bromide) during combustion are strongly required to be self-reliant.
- a halogen-based flame retardant For this reason, several methods for imparting flame retardancy to a synthetic resin without using a halogen-based flame retardant have been proposed.
- One of them is a method of adding an inorganic hydroxide such as aluminum hydroxide or magnesium hydroxide.
- the inorganic hydroxide exhibits flame retardancy due to water generated by thermal decomposition, the flame retardancy is not exhibited unless added in a considerably large amount. Due to such a large amount of addition, there is a problem that functions inherent to the resin such as processability and mechanical properties are remarkably lowered.
- phosphates such as ammonium polyphosphate has been proposed as a non-halogen flame retardant.
- this type of phosphates when a large amount of this type of phosphates is added, the phosphates are low in flame retardancy and inferior in moisture resistance, so the appearance and mechanical properties of the molded product are greatly reduced.
- phosphates if a resin molded article made of this flame retardant composition is used under high humidity, phosphates bleed out on the surface, and there are also fatal defects that cause numerous blooming phenomena. .
- Ammonium polyphosphate coated with a surface treatment agent of melamine cross-linking type, phenol cross-linking type, epoxy cross-linking type or silane coupling agent and end-capped polyethylene glycol cross-linking type with improved moisture resistance has also been proposed.
- these have a problem that resin compatibility or dispersibility is poor and high mechanical strength cannot be obtained.
- the coating is broken by heat and stress, and problems similar to the above (problems such as bleeding out due to moisture absorption) often occur.
- condensed ammonium phosphate salts such as ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate are basically water-soluble or water-absorbing substances, and therefore their addition is heat resistance and moisture resistance of the resin composition. Is a direct cause of decline.
- organic salts such as aliphatic amine salts of aromatic phosphoric acid monoesters have been proposed (Patent Documents 5 to 7).
- the aliphatic amine salt of the aromatic phosphoric acid monoester is a water-soluble organic salt having a very strong water absorption property although having a predetermined flame retardancy.
- a monotolylpiperazine phosphate salt represented by the following chemical formula (1) corresponds to this.
- This substance is an onium salt in which tolyl dihydrogen phosphate ion, which is an anionic component, and piperazine ion, which is a cation component, are alternately coordinated, and is highly water-soluble and insoluble in most organic solvents.
- the resin compatibility is also very poor.
- monotolylpiperazine phosphate has low heat resistance, and particularly when it is kneaded as a resin composition, a large amount of highly toxic p-cresol gas is generated by thermal decomposition at a kneading temperature of 180 to 200 ° C. It has a fatal defect that it is not practically satisfactory.
- the main object of the present invention is to solve the problems of the prior art and to provide a flame retardant capable of imparting more excellent flame retardancy, and further to a flame retardant resin composition containing the composition and molding the same. It is to provide a molded article.
- a flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
- Y represents an imino group.
- Z represents an oxygen atom, a sulfur atom or an imino group.
- n represents an integer of 1 to 10.
- m represents an integer of 0 to 9.
- l represents an integer of 1 to 10.
- R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- Y represents an imino group.
- Z represents an oxygen atom, a sulfur atom or an imino group.
- m represents an integer of 0 to 9. ] 2.
- the flame retardant composition according to item 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component 0.8 / 1.0 to 1.0 / 1.2 . 3.
- Item 2 The flame retardant composition according to Item 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition. 4).
- Item 2 The flame retardant composition according to Item 1, further comprising at least one phosphate. 5.
- a flame retardant composition comprising the flame retardant composition according to item 1 and a resin component, the flame retardant comprising 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component Resin composition. 6). 5.
- a resin composition comprising the flame retardant composition according to item 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates
- a flame retardant resin composition comprising 1 to 50 parts by weight. 7.
- Item 7 The flame retardant resin composition according to Item 5 or 6, wherein the resin component is a polyolefin resin. 8).
- Item 9 The flame-retardant resin molded article according to Item 8, which is used for electrical / electronic parts, OA equipment parts, household electrical equipment parts, automotive parts or equipment mechanism parts.
- R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
- Y represents an imino group.
- Z represents an oxygen atom, a sulfur atom or an imino group.
- n represents an integer of 1 to 10.
- m represents an integer of 0 to 9.
- l represents an integer of 1 to 10.
- IV The following general formula (IV) [Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ] Is reacted with phosphorus oxyhalide in the presence of an amine, The following general formula (V) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- a method for producing a cyclic amine salt of an aromatic phosphoric diester comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).
- the flame retardant of the present invention contains a cyclic amine salt having a specific chemical structure, it can exhibit flame retardancy superior to conventional flame retardants. Therefore, the desired flame retardancy can be imparted even with a relatively small amount of addition. That is, it is possible to provide excellent flame retardancy while effectively maintaining the original characteristics of the material to be added (resin etc.).
- the flame retardant of the present invention is excellent in moisture resistance, problems such as bleeding out and blooming due to moisture absorption, and deterioration of flame resistance due to bleeding out can be effectively suppressed or prevented.
- the cyclic amine salt which is an active ingredient of the flame retardant of the present invention, does not contain a halogen element in the molecule, it can effectively suppress the generation of harmful gases even when the flame retardant resin and the molded product burn. it can.
- the present invention when applied as a flame retardant such as a polyolefin resin, it is possible to exhibit excellent flame retardancy with a smaller amount of flame retardant by using phosphates together with the cyclic amine salt. it can.
- phosphates such as polyphosphates have high water solubility or high water absorption.
- the flame-retardant resin composition and molded product containing phosphate as a flame retardant cannot effectively suppress mold deposits and bleed-out (or blooming) of the flame retardant.
- the flame-retardant resin composition and molded product containing the flame retardant of the present invention can highly compatibilize polyphosphates with the resin while maintaining good physical properties of various resins.
- the flame retardant of the present invention can be suitably used as a flame retardant for adding to a material containing an organic component, for example.
- it can be preferably used as a flame retardant for addition to a composition containing a resin component (for example, a composition containing 50% by weight or more of a resin component).
- the flame retardant for resin of the present invention is 1) an aromatic phosphate diester as an anionic component and 2) A flame retardant comprising a cyclic amine salt of an aromatic phosphoric diester composed of a cyclic amine which is a cationic component,
- the cyclic amine salt of the aromatic phosphoric diester is The following general formula (I) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
- Y represents an imino group.
- Z represents an oxygen atom, a sulfur atom or an imino group.
- n represents an integer of 1 to 10.
- m represents an integer of 0 to 9.
- l represents an integer of 1 to 10.
- a cyclic amine salt of an aromatic phosphoric acid diester represented by the formula:
- the aromatic phosphoric diester cyclic amine salt represented by the following general formula (I) (hereinafter also referred to as “the present cyclic amine salt”) functions as an active ingredient of the present flame retardant.
- the flame retardant of the present invention contains one or more of the cyclic amine salts of the present invention.
- the cyclic amine salt of the present invention contains an aromatic phosphate diester as an anion component (component A) and is composed of a cyclic amine as a cation component (component B).
- component A aromatic phosphate diester
- component B a cyclic amine as a cation component
- a known or commercially available one can also be used.
- the cyclic amine salt of the present invention will be described separately for component A and component B.
- a component The aromatic phosphoric acid diester which comprises A component among cyclic amine salt of this invention is shown by the following general formula (II). [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
- R 1 to R 10 in the general formula (II) represent a hydrogen atom or a hydrocarbon group which may have a substituent. Further, each of R 1 to R 10 may be the same substituent as each other, or may be different from each other. In particular, in the present invention, R 1 to R 10 are more preferably a hydrogen atom than an optionally substituted hydrocarbon group from an economical viewpoint.
- the hydrocarbon group is not particularly limited, and may be any of a chain (which may be either a straight chain or a branched chain) or a ring (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring). Also good.
- a cyclic hydrocarbon group having a side chain can also be used.
- the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- hydrocarbon group examples include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group.
- the total number of carbon atoms of these hydrocarbon groups is not limited, but is generally about 1 to 18, and preferably about 1 to 4. . More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and the like can be exemplified.
- a substituent may be introduced into the hydrocarbon group.
- substituents include an amino group, hydroxyl group, alkoxyl group, nitro group, cyano group, carbonyl group, aldehyde group, carboxyl group, sulfone group, and sulfhydryl group.
- R 1 , R 3 , R 5 , R 6 , R 8 and R 10 are hydrogen atoms or methyl groups, and R 2 , R 4 , R 7 and R 9. Is a hydrogen atom.
- aromatic phosphoric acid diester represented by the general formula (I) include compounds represented by the following formulas (1) to (5). As these compounds themselves, known or commercially available compounds can also be used.
- the cyclic amine constituting the B component is represented by the following general formula (III).
- A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
- Y represents an imino group.
- Z represents an oxygen atom, a sulfur atom or an imino group.
- m represents an integer of 0 to 9.
- m 0, for example, piperidine, pyrrolidine and the like are applicable.
- alkylene group examples include a methylene group, an ethylene group, a propylene group, and a butylene group.
- an alkylene group having 2 to 6 carbon atoms is particularly preferable.
- a cyclic amine for example, a compound in which one or more imino groups (—NH—) are cyclically bonded through an oxygen atom, a sulfur atom or an imino group and an alkylene group can be used. More preferably, a cyclic amine in which two or more imino groups are bonded cyclically via an alkylene group is used.
- cyclic amine examples include aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, azonan, azecan, diazetidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, 1,4,7-triazacyclononane. 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13-pentaazacyclopentadecane, 1,4,7,10,13,16-hexaazacyclooctadecane and the like.
- cyclic amine A cyclic amines or cyclic polyamines can be appropriately selected and used.
- cyclic amines include pyrrolidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, and the like.
- the cyclic polyamines include cyclic polyamines in which two or more combinations of imino group (—NH—) and ethylene group (—CH 2 —CH 2 —) are linked in a cyclic manner.
- piperazine is most preferable from the viewpoint of being inexpensive and easy to obtain.
- cyclic amine represented by the general formula (III) include compounds represented by the following formulas (6) to (10).
- the cyclic amine salt of the present invention those having high heat resistance during kneading or molding with a resin component can be suitably used.
- the cyclic amine A is preferably a secondary amine or a tertiary amine rather than a primary amine.
- a cyclic amine can be used more suitably than an aliphatic amine having low heat resistance.
- the component ratio of the A component and the B component in the cyclic amine salt of the present invention is not particularly limited, but in order to more effectively retain flame retardancy, moisture resistance, etc., the respective ion equivalents of the A component and the B component Are preferably equal.
- each ion equivalent By making each ion equivalent equal, the content of excess ionic components can be lowered, so that the expression of water solubility or hygroscopicity can be effectively suppressed or prevented, resulting in poor appearance of molded products, etc. In addition, deterioration of physical properties can be avoided.
- cyclic amine salt of the present invention The role of the cyclic amine salt of the present invention in the flame retardant resin composition of the present invention and its molded article is not only to function as a flame retardant, but also to a moisture absorption inhibitor, blooming inhibitor, etc. Can exhibit various functions.
- specific examples of the more preferred cyclic amine salt of the present invention are shown by the following formulas (11) to (16) when piperazine is selected as a preferred example of the constituent B component. Compounds.
- the cyclic amine salt of the aromatic phosphoric acid diester obtained by a well-known manufacturing method can also be used.
- the cyclic amine salt of the present invention can be produced by a known production method, but is particularly preferably produced by the production method of the present invention.
- triphenyl phosphate (triester form) can be preferentially synthesized with good yield.
- synthesis route of the above publication it is difficult to selectively synthesize preferentially only monochlorodiphenyl phosphate (diester).
- the compound represented by the chemical formula (IV) is reacted with phosphorus oxyhalide in the presence of an amine via the compound represented by the general formula (V).
- This is a synthetic route for producing a cyclic amine salt represented by the general formula (I).
- the target compound can be obtained directly in one pot with higher yield. More specifically, in each process leading to the synthesis of the cyclic amine salt of the present invention which is the target compound, the intermediate product can be continuously transferred to the next process without performing the isolation and production process.
- the production method of the present invention in the production of the cyclic amine salt of the present invention.
- the production method of the present invention comprises: (1) The following chemical formula (IV) [Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ] Is reacted with phosphorus oxyhalide in the presence of an amine, The following general formula (V) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
- a step of obtaining a compound represented by the general formula (I) by adding a compound represented by formula (I) in an organic solvent (step C) It is a manufacturing method containing.
- Step A an amine is added to a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction.
- a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction.
- ) -Containing halogen-containing aromatic phosphate ester derivatives.
- the amine added at this time functions as a catalyst that efficiently promotes the selective ester reaction.
- the compound represented by the general formula (IV) may be reacted using commercially available phenol and phosphorus oxyhalide as raw materials.
- phosphorus oxyhalide for example, phosphorus oxychloride, phosphorus oxybromide and the like can be used. If phosphorus oxychloride is used, the halogen atom of the compound represented by the general formula (V) becomes chlorine. If phosphorus oxybromide is used instead of phosphorus oxychloride, the halogen atom of the compound represented by the general formula (V) is bromine.
- an amine is allowed to coexist in the reaction system as a catalyst for efficiently promoting the selective esterification reaction.
- the type of amine is not particularly limited.
- triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] At least one of -5-nonene, 4-dimethylaminopyridine and the like.
- triethylamine is preferable from an economical viewpoint.
- an amine that serves as a dehydrohalogenation catalyst is added to both the phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) at about room temperature (about 10 to 40 ° C.).
- the reaction temperature is lower than 10 ° C., the reaction rate decreases, so the reaction time becomes longer.
- the reaction temperature exceeds 40 ° C., the reaction runs away, and by-products such as triesters are generated in addition to the diesters represented by the general formula (V), resulting in a reduction in reaction yield. There is.
- the mixing ratio of each raw material is about 0.4 to 0.6 mol, preferably about 0.45 to 0.55 mol of phosphorus oxyhalide with respect to 1 mol of the phenol derivative represented by the general formula (IV). Just do it. Further, the amount of amine is about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, per mol of the phenol derivative represented by the general formula (IV). When the charging ratio of the raw material is out of the above range, there is a risk that by-products such as monoesters and triesters other than the diesters represented by the general formula (V) may be generated.
- an amine hydrogen halide salt is always generated, and therefore the above reaction is preferably carried out in a solvent.
- the solvent include, but are not limited to, hydrocarbon solvents such as benzene, toluene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; aprotic organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform.
- a solvent etc. can be used conveniently.
- the amine hydrohalide salt is made into an aqueous solution and separated. It is necessary to remove the aqueous hydrogen halide salt solution. Therefore, in order to perform a continuous reaction, it is more preferable to use a water-insoluble light solvent (a solvent having a specific gravity lighter than water) as the reaction solvent.
- a water-insoluble light solvent a solvent having a specific gravity lighter than water
- the aromatic phosphate diester represented by the general formula (II) it is preferable to continuously synthesize the aromatic phosphate diester represented by the general formula (II) in the same reaction vessel.
- the amine hydrogen halide salt formed as a by-product in the previous reaction is made into an aqueous solution as described above and separated into layers, and the diester represented by the general formula (V) (present in the organic solvent layer) is obtained by liquid-liquid extraction.
- the hydrolysis reaction proceeds slightly from the diester represented by the general formula (V), and is acidic in the general formula (II). Since it is considered that the phosphoric acid diester is generated and slightly moves from the organic solvent layer to the aqueous layer, the reaction yield may be lowered as a result.
- step A the phenol derivative represented by the general formula (III) and the oxyhalogenation necessary for obtaining one equivalent of the aromatic phosphoric diester represented by the general formula (II)
- the charging ratio of phosphorus is about 1 equivalent for the phenol derivative and about 0.5 equivalent for phosphorus oxyhalide, which is very economically advantageous because it can be synthesized without loss of stoichiometry.
- Step B an aromatic phosphate diester is synthesized by hydrolyzing a halogen-containing aromatic phosphate ester derivative. That is, in order to obtain the aromatic phosphoric acid diester represented by the general formula (II) from the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V), Hydrolysis may be promoted by adding water to the halogen-containing aromatic phosphate ester derivative.
- the amount of water required for the hydrolysis can be obtained by adding a stoichiometric amount of water equal to or greater than the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V). It ’s fine.
- the reaction temperature is not critical, but the stirring is preferably performed at a temperature not lower than room temperature (particularly a temperature exceeding 40 ° C.), more preferably 80 to 120 ° C.
- the organic solvent used in the previous reaction may be used continuously as it is, or another organic solvent may be used in addition, and after the organic solvent in the reaction system is removed under reflux. You may perform the solvent exchange which throws in another organic solvent in a reaction system.
- the kind of solvent that can be used the same solvents as those mentioned in the above step A can be used.
- step B the removal of excess water after hydrolysis can also remove the aromatic phosphate monoester, which is slightly by-produced, out of the reaction system.
- Aromatic phosphoric acid monoesters are very water-soluble, so when liquid-liquid extraction is performed, the aromatic phosphoric acid monoester does not exist in the organic solvent layer and moves completely to the aqueous layer, contrary to the aromatic phosphoric acid diester.
- the cyclic amine salt of the aromatic phosphoric acid monoester and the cyclic amine salt of the aromatic phosphoric acid diester also exhibit the above-described properties.
- non-uniform hydrolysis of the water-insoluble organic solvent layer and the water layer not only contributes to the one-pot continuous reaction, but also increases the selectivity of the monoester and diester forms. It can be said that this is an excellent synthesis method that contributes to this.
- the aromatic phosphate diester can be recovered in accordance with a known purification method, solid-liquid separation method, etc., so that it is prepared separately when the flame retardant is kneaded into the resin after the recovery.
- the dry aromatic phosphate diester and the cyclic amine are dry blended, they may be added to the resin component.
- aromatic phosphoric diesters do not have very strong water absorption, but most cyclic amines and cyclic polyamines are water-absorbing or hydrated. It is necessary to do this, and it may take much time to obtain the flame retardant of the present invention later.
- Step C the aromatic amine represented by the general formula (I) is continuously added by adding a cyclic amine represented by the general formula (III) to the reaction system after the completion of the step B and stirring and mixing.
- a phosphoric diester cyclic amine salt can be synthesized.
- the amount of cyclic amine represented by the general formula (III) is represented by the general formula (II) so that the ionic equivalents of both are equal to each other in order to maintain high flame retardancy and moisture resistance as described above. It is preferable to add an equal amount of an appropriately selected cyclic amine salt with respect to the stoichiometric amount contained in the aromatic phosphate diester.
- a known or commercially available cyclic amine may be used as the cyclic amine represented by the general formula (III).
- the C step it can be carried out in a solvent as necessary.
- the solvent include hydrocarbon solvents such as benzene, toluene and n-hexane; alcohol solvents such as methanol and isopropyl alcohol; halogenated hydrocarbon solvents such as dichloromethane and chloroform.
- the cyclic amine salt of the present invention can be recovered according to a known purification method, solid-liquid separation method, or the like.
- synthesizing the cyclic amine salt of the present invention represented by the general formula (I) by the production method of the present invention it can be produced with a very high yield and can be efficiently produced.
- the target product can be obtained in a very high yield of 80% or more (relative to the phenol derivative) in the total process yield.
- cyclic amine salts of the present invention for example, when diphenyl hydrogen phosphate (DPHP) is selected as the aromatic phosphate diester represented by the general formula (II), and piperazine is selected as the cyclic amine represented by the general formula (III),
- DPHP diphenyl hydrogen phosphate
- piperazine is selected as the cyclic amine represented by the general formula (III)
- DPHP phosphorus
- the flame retardant composition of the present invention contains one or more of the cyclic amine salts of the present invention. That is, it contains at least one of the cyclic amine salts shown in (1) as an active ingredient.
- the presence of an aromatic phosphate monoester that can be mixed in the cyclic amine salt causes deterioration of the performance. Therefore, the smaller the amount of the aromatic phosphate monoester mixed in the flame retardant of the present invention, the better. That is, the content of the aromatic phosphoric acid monoester in the flame retardant of the present invention is preferably 1% by weight or less, more preferably 0.1% by weight or less, and further preferably 0% by weight. Is most preferred.
- the abundance ratio of the aromatic phosphoric acid monoester and the aromatic phosphoric acid diester as the component A can be examined by measuring, for example, LC / MS or GC / MS. Further, by measuring 31 P-NMR, it can be easily confirmed that the chemical shift of the diester is about ⁇ -12 to -10 ppm and the chemical shift of the monoester is about ⁇ -3 to -4 ppm. it can.
- the flame retardant of the present invention may contain additives blended with known flame retardants in addition to the cyclic amine salt of the present invention.
- phosphates can be preferably used in the flame retardant of the present invention. Even if only phosphates are used as flame retardants, it is very difficult to simultaneously acquire flame retardancy, moisture resistance, and blooming resistance.
- the cyclic amine salt of the present invention and phosphates should be contained at the same time. Thus, in addition to highly enhancing the flame retardancy and moisture resistance, it is possible to obtain an effect of more effectively preventing the blooming phenomenon.
- phosphates are basically difficult to mix with the synthetic resin and difficult to stabilize.
- the cyclic amine salt of the present invention is superior to the prior art in that it functions as a dispersion stabilizer and / or a compatibilizer in the synthetic resin with respect to phosphates. is there.
- phosphates For example, 1) Inorganic condensed ammonium phosphate salts, such as ammonium polyphosphate, 2) Inorganic condensed ammonium phosphate salts, such as coated ammonium polyphosphate, 3) Phosphoric acid, pyrroline Examples thereof include at least one of organic salts composed of an acid or condensed phosphoric acid and a triazine derivative.
- inorganic condensed ammonium phosphate such as ammonium polyphosphate
- examples of commercially available products of inorganic condensed ammonium phosphates such as C component 1) inorganic condensed ammonium phosphate such as ammonium polyphosphate include product names “Exorit AP422”, “Exorit AP700” (both manufactured by Clariant), and product names “Terrage S”. -10 ",” Terrage S-20 “(all manufactured by Chisso Corporation), and the product name” Sumisafe P "(manufactured by Sumitomo Chemical Co., Ltd.).
- the coated inorganic condensed ammonium phosphate salt such as ammonium polyphosphate coated with component C may be microencapsulated with a thermosetting resin to compensate for the disadvantages of the ammonium polyphosphate salt that is easily hydrolyzed by moisture absorption. Further, surface treatment such as coating is performed by melamine cross-linking, and surface treatment of granules is performed by a surfactant, a silicon compound, or the like. Examples of these commercially available products are product names “Exorit AP462” (manufactured by Clariant), product names “Terrage C-30”, “Terrage C-60”, “Terrage C-70”, “Terrage C-80” ( All of them are manufactured by Chisso Corporation).
- organic salts composed of 3) phosphoric acid, pyrophosphoric acid or condensed phosphoric acid of the C component and an amine composed of a triazine derivative include melamine, guanamine, methylguanamine, ethylguanamine, benzoguanamine, benzylguanamine, Guanidine, guanidine, phosphates of triazine derivatives such as 2,4-diamino-6-morpholino-1,3,5-triazine, 2,4-diamino-6-thiomorpholino-1,3,5-triazine, pyrroline An acid salt, and a polyphosphate condensed with three or more molecules of phosphoric acid.
- a flame retardant composition containing at least one phosphate among the C components is mixed with various resin components to make a synthetic resin composition and the like highly advanced.
- the flame retardant of the present invention is a char-forming phosphorus / nitrogen flame retardant, but typical char-forming flame retardants include red phosphorus, polyphosphate amine salts, most phosphate esters, and triazine derivatives. Susceptible to moisture. That is, characteristics of phosphorus compounds that are fatal defects as flame retardants, such as generation of phosphine (PH 3 ) gas derived from red phosphorus, occurrence of blooming phenomenon derived from polyphosphate amine salt, hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitrogen) -based decomposition gas, resin coloring and molecular weight reduction are caused by moisture caused by moisture absorption and active radicals derived from moisture.
- phosphine (PH 3 ) gas derived from red phosphorus occurrence of blooming phenomenon derived from polyphosphate amine salt
- hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitro
- the most important performance in practical use as a char-forming phosphorus-based flame retardant is to impart high flame resistance to the synthetic resin and at the same time have high moisture absorption resistance.
- Some flame retardants composed of phosphate esters have excellent resin compatibility, but most liquids have a low melting point and low thermal decomposition starting temperature, so the plasticity is too strong and the moldability is low. In many cases, the flame retardancy may be lowered, and high flame retardancy may not be imparted to the molded product.
- the cyclic amine salt of the present invention alone is a non-hygroscopic flame retardant, but the cyclic amine salt of the present invention is also contained in the resin even when a C component having hygroscopicity is added at the same time in order to further enhance the flame retardancy. Since it acts as a kind of protective buffer that can stably disperse or compatibilize the components, it suppresses hygroscopicity and also maintains dispersion uniformity in the resin of the flame retardant composition. Transferability to the product surface, blooming phenomenon, or surface roughness of the molded product can be suppressed at the same time.
- Flame retardant resin composition containing the flame retardant of the present invention (the composition of the present invention)
- Flame Retardant Resin Composition is a resin composition comprising the flame retardant of the present invention and a resin component, and comprises 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. Includes flammable resin composition.
- the resin component is not particularly limited, and can be selected from, for example, known synthetic resins. More specifically, polyolefin resins, polystyrene resins, polyvinyl resins, polyamide resins, poly-meaning clock resins, polyester resins, polyether resins, polycarbonate resins, polyacetal resins, polyether ether ketone resins. , Thermoplastic resins such as polyphenylene / sulfide resin, polyamide / imide resin, polyether / sulfone resin, polysulfone resin, polymethyl / pentene resin, urea resin, melamine resin, epoxy resin, polyurethane resin, phenol resin, etc. And resin alloys by homopolymers or copolymers alone or in combination thereof.
- Suitable polyolefin resins in the composition of the present invention include homopolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above ⁇ - Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used.
- ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above ⁇ - Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used.
- polypropylene resins such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer, low density ethylene homopolymer
- polyethylene resins such as high-density ethylene homopolymer, ethylene- ⁇ -olefin random copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer.
- a polyethylene-based synthetic rubber, a polyolefin-based synthetic rubber, or the like can be blended as necessary.
- polystyrene resin examples include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.
- polyvinyl resin examples include homopolymers of vinyl monomers such as alkyl acrylates, alkyl methacrylates, vinyl acetate, vinyl alcohol and the like, and copolymers of these vinyl monomers and the aforementioned ⁇ -olefins. Etc.
- polyamide-based resin examples include polyamide 6, polyamide 6 • 6, polyamide 11, polyamide 12, polyamide 6 • 3, polyamide 6 • 4, polyamide 4 • 6, polyamide 6 • 10, and the like.
- polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate), and the like.
- polyether resins examples include polyphenylene ether and polyethylene ether.
- polycarbonate resin examples include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like.
- bisphenol such as 2,2-bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, etc.
- Polymers or copolymers consisting of the above are mentioned.
- alloy resins include polypropylene / polyamide, polypropylene / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polyamide, and polycarbonate / acrylonitrile / butadiene / styrene copolymer.
- a modified product of the above-described synthetic resin for example, a synthetic resin is obtained by unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.)
- unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.
- the combination of the polyolefin resin and the flame retardant of the present invention is particularly preferred from the viewpoint that a molded product having higher versatility, lower cost, and balance of various physical properties can be obtained.
- a flame retardant resin composition containing at least one of a polypropylene homopolymer, an ethylene-propylene random copolymer, and an ethylene-propylene block copolymer and the flame retardant of the present invention has moldability, heat resistance, and moisture absorption resistance. With regard to the properties and particularly high flame retardancy, it is more preferable because it can exhibit particularly excellent performance that has not been achieved in the past.
- the blending ratio of the cyclic amine salt of the present invention is not particularly limited, and a blending amount sufficient to maintain various physical properties and flame retardancy may be added.
- the cyclic amine salts 1 to 100 of the present invention are added to 100 parts by weight of the resin component in order to keep the kneading stability and moldability, and to give the molded article moisture resistance and high flame retardancy. What is necessary is just to mix
- the char forming ability characteristic of the composition of the present invention is enhanced by the effect of promoting carbonization by foaming (phosphorus such as amine, triazine and melamine).
- phosphorus such as amine, triazine and melamine
- the blending ratio is 1 to 50 parts by weight of the cyclic amine salt of the present invention and 1 to 50 parts by weight of the C component with respect to 100 parts by weight of the resin component.
- the cyclic amine salt of the present invention is preferably 10 to 30 parts by weight, and the C component is more preferably 10 to 30 parts by weight.
- composition of the present invention can be appropriately blended with known or commercially available additives as necessary within the range not impeding the effects of the present invention.
- antioxidants such as phenol compounds, phosphine compounds, thioether compounds, UV absorbers or light stabilizers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, hindered amine compounds; cationic compounds, anions Compounds, nonionic compounds, amphoteric compounds, metal oxides, ⁇ -based conductive polymer compounds, carbon and other antistatic agents and conductive agents; fatty acids, fatty acid amides, fatty acid esters, fatty acid metal salts and other lubricants; benzylidene sorbitols Nucleating agents such as compounds; in addition to fillers such as talc, calcium carbonate, barium sulfate, mica, glass fiber, glass beads, low melting glass, metal deactivators, colorants, antiblooming agents, surface modifiers, Anti-
- polytetrafluoroethylene-containing mixed particle powder having fibril forming ability can be added as the drip control agent of the composition of the present invention. Addition of polytetrafluoroethylene-containing mixed particle powder having fibril-forming ability enables drip of test pieces during combustion in a flammability test of a flame retardant resin composition, particularly in a UL standard vertical combustion test (UL94V) The prevention performance can be further increased.
- UL94V UL standard vertical combustion test
- polytetrafluoroethylene-containing mixed particle powder having a fibril-forming ability examples include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer, and polytetrafluoroethylene (PTFE) is preferable.
- PTFE polytetrafluoroethylene
- the average particle size of the powder is not limited, but it is usually about 0.1 to 1000 ⁇ m.
- the addition amount can be appropriately set according to the desired drip prevention performance and the like, but is generally preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component.
- composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can manufacture by melt-kneading said each component.
- the kneading order in that case is not particularly limited, either may be mixed at the same time, or several types may be mixed in advance and the rest may be mixed later.
- the mixing method is not limited.
- a high-speed stirrer such as a tumbler type V-type blender, a Henschel mixer, or a ribbon mixer, a single-screw or twin-screw continuous kneader, or a method that uses a roll mixer alone or in combination. Can be adopted.
- a synthetic resin and a high-concentration composition can be prepared using several types of master batches in advance, and then further mixed and diluted with the resin to obtain a predetermined resin composition.
- the composition of the present invention achieves excellent flame retardancy and can effectively suppress bleed, and therefore can be suitably used as a molded product. That is, the flame retardant resin composition of the present invention can be suitably used as a resin composition for producing a molded product. Thereby, the molded article excellent in the flame retardance can be provided.
- the present invention includes a flame retardant resin molded article obtained by molding the flame retardant resin composition of the present invention.
- the molding method is not particularly limited, and known molding methods such as injection molding and extrusion molding can be used.
- known molding methods such as injection molding and extrusion molding can be used.
- a method using an extrusion molding machine, a sheet once prepared, a method using secondary processing such as vacuum molding and press molding, a method using an injection molding machine, and the like can be mentioned, but the present invention is highly versatile.
- injection molding is preferred.
- a molded product can be manufactured not only by a normal cold runner injection molding method but also by a hot runner method that enables runnerless operation.
- gas assist injection molding, injection compression molding, ultra-high speed injection molding, or the like can be employed.
- the molded article made of the flame-retardant resin composition of the present invention can be applied to uses that require flame retardancy in home appliances, OA products, automobile fields, and the like.
- insulation coating materials such as electric wires and cables or various electric parts, meter boxes, lamp housings, corrugated tubes, electric wire coating materials, various automobiles such as battery parts, ships, aircraft parts, wash basin parts, toilet parts,
- Various bathroom equipment parts, floor heating parts, lighting fixtures, various housing equipment parts such as air conditioners, roofing materials, ceiling materials, wall materials, flooring materials, TVs, radios, recording / recording equipment, washing machines, refrigerators, cleaning It is suitably used for home appliances such as a machine, rice cooker, and lighting equipment.
- a calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and stirring was then started in a nitrogen atmosphere while maintaining the flask at 30 ° C. in a constant temperature water bath. After the start of stirring, triethylamine was dropped from the dropping funnel over 2 hours so that the temperature of the reaction product did not exceed 40 ° C. After the reaction ripening for 1 hour from the end of the dropwise addition, the reaction product was sampled and GC / MS was measured. As a result, the purity of the obtained reaction intermediate of the slightly yellow transparent liquid was 98% or more.
- reaction product was converted to a diphenyl hydrogen phosphate piperazine salt represented by the above formula (19) ( DHPPP).
- phenyl dihydrogen phosphate piperazine salt (PDHPP) 110.85 g (0.64 mol) of phenyl dihydrogen phosphate and 998 g of methanol were charged into a four-necked flask equipped with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer. To the dropping funnel with a side tube, 86.14 g (0.64 mol) of piperazine previously dissolved in 494 g of methanol was added. After the start of stirring, the piperazine solution was dropped from the dropping funnel over 1 hour at room temperature, and further stirring was continued for 1 hour after completion of the dropping, whereby a white cotton-like product was precipitated.
- PDHPP phenyl dihydrogen phosphate piperazine salt
- a flame retardant synthetic resin composition was prepared using the cyclic amine salt obtained in each of the above synthesis examples.
- the component which comprises a flame-retardant synthetic resin composition consists of a synthetic resin and a flame retardant, and shows each component below.
- the following components were dry blended according to the blending ratio (parts by weight) described in Tables 1 and 2, and then melt-mixed and extruded and kneaded in a twin-screw extruder, cut into strands, and pellets.
- a flame retardant resin composition was obtained.
- Flammability Evaluation of flammability is based on the UL94 vertical combustion test method, and 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness UL test pieces are prepared and a combustion test is performed. went. As a result of the UL94 vertical combustion test, a four-level evaluation of “V-0”, “V-1”, “V-2”, and “impossible” was performed.
- Bleed test A black flat plate test piece (with 1 phr of carbon black added) having a thickness of 2 mm / 3 mm was prepared and heated at 150 ° C. for 7 days, and then the test piece was aged for 48 hours at 23 ° C. and 50% Rh.
- test piece was subjected to an aging treatment for 48 hours under the conditions of 23 ° C. and 50% Rh, and then the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed.
- the results of the moisture resistance test are “ ⁇ (no seepage)”, “ ⁇ (some exudation is seen)”, “ ⁇ (significant seepage or blooming is observed). It was evaluated in three stages.
- the aromatic phosphate diester when the aromatic phosphate diester, aromatic phosphate monoester and ammonium polyphosphate are used in combination, the aromatic phosphate diester has high moisture absorption, so that the aromatic phosphate diester has moisture resistance and bleed resistance. Inhibited (Comparative Examples 13 to 14).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Disclosed is a fire retarding agent that is for a resin, does not contain a halogen, has excellent fire retarding properties, and suppresses problems with moisture resistance and blooming. Specifically disclosed are: a fire retarding agent containing a cyclic amine salt having a particular chemical structure; and a fire retarding resin composition that contains said fire retarding agent and a resin component and that contains 1-100 parts by weight of said cyclic amine salt for every 100 parts by weight of the resin component.
Description
本発明は、新規な難燃剤及び難燃性樹脂組成物に関する。特に、環状アミン塩を含む難燃剤、当該難燃剤を含有する難燃性樹脂組成物及びその成形品に関する。より詳しくは、射出成形品及び押出成形品の成形で有用であり、例えば家電製品、OA機器、自動車部品、電線被覆材料等として適した、環境負荷の少ないノンハロゲン系難燃性合成樹脂組成物及び成形品に関する。
The present invention relates to a novel flame retardant and a flame retardant resin composition. In particular, the present invention relates to a flame retardant containing a cyclic amine salt, a flame retardant resin composition containing the flame retardant, and a molded product thereof. More specifically, it is useful for molding injection-molded articles and extrusion-molded articles. For example, it is suitable for home appliances, OA equipment, automobile parts, wire coating materials, etc. It relates to molded products.
ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリアクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂等の熱可塑性樹脂、フェノール樹脂、エポキシ樹脂等の熱硬化性樹脂、あるいはこれらの組み合わせによる樹脂アロイ類は、それぞれ特有の機械的特性、熱的特性、成形加工性等の特徴に応じて、例えば建築材料、電気機器用材料、車輌部品、自動車内装部品、家庭用品のほか、種々の工業用品に幅広く使用されている。
Polyolefin resins, polystyrene resins, polyacrylic resins, polyamide resins, polyester resins, polyether resins, thermoplastic resins such as polycarbonate resins, thermosetting resins such as phenol resins and epoxy resins, or these Resin alloys by combination, for example, various materials in addition to building materials, electrical equipment materials, vehicle parts, automobile interior parts, household goods, etc., depending on the characteristics such as specific mechanical characteristics, thermal characteristics, moldability, etc. Widely used in industrial products.
しかし、これらの合成樹脂は一般的に燃焼しやすいという欠点を有しているため、合成樹脂を難燃化するための種々の方法が多数提案されている。一般的な合成樹脂の難燃化の方法は、難燃剤を樹脂に配合する方法が採用されている。従来の難燃化するための方法のうち、最も使用されている例が、酸化アンチモンとハロゲン系有機化合物を添加する方法である。ハロゲン系有機化合物としては、テトラブロモビスフェノールA、ヘキサブロモシクロドデカン、テトラブロモビスフェノールAのビスジブロモプロピルエーテル、テトラブロモビスフェノールSのビスジブロモプロピルエーテル、トリス2,3-ジブロモプロピルイソシアヌレート、ビストリブロモフェノキシエタン、ヘキサブロモベンゼン、デカブロモビフェニルエーテル、デカブロモビフェニルエタン等が挙げられる。
However, since these synthetic resins generally have the disadvantage of being easily combusted, many various methods for making the synthetic resins flame-retardant have been proposed. As a general method for flame-retarding a synthetic resin, a method of blending a flame retardant with a resin is employed. Of the conventional methods for making flame retardant, the most used example is a method of adding antimony oxide and a halogen-based organic compound. Examples of halogen-based organic compounds include tetrabromobisphenol A, hexabromocyclododecane, bisdibromopropyl ether of tetrabromobisphenol A, bisdibromopropyl ether of tetrabromobisphenol S, tris 2,3-dibromopropyl isocyanurate, bistribromophenoxy Examples include ethane, hexabromobenzene, decabromobiphenyl ether, decabromobiphenyl ethane, and the like.
ところが、近年の世界的な環境問題への取り組みを考慮すると、燃焼時に有害ガス(臭化水素)が発生しやすいハロゲン系有機化合物は、使用の自粛が強く求められている。このため、ハロゲン系難燃剤を使用せずに合成樹脂に難燃性を付与させるいくつかの方法が提案されている。そのうちの一つが水酸化アルミニウム、水酸化マグネシウム等の無機水酸化物を添加する方法である。しかし、無機水酸化物は、熱分解で生じる水により難燃性が発現されるため、かなり多量に添加しなければ難燃性が発現しない。かかる大量添加のため、加工性、機械的性質等の樹脂本来が有する機能を著しく低下させてしまうという問題がある。
However, in view of recent efforts to deal with global environmental problems, halogen-based organic compounds that easily generate harmful gases (hydrogen bromide) during combustion are strongly required to be self-reliant. For this reason, several methods for imparting flame retardancy to a synthetic resin without using a halogen-based flame retardant have been proposed. One of them is a method of adding an inorganic hydroxide such as aluminum hydroxide or magnesium hydroxide. However, since the inorganic hydroxide exhibits flame retardancy due to water generated by thermal decomposition, the flame retardancy is not exhibited unless added in a considerably large amount. Due to such a large amount of addition, there is a problem that functions inherent to the resin such as processability and mechanical properties are remarkably lowered.
ハロゲン系難燃剤を使用しない別方法として、トリフェニルホスフェート、トリクレジルホスフェート等の有機リン化合物を用いる方法がある。しかし、これらの有機リン化合物はリン酸エステル型難燃剤に属するものであり、ポリエステル等の合成樹脂と高温で加熱混練した場合にはエステル交換反応を起こし、合成樹脂の分子量を著しく低下させ、合成樹脂本来の物性を損なう結果となる。しかも、リン酸エステル型難燃剤自体も空気中の水分等で徐々に加水分解し、リン酸を生成する可能性があり、合成樹脂中でリン酸を生成した場合には、合成樹脂の分子量を低下させたり、電気・電子部品等の用途に用いた場合には短絡を起こす危険性がある。
There is a method using an organic phosphorus compound such as triphenyl phosphate and tricresyl phosphate as another method not using a halogen-based flame retardant. However, these organophosphorus compounds belong to phosphate ester type flame retardants. When heat-kneaded with synthetic resins such as polyester at high temperatures, transesterification occurs and the molecular weight of the synthetic resin is significantly reduced. As a result, the original physical properties of the resin are impaired. Moreover, the phosphoric ester-type flame retardant itself may gradually hydrolyze with moisture in the air to produce phosphoric acid. When phosphoric acid is produced in a synthetic resin, the molecular weight of the synthetic resin is reduced. There is a danger of causing a short circuit when used for electrical or electronic parts.
これに対し、ノンハロゲン系難燃剤としてポリリン酸アンモニウムをはじめとするリン酸塩類の使用が多数提案されている。ところが、この種のリン酸塩類を多量に添加した場合、リン酸塩類は難燃性が低いうえに耐湿性も劣っているために、成形品の外観、機械物性等が大幅に低下してしまう。また、この難燃剤組成物からなる樹脂成形品を高湿度下で使用すれば、表面にリン酸塩類のブリードアウトが発生し、なおかつ、多数のブルーミング現象を引き起こしてしまうという致命的な欠陥もある。
On the other hand, the use of phosphates such as ammonium polyphosphate has been proposed as a non-halogen flame retardant. However, when a large amount of this type of phosphates is added, the phosphates are low in flame retardancy and inferior in moisture resistance, so the appearance and mechanical properties of the molded product are greatly reduced. . In addition, if a resin molded article made of this flame retardant composition is used under high humidity, phosphates bleed out on the surface, and there are also fatal defects that cause numerous blooming phenomena. .
上記の欠点を改善するために、特に耐湿性を改良したメラミン架橋型、フェノール架橋型、エポキシ架橋型、あるいはシランカップリング剤及び末端封鎖されたポリエチレングリコール架橋型の表面処理剤による被覆ポリリン酸アンモニウムも提案されている。ところが、これらは樹脂相溶性又は分散性が悪く、高い機械的強度が得られないという問題点がある。また、多くの被覆ポリリン酸アンモニウムを含む樹脂組成物を混練する場合、熱及び応力によって被覆が壊れてしまい、上記と同様の問題(吸湿によるブリードアウト等の問題)が発生することが多い。
Ammonium polyphosphate coated with a surface treatment agent of melamine cross-linking type, phenol cross-linking type, epoxy cross-linking type or silane coupling agent and end-capped polyethylene glycol cross-linking type with improved moisture resistance, in order to improve the above-mentioned drawbacks Has also been proposed. However, these have a problem that resin compatibility or dispersibility is poor and high mechanical strength cannot be obtained. Further, when a resin composition containing a large amount of coated ammonium polyphosphate is kneaded, the coating is broken by heat and stress, and problems similar to the above (problems such as bleeding out due to moisture absorption) often occur.
一般的に、ポリリン酸アンモニウムを含む樹脂組成物は、混練時に200℃を超えたあたりから熱分解を起こすので、熱分解物が混練中にもブリードアウトしてしまい、ストランドの水濡れを引き起こす。このことが、難燃性樹脂組成物の物性及び生産性を極端に悪くしてしまう原因となっている。例えば、従来技術では、ポリリン酸ピペラジン塩等が提案されている(特許文献1~4)。ところが、これらの従来技術においても、上記と同様の問題を抱えており、実用上改善すべき点も多い。つまり、リン酸アンモニウム、ピロリン酸アンモニウム、ポリリン酸アンモニウム等の縮合リン酸アンモニウム塩類等は基本的に水溶性又は吸水性の物質であるがゆえに、これらの添加が樹脂組成物の耐熱性及び耐湿性が低下させる直接的な原因となる。
Generally, since a resin composition containing ammonium polyphosphate undergoes thermal decomposition from around 200 ° C. during kneading, the pyrolyzed product bleeds out even during kneading, causing strand wetness. This is a cause of extremely worsening the physical properties and productivity of the flame retardant resin composition. For example, in the prior art, polyphosphate piperazine salts have been proposed (Patent Documents 1 to 4). However, these conventional techniques have the same problems as described above, and there are many points that should be improved in practice. In other words, condensed ammonium phosphate salts such as ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate are basically water-soluble or water-absorbing substances, and therefore their addition is heat resistance and moisture resistance of the resin composition. Is a direct cause of decline.
これを改善するために、芳香族リン酸モノエステルの脂肪族アミン塩のような有機塩類が提案されている(特許文献5~7)。しかし、芳香族リン酸モノエステルの脂肪族アミン塩は、所定の難燃性を有するものの、非常に強い吸水性を持っている水溶性有機塩である。例として、下記化学式(1)に表されるようなリン酸モノトリルピペラジン塩がこれに該当する。
In order to improve this, organic salts such as aliphatic amine salts of aromatic phosphoric acid monoesters have been proposed (Patent Documents 5 to 7). However, the aliphatic amine salt of the aromatic phosphoric acid monoester is a water-soluble organic salt having a very strong water absorption property although having a predetermined flame retardancy. As an example, a monotolylpiperazine phosphate salt represented by the following chemical formula (1) corresponds to this.
この物質は、アニオン成分であるトリルジヒドロゲンホスフェートイオンとカチオン成分であるピペラジンイオンとが交互に配位結合しているオニウム塩であり、水溶性が高く、ほとんどの有機溶剤に不溶であるために樹脂相溶性も非常に悪い。このため、リン酸モノトリルピペラジン塩は耐熱性も低く、特にこれを樹脂組成物として混練した場合、混練温度180~200℃で熱分解することによって毒性の高いp-クレゾールガスが大量に発生してしまうという致命的な欠点を有するため、実用上とても満足できるものではない。
This substance is an onium salt in which tolyl dihydrogen phosphate ion, which is an anionic component, and piperazine ion, which is a cation component, are alternately coordinated, and is highly water-soluble and insoluble in most organic solvents. The resin compatibility is also very poor. For this reason, monotolylpiperazine phosphate has low heat resistance, and particularly when it is kneaded as a resin composition, a large amount of highly toxic p-cresol gas is generated by thermal decomposition at a kneading temperature of 180 to 200 ° C. It has a fatal defect that it is not practically satisfactory.
従って、本発明の主な目的は、従来技術の諸問題を解消し、より優れた難燃性を付与できる難燃剤、さらには前記組成物を含む難燃性樹脂組成物及びそれを成形してなる成形品を提供することにある。
Accordingly, the main object of the present invention is to solve the problems of the prior art and to provide a flame retardant capable of imparting more excellent flame retardancy, and further to a flame retardant resin composition containing the composition and molding the same. It is to provide a molded article.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、特定の芳香族リン酸エステルの環状アミン塩を難燃剤の有効成分として採用することによって、上記目的を達成できることを見出し、本発明を完成するに至った。
As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by employing a cyclic amine salt of a specific aromatic phosphate as an active ingredient of a flame retardant, The present invention has been completed.
すなわち、本発明は、特に、下記の環状アミン塩を含む難燃剤及び難燃性樹脂組成物に係る。
1. 1)アニオン成分である芳香族リン酸ジエステル及び2)カチオン成分である環状アミンから構成される芳香族リン酸ジエステルの環状アミン塩を含む難燃剤組成物であって、当該環状アミン塩が下記一般式(I)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。nは1~10の整数を示す。mは0~9の整数を示す。lは1~10の整数を示す。〕
で表される、環状アミン塩を含む難燃剤組成物。
2. 当該芳香族リン酸ジエステルの環状アミン塩において、
下記一般式(II)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表されるA成分と、
下記一般式(III)
〔式中、Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。mは0~9の整数を示す。〕
で表されるB成分との構成比率が、イオン当量比でA成分/B成分=0.8/1.0~1.0/1.2である、前記項1に記載の難燃剤組成物。
3. 芳香族リン酸モノエステルの含有量が難燃剤組成物中1重量%以下である、前記項1に記載の難燃剤組成物。
4. リン酸塩類の少なくとも1種をさらに含む、前記項1に記載の難燃剤組成物。
5. 前記項1に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~100重量部を含む難燃性樹脂組成物。
6. 前記項4に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~50重量部、当該リン酸塩類1~50重量部を含む難燃性樹脂組成物。
7. 当該樹脂成分がポリオレフィン系樹脂である、前記項5又は6に記載の難燃剤樹脂組成物。
8. 前記項5~7のいずれかに記載の難燃性樹脂組成物を成形してなる難燃性樹脂成形品。
9. 電気・電子部品、OA機器部品、家電機器部品、自動車用部品又は機器機構部品に用いられる、前記項8に記載の難燃性樹脂成形品。
10. 下記一般式(I)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。nは1~10の整数を示す。mは0~9の整数を示す。lは1~10の整数を示す。〕
で表される芳香族リン酸ジエステルの環状アミン塩を製造する方法であって、
(1)下記一般式(IV)
〔式中、R1~R5は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される化合物を、アミンの存在下においてオキシハロゲン化リンと反応させることにより、
下記一般式(V)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する工程、
(2)当該含ハロゲン芳香族リン酸エステル酸誘導体を加水分解させることにより、
下記一般式(II)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される芳香族リン酸ジエステルを合成する工程、
(3)当該芳香族リン酸ジエステルに対し、下記一般式(VI)
〔式中、Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。mは0~9の整数を示す。〕
で表される化合物を添加することによって、前記一般式(I)で表される化合物を合成する工程
を含む、芳香族リン酸ジエステルの環状アミン塩の製造方法。 That is, the present invention particularly relates to a flame retardant and a flame retardant resin composition containing the following cyclic amine salt.
1. A flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
The flame retardant composition containing cyclic amine salt represented by these.
2. In the cyclic amine salt of the aromatic phosphoric diester,
The following general formula (II)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A component represented by
The following general formula (III)
[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
2. The flame retardant composition according to item 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component = 0.8 / 1.0 to 1.0 / 1.2 .
3. Item 2. The flame retardant composition according to Item 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition.
4). Item 2. The flame retardant composition according to Item 1, further comprising at least one phosphate.
5. A flame retardant composition comprising the flame retardant composition according to item 1 and a resin component, the flame retardant comprising 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component Resin composition.
6). 5. A resin composition comprising the flame retardant composition according to item 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates A flame retardant resin composition comprising 1 to 50 parts by weight.
7. Item 7. The flame retardant resin composition according to Item 5 or 6, wherein the resin component is a polyolefin resin.
8). 8. A flame retardant resin molded product obtained by molding the flame retardant resin composition according to any one of items 5 to 7.
9. Item 9. The flame-retardant resin molded article according to Item 8, which is used for electrical / electronic parts, OA equipment parts, household electrical equipment parts, automotive parts or equipment mechanism parts.
10. The following general formula (I)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
A process for producing a cyclic amine salt of an aromatic phosphoric diester represented by
(1) The following general formula (IV)
[Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing a halogen-containing aromatic phosphate ester derivative represented by:
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing an aromatic phosphate diester represented by:
(3) For the aromatic phosphoric acid diester, the following general formula (VI)
[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
A method for producing a cyclic amine salt of an aromatic phosphoric diester, comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).
1. 1)アニオン成分である芳香族リン酸ジエステル及び2)カチオン成分である環状アミンから構成される芳香族リン酸ジエステルの環状アミン塩を含む難燃剤組成物であって、当該環状アミン塩が下記一般式(I)
で表される、環状アミン塩を含む難燃剤組成物。
2. 当該芳香族リン酸ジエステルの環状アミン塩において、
下記一般式(II)
で表されるA成分と、
下記一般式(III)
で表されるB成分との構成比率が、イオン当量比でA成分/B成分=0.8/1.0~1.0/1.2である、前記項1に記載の難燃剤組成物。
3. 芳香族リン酸モノエステルの含有量が難燃剤組成物中1重量%以下である、前記項1に記載の難燃剤組成物。
4. リン酸塩類の少なくとも1種をさらに含む、前記項1に記載の難燃剤組成物。
5. 前記項1に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~100重量部を含む難燃性樹脂組成物。
6. 前記項4に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~50重量部、当該リン酸塩類1~50重量部を含む難燃性樹脂組成物。
7. 当該樹脂成分がポリオレフィン系樹脂である、前記項5又は6に記載の難燃剤樹脂組成物。
8. 前記項5~7のいずれかに記載の難燃性樹脂組成物を成形してなる難燃性樹脂成形品。
9. 電気・電子部品、OA機器部品、家電機器部品、自動車用部品又は機器機構部品に用いられる、前記項8に記載の難燃性樹脂成形品。
10. 下記一般式(I)
で表される芳香族リン酸ジエステルの環状アミン塩を製造する方法であって、
(1)下記一般式(IV)
で表される化合物を、アミンの存在下においてオキシハロゲン化リンと反応させることにより、
下記一般式(V)
で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する工程、
(2)当該含ハロゲン芳香族リン酸エステル酸誘導体を加水分解させることにより、
下記一般式(II)
で表される芳香族リン酸ジエステルを合成する工程、
(3)当該芳香族リン酸ジエステルに対し、下記一般式(VI)
で表される化合物を添加することによって、前記一般式(I)で表される化合物を合成する工程
を含む、芳香族リン酸ジエステルの環状アミン塩の製造方法。 That is, the present invention particularly relates to a flame retardant and a flame retardant resin composition containing the following cyclic amine salt.
1. A flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I)
The flame retardant composition containing cyclic amine salt represented by these.
2. In the cyclic amine salt of the aromatic phosphoric diester,
The following general formula (II)
A component represented by
The following general formula (III)
2. The flame retardant composition according to item 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component = 0.8 / 1.0 to 1.0 / 1.2 .
3. Item 2. The flame retardant composition according to Item 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition.
4). Item 2. The flame retardant composition according to Item 1, further comprising at least one phosphate.
5. A flame retardant composition comprising the flame retardant composition according to item 1 and a resin component, the flame retardant comprising 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component Resin composition.
6). 5. A resin composition comprising the flame retardant composition according to item 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates A flame retardant resin composition comprising 1 to 50 parts by weight.
7. Item 7. The flame retardant resin composition according to Item 5 or 6, wherein the resin component is a polyolefin resin.
8). 8. A flame retardant resin molded product obtained by molding the flame retardant resin composition according to any one of items 5 to 7.
9. Item 9. The flame-retardant resin molded article according to Item 8, which is used for electrical / electronic parts, OA equipment parts, household electrical equipment parts, automotive parts or equipment mechanism parts.
10. The following general formula (I)
A process for producing a cyclic amine salt of an aromatic phosphoric diester represented by
(1) The following general formula (IV)
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)
A step of synthesizing a halogen-containing aromatic phosphate ester derivative represented by:
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)
A step of synthesizing an aromatic phosphate diester represented by:
(3) For the aromatic phosphoric acid diester, the following general formula (VI)
A method for producing a cyclic amine salt of an aromatic phosphoric diester, comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).
本発明の難燃剤は、特定の化学構造を有する環状アミン塩を含有することから、従来の難燃剤よりも優れた難燃性を発揮することができる。そのため、比較的少量の添加であっても所望の難燃性を付与することができる。すなわち、添加対象となる材料(樹脂等)の本来の特性を効果的に維持しつつ、優れた難燃性を与えることが可能となる。
Since the flame retardant of the present invention contains a cyclic amine salt having a specific chemical structure, it can exhibit flame retardancy superior to conventional flame retardants. Therefore, the desired flame retardancy can be imparted even with a relatively small amount of addition. That is, it is possible to provide excellent flame retardancy while effectively maintaining the original characteristics of the material to be added (resin etc.).
また、本発明の難燃剤は、耐湿性に優れるので、吸湿によるブリードアウト、ブルーミング等の問題、ブリードアウト等による難燃性低下の問題も効果的に抑制ないしは防止することができる。
Further, since the flame retardant of the present invention is excellent in moisture resistance, problems such as bleeding out and blooming due to moisture absorption, and deterioration of flame resistance due to bleeding out can be effectively suppressed or prevented.
さらに、本発明難燃剤の有効成分である前記環状アミン塩は分子中にハロゲン元素を含まないため、難燃性樹脂及び成形品が燃焼した場合でも有害ガスの発生を効果的に抑制することができる。
Furthermore, since the cyclic amine salt, which is an active ingredient of the flame retardant of the present invention, does not contain a halogen element in the molecule, it can effectively suppress the generation of harmful gases even when the flame retardant resin and the molded product burn. it can.
特に、本発明では、ポリオレフィン系樹脂等の難燃剤として適用する場合、前記環状アミン塩とともにリン酸塩類を併用することによって、より少ない添加量の難燃剤で優れた難燃性を発揮することができる。従来、ポリリン酸塩類等のリン酸塩類は水溶性又は吸水性が高い。このために、リン酸塩を難燃剤として含む難燃性樹脂組成物及び成形品は、難燃剤のモールドデポジット及びブリードアウト(又はブルーミング)を有効に抑制することが不可能である。これに対し、本発明難燃剤を含む難燃性樹脂組成物及び成形品は、種々の樹脂の本来持つ物性を良好に維持しつつ、ポリリン酸塩類を樹脂に対して高度に相溶化させることができ、なおかつ、ポリリン酸塩類のモールドデポジット及びブリードアウト(又はブルーミング)を有効に抑制しつつ、従来技術と同等以上の高度な難燃性をポリオレフィン系樹脂等に対して付与することができる。
In particular, in the present invention, when applied as a flame retardant such as a polyolefin resin, it is possible to exhibit excellent flame retardancy with a smaller amount of flame retardant by using phosphates together with the cyclic amine salt. it can. Conventionally, phosphates such as polyphosphates have high water solubility or high water absorption. For this reason, the flame-retardant resin composition and molded product containing phosphate as a flame retardant cannot effectively suppress mold deposits and bleed-out (or blooming) of the flame retardant. On the other hand, the flame-retardant resin composition and molded product containing the flame retardant of the present invention can highly compatibilize polyphosphates with the resin while maintaining good physical properties of various resins. In addition, it is possible to impart a high degree of flame retardancy equal to or higher than that of the prior art to the polyolefin resin and the like while effectively suppressing mold deposits and bleed out (or blooming) of polyphosphates.
このように、本発明の難燃剤は、例えば有機成分を含む材料に添加するための難燃剤として好適に用いることができる。特に、樹脂成分を含む組成物(例えば樹脂成分を50重量%以上含む組成物)に添加するための難燃剤として好ましく用いることができる。
Thus, the flame retardant of the present invention can be suitably used as a flame retardant for adding to a material containing an organic component, for example. In particular, it can be preferably used as a flame retardant for addition to a composition containing a resin component (for example, a composition containing 50% by weight or more of a resin component).
以下において、本発明の環状アミン塩を主たる成分とした難燃剤組成物、及びこれを樹脂成分に配合した難燃性樹脂組成物、並びにこの組成物を成形してなる成形品について詳細に説明する。
Hereinafter, a flame retardant composition containing the cyclic amine salt of the present invention as a main component, a flame retardant resin composition containing this as a resin component, and a molded product formed by molding this composition will be described in detail. .
1.環状アミン塩を含む難燃剤組成物
(1)環状アミン塩及びその合成方法
(1-1)環状アミン塩
本発明の樹脂用難燃剤は、1)アニオン成分である芳香族リン酸ジエステル及び2)カチオン成分である環状アミンから構成される芳香族リン酸ジエステルの環状アミン塩を含む難燃剤であって、
前記芳香族リン酸ジエステルの環状アミン塩が、
下記一般式(I)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。nは1~10の整数を示す。mは0~9の整数を示す。lは1~10の整数を示す。〕で表される芳香族リン酸ジエステルの環状アミン塩を含むことを特徴とする。
1. Flame retardant composition containing cyclic amine salt (1) Cyclic amine salt and synthesis method thereof (1-1) Cyclic amine salt The flame retardant for resin of the present invention is 1) an aromatic phosphate diester as an anionic component and 2) A flame retardant comprising a cyclic amine salt of an aromatic phosphoric diester composed of a cyclic amine which is a cationic component,
The cyclic amine salt of the aromatic phosphoric diester is
The following general formula (I)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. And a cyclic amine salt of an aromatic phosphoric acid diester represented by the formula:
(1)環状アミン塩及びその合成方法
(1-1)環状アミン塩
本発明の樹脂用難燃剤は、1)アニオン成分である芳香族リン酸ジエステル及び2)カチオン成分である環状アミンから構成される芳香族リン酸ジエステルの環状アミン塩を含む難燃剤であって、
前記芳香族リン酸ジエステルの環状アミン塩が、
下記一般式(I)
The cyclic amine salt of the aromatic phosphoric diester is
The following general formula (I)
すなわち、下記一般式(I)で示される芳香族リン酸ジエステル環状アミン塩(以下、「本発明環状アミン塩」ともいう。)は、本発明難燃剤の有効成分として機能するものである。本発明難燃剤は、本発明環状アミン塩の1種又は2種以上を含有する。
That is, the aromatic phosphoric diester cyclic amine salt represented by the following general formula (I) (hereinafter also referred to as “the present cyclic amine salt”) functions as an active ingredient of the present flame retardant. The flame retardant of the present invention contains one or more of the cyclic amine salts of the present invention.
本発明環状アミン塩は、アニオン成分(A成分)として芳香族リン酸ジエステルを含み、カチオン成分(B成分)として環状アミンから構成される。このような環状アミン塩は、公知又は市販のものを使用することもできる。以下、本発明環状アミン塩についてA成分及びB成分に分けて説明する。
The cyclic amine salt of the present invention contains an aromatic phosphate diester as an anion component (component A) and is composed of a cyclic amine as a cation component (component B). As such a cyclic amine salt, a known or commercially available one can also be used. Hereinafter, the cyclic amine salt of the present invention will be described separately for component A and component B.
A成分
本発明環状アミン塩のうちA成分を構成する芳香族リン酸ジエステルは、下記一般式(II)で示される。
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
A component The aromatic phosphoric acid diester which comprises A component among cyclic amine salt of this invention is shown by the following general formula (II).
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
本発明環状アミン塩のうちA成分を構成する芳香族リン酸ジエステルは、下記一般式(II)で示される。
一般式(II)中のR1~R10は、水素原子又は置換基を有していても良い炭化水素基を示す。また、それぞれのR1~R10は、互いに同一の置換基であっても良く、あるいは互いに異なる置換基であっても良い。特に、本発明では、R1~R10は、置換基を有していても良い炭化水素基よりも水素原子の方が経済的な見地より好ましい。
R 1 to R 10 in the general formula (II) represent a hydrogen atom or a hydrocarbon group which may have a substituent. Further, each of R 1 to R 10 may be the same substituent as each other, or may be different from each other. In particular, in the present invention, R 1 to R 10 are more preferably a hydrogen atom than an optionally substituted hydrocarbon group from an economical viewpoint.
炭化水素基としては特に限定されず、鎖状(直鎖及び分岐鎖のいずれでも良い。)又は環状(単環、縮合多環、架橋環又はスピロ環のいずれでも良い。)のいずれでもあっても良い。例えば、側鎖を有する環状炭化水素基を用いることもできる。また、炭化水素基は、飽和炭化水素基又は不飽和炭化水素基のいずれであっても良い。
The hydrocarbon group is not particularly limited, and may be any of a chain (which may be either a straight chain or a branched chain) or a ring (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring). Also good. For example, a cyclic hydrocarbon group having a side chain can also be used. Further, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
炭化水素基としては、例えばアルキル基、シクロアルキル基、アリル基、アリール基、アルキルアリール基、アリールアルキル基等が挙げられる。これらの炭化水素基の総炭素数(置換基を有する場合は置換基の炭素数も含む。)は制限されないが、一般的には1~18程度とすれば良く、特に1~4程度が好ましい。より具体的には、メチル基、エチル基、プロピル基、ブチル基、ビニル基等を例示することができる。
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group. The total number of carbon atoms of these hydrocarbon groups (including the number of carbon atoms of the substituent group if it has a substituent group) is not limited, but is generally about 1 to 18, and preferably about 1 to 4. . More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and the like can be exemplified.
また、炭化水素基には置換基が導入されていても良い。置換基としては、例えばアミノ基、ヒドロキシル基、アルコキシル基、ニトロ基、シアノ基、カルボニル基、アルデヒド基、カルボキシル基、スルホン基、スルフィドリル基等を挙げることができる。
In addition, a substituent may be introduced into the hydrocarbon group. Examples of the substituent include an amino group, hydroxyl group, alkoxyl group, nitro group, cyano group, carbonyl group, aldehyde group, carboxyl group, sulfone group, and sulfhydryl group.
これらのうち、最も好ましい具体例としては、R1、R3、R5、R6、R8及びR10が水素原子又はメチル基であり、なおかつ、R2、R4、R7及びR9が水素原子であるものである。
Among these, the most preferred specific examples are R 1 , R 3 , R 5 , R 6 , R 8 and R 10 are hydrogen atoms or methyl groups, and R 2 , R 4 , R 7 and R 9. Is a hydrogen atom.
一般式(I)で表される芳香族リン酸ジエステルのより具体的な例としては、下記式(1)~(5)で表される化合物が挙げられる。これらの化合物自体は、公知又は市販のものを用いることもできる。
More specific examples of the aromatic phosphoric acid diester represented by the general formula (I) include compounds represented by the following formulas (1) to (5). As these compounds themselves, known or commercially available compounds can also be used.
B成分
本発明環状アミン塩のうちB成分を構成する環状アミンは、下記一般式(III)で示される。
〔Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。mは0~9の整数を示す。〕
B component Among the cyclic amine salts of the present invention, the cyclic amine constituting the B component is represented by the following general formula (III).
[A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
本発明環状アミン塩のうちB成分を構成する環状アミンは、下記一般式(III)で示される。
前記Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンである。従って、m=0である場合は、Zはイミノ基となる。m=0の場合は、例えばピペリジン、ピロリジン等が該当する。
A is a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Therefore, when m = 0, Z becomes an imino group. In the case of m = 0, for example, piperidine, pyrrolidine and the like are applicable.
前記のアルキレン基としては、例えばメチレン基、エチレン基、プロピレン基、ブチレン基等を挙げることができる。特に、本発明では、総炭素数2~6のアルキレン基が好ましい。
Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. In the present invention, an alkylene group having 2 to 6 carbon atoms is particularly preferable.
このような環状アミンとしては、例えば1つ以上のイミノ基(-NH-)が酸素原子、硫黄原子又はイミノ基とアルキレン基とを介して環状に結合している化合物を用いることができる。より好ましくは、2つ以上のイミノ基がアルキレン基を介して環状に結合してなる環状アミンを用いる。
As such a cyclic amine, for example, a compound in which one or more imino groups (—NH—) are cyclically bonded through an oxygen atom, a sulfur atom or an imino group and an alkylene group can be used. More preferably, a cyclic amine in which two or more imino groups are bonded cyclically via an alkylene group is used.
前記の環状アミンの具体例としては、アジリジン、アゼチジン、ピロリジン、ピペリジン、アゼパン、アゾカン、アゾナン、アゼカン、ジアゼチジン、イミダゾリジン、ピラゾリジン、ピペラジン、モルホリン、チオモルホリン、1,4,7-トリアザシクロノナン、1,4,7,10-テトラアザシクロドデカン、1,4,7,10,13-ペンタアザシクロペンタデカン、1,4,7,10,13,16-ヘキサアザシクロオクタデカン等が挙げられる。
Specific examples of the cyclic amine include aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, azonan, azecan, diazetidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, 1,4,7-triazacyclononane. 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13-pentaazacyclopentadecane, 1,4,7,10,13,16-hexaazacyclooctadecane and the like.
これらのうち、本発明では、前記環状アミンAとしては、環状アミン類又は環状ポリアミン類を適宜選択して使用することができる。環状アミン類としては、例えばピロリジン、イミダゾリジン、ピラゾリジン、ピペラジン、モルホリン、チオモルホリン等が挙げられる。また、環状ポリアミン類としては、例えばイミノ基(-NH-)とエチレン基(-CH2-CH2-)の組合せの2つ以上が環状に連結した環状ポリアミン類が挙げられる。この中でも、特に安価で入手しやすいという見地よりピペラジンが最も好ましい。
Among these, in the present invention, as the cyclic amine A, cyclic amines or cyclic polyamines can be appropriately selected and used. Examples of cyclic amines include pyrrolidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, and the like. Examples of the cyclic polyamines include cyclic polyamines in which two or more combinations of imino group (—NH—) and ethylene group (—CH 2 —CH 2 —) are linked in a cyclic manner. Among these, piperazine is most preferable from the viewpoint of being inexpensive and easy to obtain.
一般式(III)で表される環状アミンの具体例としては、下記式(6)~(10)で表される化合物が挙げられる。
Specific examples of the cyclic amine represented by the general formula (III) include compounds represented by the following formulas (6) to (10).
本発明環状アミン塩は、樹脂成分との混練時又は成形時における耐熱性が高いものが好適に使用できる。このため、前記環状アミンAは、第1アミンより第2アミン又は第3アミンが好ましい。また、成形時に起こり得る熱分解ガスによるフラッシングを防止するという見地からも、耐熱性の低い脂肪族アミンよりも環状アミンの方がより好適に使用することができる。
As the cyclic amine salt of the present invention, those having high heat resistance during kneading or molding with a resin component can be suitably used. For this reason, the cyclic amine A is preferably a secondary amine or a tertiary amine rather than a primary amine. Also, from the viewpoint of preventing flushing due to pyrolysis gas that may occur during molding, a cyclic amine can be used more suitably than an aliphatic amine having low heat resistance.
本発明環状アミン塩におけるA成分とB成分との構成比は、特に限定されないが、より難燃性、耐湿性等を効果的に保持するためには、A成分とB成分のそれぞれのイオン当量が等しくなることが好ましい。それぞれのイオン当量が等しくすることによって、剰余のイオン成分の含有量を低くすることができるため、水溶性又は吸湿性の発現を効果的に抑制ないしは防止できる結果、それによる成形品等の外観不良、物性低下等も回避することができる。
The component ratio of the A component and the B component in the cyclic amine salt of the present invention is not particularly limited, but in order to more effectively retain flame retardancy, moisture resistance, etc., the respective ion equivalents of the A component and the B component Are preferably equal. By making each ion equivalent equal, the content of excess ionic components can be lowered, so that the expression of water solubility or hygroscopicity can be effectively suppressed or prevented, resulting in poor appearance of molded products, etc. In addition, deterioration of physical properties can be avoided.
かかる見地より、本発明環状アミン塩におけるA成分とB成分との構成比率(イオン当量比)は、A成分/B成分=0.8/1.0~1.0/1.2の範囲にあれば、前記の不具合を引き起こさずに難燃剤としてより好適に使用することができる。さらには、本発明では、A成分とB成分との構成比が完全に等量であることが最も好ましい。
From this viewpoint, the component ratio (ion equivalent ratio) of the A component and the B component in the cyclic amine salt of the present invention is in the range of A component / B component = 0.8 / 1.0 to 1.0 / 1.2. If it exists, it can be used more suitably as a flame retardant without causing the above-mentioned problems. Furthermore, in the present invention, it is most preferable that the constituent ratio of the A component and the B component is completely equal.
本発明環状アミン塩の好ましい実施態様
本発明の難燃性樹脂組成物及びその成形品における本発明環状アミン塩の役割としては、難燃剤として機能することはもとより、吸湿防止剤、ブルーミング防止剤等の様々な機能を発揮し得る。この点を鑑みて、より好適な本発明環状アミン塩を具体的に例示すると、構成するB成分の好適な例としてピペラジンを選択した場合には、下記式(11)~(16)で表される化合物が挙げられる。
Preferred embodiments of the cyclic amine salt of the present invention The role of the cyclic amine salt of the present invention in the flame retardant resin composition of the present invention and its molded article is not only to function as a flame retardant, but also to a moisture absorption inhibitor, blooming inhibitor, etc. Can exhibit various functions. In view of this point, specific examples of the more preferred cyclic amine salt of the present invention are shown by the following formulas (11) to (16) when piperazine is selected as a preferred example of the constituent B component. Compounds.
本発明の難燃性樹脂組成物及びその成形品における本発明環状アミン塩の役割としては、難燃剤として機能することはもとより、吸湿防止剤、ブルーミング防止剤等の様々な機能を発揮し得る。この点を鑑みて、より好適な本発明環状アミン塩を具体的に例示すると、構成するB成分の好適な例としてピペラジンを選択した場合には、下記式(11)~(16)で表される化合物が挙げられる。
なお、本発明の環状アミン塩を構成するA成分である芳香族リン酸ジエステルとB成分である環状アミンとは、それぞれ公知のものを使用することができる。また、公知の製造方法によって得られる芳香族リン酸ジエステルの環状アミン塩を使用することもできる。
In addition, a well-known thing can be used for the aromatic phosphoric acid diester which is A component which comprises the cyclic amine salt of this invention, and the cyclic amine which is B component, respectively. Moreover, the cyclic amine salt of the aromatic phosphoric acid diester obtained by a well-known manufacturing method can also be used.
(1-2)本発明環状アミン塩の合成方法
本発明環状アミン塩は公知の製造方法によっても製造することができるが、特に本発明の製造方法により製造することが好ましい。 (1-2) Method for Synthesizing the Cyclic Amine Salt of the Present Invention The cyclic amine salt of the present invention can be produced by a known production method, but is particularly preferably produced by the production method of the present invention.
本発明環状アミン塩は公知の製造方法によっても製造することができるが、特に本発明の製造方法により製造することが好ましい。 (1-2) Method for Synthesizing the Cyclic Amine Salt of the Present Invention The cyclic amine salt of the present invention can be produced by a known production method, but is particularly preferably produced by the production method of the present invention.
一般式(IV)で表される化合物から一般式(II)で表される芳香族リン酸エステル酸誘導体を合成する公知の方法としては、従来、Phosphorus and its compounds Volume 2, 1961, Interscience
Pubublishers, Inc., New York, 1230-に記載された方法、すなわちトリアルキルホスフェートからアルカリを使った部分加水分解法による製造方法、モノアルキルジヒドロキシホスフェートとジアルキルヒドロキシホスフェートの混合物を製造した後、水溶性の差により選択分配する製造方法等がある。 As a known method for synthesizing the aromatic phosphate ester derivative represented by the general formula (II) from the compound represented by the general formula (IV), conventionally, Phosphorus and its compounds Volume 2, 1961, Interscience
The method described in Pubublishers, Inc., New York, 1230-, ie, a method of production by partial hydrolysis using alkali from trialkyl phosphate, after producing a mixture of monoalkyl dihydroxy phosphate and dialkyl hydroxy phosphate, There are manufacturing methods for selective distribution according to the difference.
Pubublishers, Inc., New York, 1230-に記載された方法、すなわちトリアルキルホスフェートからアルカリを使った部分加水分解法による製造方法、モノアルキルジヒドロキシホスフェートとジアルキルヒドロキシホスフェートの混合物を製造した後、水溶性の差により選択分配する製造方法等がある。 As a known method for synthesizing the aromatic phosphate ester derivative represented by the general formula (II) from the compound represented by the general formula (IV), conventionally, Phosphorus and its compounds Volume 2, 1961, Interscience
The method described in Pubublishers, Inc., New York, 1230-, ie, a method of production by partial hydrolysis using alkali from trialkyl phosphate, after producing a mixture of monoalkyl dihydroxy phosphate and dialkyl hydroxy phosphate, There are manufacturing methods for selective distribution according to the difference.
上記刊行物に開示の合成経路を応用すると、過剰の上記一般式(IV)で表される化合物を五酸化リン又はオキシ塩化リンと反応することにより、芳香族モノリン酸エステル、芳香族ジリン酸エステル及び芳香族トリリン酸エステルの混合物を合成することができる。しかし、この方法は収率が低い上に精製に手間取るために、経済的に有利な方法ではない。例えば、オキシ塩化リンによるフェノールのリン酸化の場合、オキシ塩化リンを大過剰に加えることによりジクロロモノフェニルホスフェート(モノエステル体)を優先して合成することが可能であり、またフェノールをオキシ塩化リンに対して3当量加えて反応することにより収率良くトリフェニルホスフェート(トリエステル体)を優先して合成することができる。ところが、上記刊行物の合成経路を応用してもモノクロロジフェニルホスフェート(ジエステル体)のみを優先して選択的に直接合成することは困難である。
When the synthetic route disclosed in the above publication is applied, by reacting an excess of the compound represented by the general formula (IV) with phosphorus pentoxide or phosphorus oxychloride, aromatic monophosphate ester, aromatic diphosphate ester And a mixture of aromatic triphosphates can be synthesized. However, this method is not economically advantageous because of low yield and labor for purification. For example, in the case of phosphorylation of phenol with phosphorus oxychloride, it is possible to preferentially synthesize dichloromonophenyl phosphate (monoester) by adding a large excess of phosphorus oxychloride. By adding 3 equivalents to the reaction, triphenyl phosphate (triester form) can be preferentially synthesized with good yield. However, even if the synthesis route of the above publication is applied, it is difficult to selectively synthesize preferentially only monochlorodiphenyl phosphate (diester).
これに対し、本発明の製造方法は、化学式(IV)で表される化合物をアミンの存在下にてオキシハロゲン化リンと反応させることにより一般式(V)で表される化合物を経由して、一般式(I)で表される環状アミン塩を製造する合成経路である。本発明の製造方法によれば、より収率良く1ポットで直接に目的化合物を得ることができる。より具体的には、目的化合物である本発明環状アミン塩の合成に至る各過程において、中間体生成物の単離及び生成工程を行うことなく、連続的に次の過程に移ることができるので、中間体精製に伴う収率低下が発生しないために高い収率が得られるうえ、工程の簡略化による製造コストの低減も図ることができるため、経済的にも非常に優れた方法となる。かかる見地より、本発明環状アミン塩の製造においては、本発明の製造方法を用いることが好ましい。
On the other hand, in the production method of the present invention, the compound represented by the chemical formula (IV) is reacted with phosphorus oxyhalide in the presence of an amine via the compound represented by the general formula (V). This is a synthetic route for producing a cyclic amine salt represented by the general formula (I). According to the production method of the present invention, the target compound can be obtained directly in one pot with higher yield. More specifically, in each process leading to the synthesis of the cyclic amine salt of the present invention which is the target compound, the intermediate product can be continuously transferred to the next process without performing the isolation and production process. In addition, since the yield reduction associated with the intermediate purification does not occur, a high yield can be obtained, and the production cost can be reduced by simplifying the process, so that it is an economically excellent method. From this viewpoint, it is preferable to use the production method of the present invention in the production of the cyclic amine salt of the present invention.
本発明の製造方法は、
(1)下記化学式(IV)
〔式中、R1~R5は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される化合物を、アミンの存在下においてオキシハロゲン化リンと反応させることにより、
下記一般式(V)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する工程(A工程)、
(2)当該含ハロゲン芳香族リン酸エステル酸誘導体を加水分解させることにより、
下記一般式(II)
〔式中、R1~R10は、互いに同一又は異なって、水素原子又は置換基を有していても良い炭化水素基を示す。〕
で表される芳香族リン酸ジエステルを合成する工程(B工程)、
(3)当該芳香族リン酸ジエステルに対し、
下記一般式(VI)
〔式中、Aは、1つ以上のイミノ基(-NH-)が少なくともアルキレン基と環状に結合してなる環状アミンを示す。Yはイミノ基を示す。Zは酸素原子、硫黄原子又はイミノ基を示す。mは0~9の整数を示す。〕
で表される化合物を有機溶媒中において添加することによって、前記一般式(I)で表される化合物を得る工程(C工程)
を含む製造方法である。 The production method of the present invention comprises:
(1) The following chemical formula (IV)
[Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing a halogen-containing aromatic phosphoric acid ester derivative represented by (A step),
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)
[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing an aromatic phosphoric diester represented by formula (step B),
(3) For the aromatic phosphoric acid diester,
The following general formula (VI)
[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
A step of obtaining a compound represented by the general formula (I) by adding a compound represented by formula (I) in an organic solvent (step C)
It is a manufacturing method containing.
(1)下記化学式(IV)
で表される化合物を、アミンの存在下においてオキシハロゲン化リンと反応させることにより、
下記一般式(V)
で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する工程(A工程)、
(2)当該含ハロゲン芳香族リン酸エステル酸誘導体を加水分解させることにより、
下記一般式(II)
で表される芳香族リン酸ジエステルを合成する工程(B工程)、
(3)当該芳香族リン酸ジエステルに対し、
下記一般式(VI)
で表される化合物を有機溶媒中において添加することによって、前記一般式(I)で表される化合物を得る工程(C工程)
を含む製造方法である。 The production method of the present invention comprises:
(1) The following chemical formula (IV)
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)
A step of synthesizing a halogen-containing aromatic phosphoric acid ester derivative represented by (A step),
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)
A step of synthesizing an aromatic phosphoric diester represented by formula (step B),
(3) For the aromatic phosphoric acid diester,
The following general formula (VI)
A step of obtaining a compound represented by the general formula (I) by adding a compound represented by formula (I) in an organic solvent (step C)
It is a manufacturing method containing.
A工程
A工程では、オキシハロゲン化リン及び前記一般式(IV)で表されるフェノール誘導体が含まれる反応系中に、アミンを添加して脱ハロゲン化水素反応させることにより、前記一般式(V)で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する。この際に添加されるアミンは、上記の選択的エステル反応を効率的に促進させる触媒として機能する。 Step A In Step A, an amine is added to a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction. ) -Containing halogen-containing aromatic phosphate ester derivatives. The amine added at this time functions as a catalyst that efficiently promotes the selective ester reaction.
A工程では、オキシハロゲン化リン及び前記一般式(IV)で表されるフェノール誘導体が含まれる反応系中に、アミンを添加して脱ハロゲン化水素反応させることにより、前記一般式(V)で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する。この際に添加されるアミンは、上記の選択的エステル反応を効率的に促進させる触媒として機能する。 Step A In Step A, an amine is added to a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction. ) -Containing halogen-containing aromatic phosphate ester derivatives. The amine added at this time functions as a catalyst that efficiently promotes the selective ester reaction.
一般式(IV)で表される化合物は、原料として市販のフェノール及びオキシハロゲン化リンを使用して反応すれば良い。オキシハロゲン化リンとして例えばオキシ塩化リン、オキシ臭化リン等を用いることができる。オキシ塩化リンを使用すれば、一般式(V)で表される化合物のハロゲン原子は塩素となる。また、オキシ塩化リンの代わりにオキシ臭化リンを使用すれば、一般式(V)で表される化合物のハロゲン原子は臭素となる。
The compound represented by the general formula (IV) may be reacted using commercially available phenol and phosphorus oxyhalide as raw materials. As phosphorus oxyhalide, for example, phosphorus oxychloride, phosphorus oxybromide and the like can be used. If phosphorus oxychloride is used, the halogen atom of the compound represented by the general formula (V) becomes chlorine. If phosphorus oxybromide is used instead of phosphorus oxychloride, the halogen atom of the compound represented by the general formula (V) is bromine.
また、上記の選択的エステル化反応を効率的に促進させる触媒として、反応系中にアミンを共存させる。アミンの種類は特に限定されないが、例えばトリエチルアミン、ピリジン、N,N-ジメチルアニリン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ[4.3.0]-5-ノネン、4-ジメチルアミノピリジン等の少なくとも1種が挙げられる。この中でも、経済的な見地よりトリエチルアミンが好ましい。
Also, an amine is allowed to coexist in the reaction system as a catalyst for efficiently promoting the selective esterification reaction. The type of amine is not particularly limited. For example, triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] At least one of -5-nonene, 4-dimethylaminopyridine and the like. Among these, triethylamine is preferable from an economical viewpoint.
一般式(V)で表される化合物を合成する方法としては、例えばオキシハロゲン化リンと一般式(IV)で表されるフェノール誘導体の両者に脱ハロゲン化水素触媒となるアミンを常温程度(約10~40℃)で混合すれば良い。反応温度は10℃を下回ると反応速度が低下するので、反応時間が長くなる。また、反応温度が40℃を超えると反応が暴走し、一般式(V)で表されるジエステル体以外にもトリエステル体等の副生成物が生成されてしまい、反応収率が低下することがある。
As a method of synthesizing the compound represented by the general formula (V), for example, an amine that serves as a dehydrohalogenation catalyst is added to both the phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) at about room temperature (about 10 to 40 ° C.). When the reaction temperature is lower than 10 ° C., the reaction rate decreases, so the reaction time becomes longer. In addition, when the reaction temperature exceeds 40 ° C., the reaction runs away, and by-products such as triesters are generated in addition to the diesters represented by the general formula (V), resulting in a reduction in reaction yield. There is.
各原料の混合割合は、一般式(IV)で表されるフェノール誘導体1モルに対して、オキシハロゲン化リン0.4~0.6モル程度、好ましくは0.45~0.55モル程度とすれば良い。また、一般式(IV)で表されるフェノール誘導体1モルに対して、アミン0.8~1.2モル程度、好ましくは0.9~1.1モル程度にすれば良い。この原料の仕込割合が上記範囲内から外れた場合には、一般式(V)で表されるジエステル体以外のモノエステル体、トリエステル体等の副生成物が生成してしまうおそれがある。
The mixing ratio of each raw material is about 0.4 to 0.6 mol, preferably about 0.45 to 0.55 mol of phosphorus oxyhalide with respect to 1 mol of the phenol derivative represented by the general formula (IV). Just do it. Further, the amount of amine is about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, per mol of the phenol derivative represented by the general formula (IV). When the charging ratio of the raw material is out of the above range, there is a risk that by-products such as monoesters and triesters other than the diesters represented by the general formula (V) may be generated.
上記反応においては、必ずアミンのハロゲン化水素塩が生成するので、上記反応を溶媒中で行うことが好ましい。溶媒としては、特に限定されないが、例えばベンゼン、トルエン、n-ヘキサン等の炭化水素系溶媒;テトラヒドロフラン、ジオキサン等のエーテル系溶媒;ジクロロメタン、クロロホルム等のハロゲン化炭化水素系溶媒等の非プロトン系有機溶媒等を好適に用いることができる。
In the above reaction, an amine hydrogen halide salt is always generated, and therefore the above reaction is preferably carried out in a solvent. Examples of the solvent include, but are not limited to, hydrocarbon solvents such as benzene, toluene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; aprotic organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform. A solvent etc. can be used conveniently.
上記溶媒に関し、アミンのハロゲン化水素塩を水溶液化して分層し、一般式(V)で表されるジエステル体(有機溶媒層中に存在)を液液抽出による分離精製を行うため、アミンのハロゲン化水素塩水溶液の除去を行う必要がある。従って、連続反応を行うためには、上記の反応溶媒は非水溶性の軽溶媒(水よりも比重の軽い溶媒)を使用するのがより好ましい。
In order to separate and purify the diester compound represented by the general formula (V) (existing in the organic solvent layer) by liquid-liquid extraction with respect to the above solvent, the amine hydrohalide salt is made into an aqueous solution and separated. It is necessary to remove the aqueous hydrogen halide salt solution. Therefore, in order to perform a continuous reaction, it is more preferable to use a water-insoluble light solvent (a solvent having a specific gravity lighter than water) as the reaction solvent.
一般式(II)で表される芳香族リン酸ジエステルの合成を連続的に同一の反応槽で行うことが好ましい。前の反応で副成したアミンのハロゲン化水素塩を、前述のように水溶液化して分層し、一般式(V)で表されるジエステル体(有機溶媒層中に存在)を液液抽出による分離精製を行うために反応系中に水を投入することが好ましい。これを常温以下(40℃以下)にて良く攪拌して、その後は放置することにより有機溶媒層と水層とに分離し、その後に水層を除去し、アミンのハロゲン化水素塩を反応系中より除去すれば良い。
It is preferable to continuously synthesize the aromatic phosphate diester represented by the general formula (II) in the same reaction vessel. The amine hydrogen halide salt formed as a by-product in the previous reaction is made into an aqueous solution as described above and separated into layers, and the diester represented by the general formula (V) (present in the organic solvent layer) is obtained by liquid-liquid extraction. In order to perform separation and purification, it is preferable to introduce water into the reaction system. The mixture is thoroughly stirred at room temperature or lower (40 ° C or lower), and then left to separate into an organic solvent layer and an aqueous layer. Thereafter, the aqueous layer is removed, and the amine hydrogen halide salt is reacted with the reaction system. Remove from inside.
このときの温度が常温以上(40℃を超える温度)である場合には、わずかながら一般式(V)で表されるジエステル体から加水分解反応が進行してしまい、一般式(II)で酸性リン酸ジエステル体が生成して若干ながら有機溶媒層より水層に移動することが考えられるので、結果として反応収率を下げてしまうことがある。
When the temperature at this time is equal to or higher than normal temperature (temperature exceeding 40 ° C.), the hydrolysis reaction proceeds slightly from the diester represented by the general formula (V), and is acidic in the general formula (II). Since it is considered that the phosphoric acid diester is generated and slightly moves from the organic solvent layer to the aqueous layer, the reaction yield may be lowered as a result.
本発明の製造方法において、特に、A工程では、一般式(II)で表される芳香族リン酸ジエステルを1当量得るために必要な一般式(III)で表されるフェノール誘導体、オキシハロゲン化リンの仕込み割合は、フェノール誘導体で約1当量、オキシハロゲン化リン約0.5当量であり、化学量論的にロスなく合成できることから非常に経済的に有利である。
In the production method of the present invention, in particular, in step A, the phenol derivative represented by the general formula (III) and the oxyhalogenation necessary for obtaining one equivalent of the aromatic phosphoric diester represented by the general formula (II) The charging ratio of phosphorus is about 1 equivalent for the phenol derivative and about 0.5 equivalent for phosphorus oxyhalide, which is very economically advantageous because it can be synthesized without loss of stoichiometry.
B工程
B工程では、含ハロゲン芳香族リン酸エステル酸誘導体を加水分解することによって芳香族リン酸ジエステルを合成する。すなわち、一般式(V)で表される含ハロゲン芳香族リン酸エステル酸誘導体(芳香族ハロゲン化リン酸ジエステル)から一般式(II)で表される芳香族リン酸ジエステルを得るには、前記含ハロゲン芳香族リン酸エステル酸誘導体に水を添加することによって加水分解を促せば良い。 Step B In Step B, an aromatic phosphate diester is synthesized by hydrolyzing a halogen-containing aromatic phosphate ester derivative. That is, in order to obtain the aromatic phosphoric acid diester represented by the general formula (II) from the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V), Hydrolysis may be promoted by adding water to the halogen-containing aromatic phosphate ester derivative.
B工程では、含ハロゲン芳香族リン酸エステル酸誘導体を加水分解することによって芳香族リン酸ジエステルを合成する。すなわち、一般式(V)で表される含ハロゲン芳香族リン酸エステル酸誘導体(芳香族ハロゲン化リン酸ジエステル)から一般式(II)で表される芳香族リン酸ジエステルを得るには、前記含ハロゲン芳香族リン酸エステル酸誘導体に水を添加することによって加水分解を促せば良い。 Step B In Step B, an aromatic phosphate diester is synthesized by hydrolyzing a halogen-containing aromatic phosphate ester derivative. That is, in order to obtain the aromatic phosphoric acid diester represented by the general formula (II) from the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V), Hydrolysis may be promoted by adding water to the halogen-containing aromatic phosphate ester derivative.
加水分解に必要な水の量は、一般式(V)で表される含ハロゲン芳香族リン酸エステル酸誘導体(芳香族ハロゲン化リン酸ジエステル)と等量以上の化学量論量の水を加えれば良い。反応温度は限定的ではないが、好ましくは常温以上の温度(特に40℃を超える温度)、より好ましくは80~120℃で攪拌すれば良い。B工程においては、好ましくは、同時に系中に存在する有機溶媒の沸点、あるいは有機溶媒と水との共沸点で還流することが好ましい。
The amount of water required for the hydrolysis can be obtained by adding a stoichiometric amount of water equal to or greater than the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V). It ’s fine. The reaction temperature is not critical, but the stirring is preferably performed at a temperature not lower than room temperature (particularly a temperature exceeding 40 ° C.), more preferably 80 to 120 ° C. In the step B, it is preferable to reflux at the boiling point of the organic solvent present in the system at the same time or the azeotropic point of the organic solvent and water.
上記の有機溶媒としては、前反応で使用した有機溶媒をそのまま連続的に使用しても良く、他の有機溶媒を追加して使用しても良く、さらに反応系中の有機溶媒を還流除去後に他の有機溶媒を反応系中に投入する溶媒交換を行っても良い。使用できる溶媒の種類としては、前記のA工程で挙げた溶媒と同様のものを使用することができる。
As the above-mentioned organic solvent, the organic solvent used in the previous reaction may be used continuously as it is, or another organic solvent may be used in addition, and after the organic solvent in the reaction system is removed under reflux. You may perform the solvent exchange which throws in another organic solvent in a reaction system. As the kind of solvent that can be used, the same solvents as those mentioned in the above step A can be used.
B工程においては、加水分解後に過剰な水の除去と同時に、わずかながら副成される芳香族リン酸モノエステルの反応系外への除去も行うことができる。芳香族リン酸モノエステルは水溶性がかなり高いので、液液抽出を行うと芳香族リン酸ジエステルとは逆に有機溶媒層中には存在せずに完全に水層に移動する。芳香族リン酸モノエステルの環状アミン塩及び芳香族リン酸ジエステルの環状アミン塩も上記と同様以上の性質を示す。
In step B, the removal of excess water after hydrolysis can also remove the aromatic phosphate monoester, which is slightly by-produced, out of the reaction system. Aromatic phosphoric acid monoesters are very water-soluble, so when liquid-liquid extraction is performed, the aromatic phosphoric acid monoester does not exist in the organic solvent layer and moves completely to the aqueous layer, contrary to the aromatic phosphoric acid diester. The cyclic amine salt of the aromatic phosphoric acid monoester and the cyclic amine salt of the aromatic phosphoric acid diester also exhibit the above-described properties.
それゆえに、B工程における最後の反応において、非水溶性有機溶媒層と水層との非均一系加水分解は1ポット連続反応に対する寄与のみならず、モノエステル体とジエステル体の選択性を高めることにも寄与する優れた合成法であるといえる。
Therefore, in the final reaction in Step B, non-uniform hydrolysis of the water-insoluble organic solvent layer and the water layer not only contributes to the one-pot continuous reaction, but also increases the selectivity of the monoester and diester forms. It can be said that this is an excellent synthesis method that contributes to this.
もちろん、B工程終了後、公知の精製方法、固液分離方法等に従って芳香族リン酸ジエステルを回収することができるので、これを回収した後、樹脂に難燃剤を混練する際に、別々に用意した芳香族リン酸ジエステル及び環状アミンをドライブレンドした後、樹脂成分に添加しても良い。この場合、芳香族リン酸ジエステルはあまり強い吸水性はないが、ほとんどの環状アミン、環状ポリアミンは吸水性、あるいは水和物となるので、樹脂成分に添加する前に非常に高度に減圧脱水乾燥する必要があり、後の本発明難燃剤を得るのに非常に手間がかかってしまうことがある。
Of course, after the completion of Step B, the aromatic phosphate diester can be recovered in accordance with a known purification method, solid-liquid separation method, etc., so that it is prepared separately when the flame retardant is kneaded into the resin after the recovery. After the dry aromatic phosphate diester and the cyclic amine are dry blended, they may be added to the resin component. In this case, aromatic phosphoric diesters do not have very strong water absorption, but most cyclic amines and cyclic polyamines are water-absorbing or hydrated. It is necessary to do this, and it may take much time to obtain the flame retardant of the present invention later.
従って、本発明の製造方法のように、B工程の終了後、連続的にC工程を行って芳香族リン酸ジエステル環状アミン塩とすることにより、たとえ脱水乾燥する必要が生じたとしても、あまり高度な乾燥をしなくても効果的に使用することができるので、より好ましい簡便な方法といえる。
Therefore, as in the production method of the present invention, after the completion of the B step, by continuously performing the C step to obtain an aromatic phosphoric diester cyclic amine salt, even if it is necessary to dehydrate and dry, Since it can be used effectively without high drying, it can be said to be a more preferable and simple method.
C工程
C工程では、B工程終了後に一般式(III)で表される環状アミンを反応系中に添加し、攪拌混合することによって、連続的に前記一般式(I)で表される芳香族リン酸ジエステル環状アミン塩が合成できる。 In Step C, Step C, the aromatic amine represented by the general formula (I) is continuously added by adding a cyclic amine represented by the general formula (III) to the reaction system after the completion of the step B and stirring and mixing. A phosphoric diester cyclic amine salt can be synthesized.
C工程では、B工程終了後に一般式(III)で表される環状アミンを反応系中に添加し、攪拌混合することによって、連続的に前記一般式(I)で表される芳香族リン酸ジエステル環状アミン塩が合成できる。 In Step C, Step C, the aromatic amine represented by the general formula (I) is continuously added by adding a cyclic amine represented by the general formula (III) to the reaction system after the completion of the step B and stirring and mixing. A phosphoric diester cyclic amine salt can be synthesized.
一般式(III)で表される環状アミンの添加量としては、前述のとおり難燃性、耐湿性を高度に保持するため、双方のイオン当量が等しくなるように一般式(II)で表される芳香族リン酸ジエステルの含まれる化学量論量に対して、等量の適宜選択された環状アミン塩を添加するのが好ましい。一般式(III)で表される環状アミンは、公知のもの又は市販品を使用すれば良い。
The amount of cyclic amine represented by the general formula (III) is represented by the general formula (II) so that the ionic equivalents of both are equal to each other in order to maintain high flame retardancy and moisture resistance as described above. It is preferable to add an equal amount of an appropriately selected cyclic amine salt with respect to the stoichiometric amount contained in the aromatic phosphate diester. A known or commercially available cyclic amine may be used as the cyclic amine represented by the general formula (III).
C工程においても、必要に応じて溶媒中で実施することもできる。溶媒としては、例えばベンゼン、トルエン、n-ヘキサン等の炭化水素系溶媒;メタノール、イソプロピルアルコール等のアルコール系溶媒;ジクロロメタン、クロロホルム等のハロゲン化炭化水素溶媒等が挙げられる。
Also in the C step, it can be carried out in a solvent as necessary. Examples of the solvent include hydrocarbon solvents such as benzene, toluene and n-hexane; alcohol solvents such as methanol and isopropyl alcohol; halogenated hydrocarbon solvents such as dichloromethane and chloroform.
C工程後は、公知の精製方法、固液分離方法等に従って本発明環状アミン塩を回収することができる。本発明の製造方法により、一般式(I)で表される本発明環状アミン塩を合成する場合には、極めて収率が高く効率的に製造を行うことができ、好条件では再結晶後の全工程収率で80%以上(フェノール誘導体に対して)の非常に高い収率で目的物を得ることができる。
After step C, the cyclic amine salt of the present invention can be recovered according to a known purification method, solid-liquid separation method, or the like. When synthesizing the cyclic amine salt of the present invention represented by the general formula (I) by the production method of the present invention, it can be produced with a very high yield and can be efficiently produced. The target product can be obtained in a very high yield of 80% or more (relative to the phenol derivative) in the total process yield.
本発明環状アミン塩のうち、例えば一般式(II)で表される芳香族リン酸ジエステルとしてジフェニルヒドロゲンホスフェート(DPHP)、一般式(III)で表される環状アミンとしてピペラジンを選択した場合、得られた化合物の1H-NMRを測定してみると、ピペラジン(メチレン)の1H-NMRのケミカルシフトがδ2.84ppmから3.23ppmへと、同様に31P-NMRでは、DPHP(リン)のケミカルシフトがδ-11.31ppmから-10.54ppmへと、双方ともに低磁場シフトする。これにより、ピペラジンとDPHPが配位結合によって、ピペラジン-1,4-ジイウムカチオン及びジフェニルヒドロゲンホスフェートアニオンからなるオニウム塩が形成されていることがわかる。
Among the cyclic amine salts of the present invention, for example, when diphenyl hydrogen phosphate (DPHP) is selected as the aromatic phosphate diester represented by the general formula (II), and piperazine is selected as the cyclic amine represented by the general formula (III), When analyzed by 1 H-NMR of the obtained compound, a 1 H-NMR chemical shifts of piperazine (methylene) from δ2.84ppm to 3.23Ppm, Similarly, in 31 P-NMR, DPHP (phosphorus ) Shifts from δ-11.31 ppm to -10.54 ppm, both of which shift by a low magnetic field. This shows that an onium salt composed of a piperazine-1,4-diium cation and a diphenylhydrogen phosphate anion is formed by coordination bond between piperazine and DPHP.
(2)本発明環状アミン塩を含む難燃剤組成物
本発明の難燃剤組成物(本発明難燃剤)は、本発明環状アミン塩の1種又は2種以上を含む。すなわち、前記(1)で示した環状アミン塩の少なくとも1種を有効成分として含むものである。 (2) Flame retardant composition containing the cyclic amine salt of the present invention The flame retardant composition of the present invention (the flame retardant of the present invention) contains one or more of the cyclic amine salts of the present invention. That is, it contains at least one of the cyclic amine salts shown in (1) as an active ingredient.
本発明の難燃剤組成物(本発明難燃剤)は、本発明環状アミン塩の1種又は2種以上を含む。すなわち、前記(1)で示した環状アミン塩の少なくとも1種を有効成分として含むものである。 (2) Flame retardant composition containing the cyclic amine salt of the present invention The flame retardant composition of the present invention (the flame retardant of the present invention) contains one or more of the cyclic amine salts of the present invention. That is, it contains at least one of the cyclic amine salts shown in (1) as an active ingredient.
本発明環状アミン塩に必須かつ最も重要な性能である耐湿性及び耐水溶性という点において、本発明では環状アミン塩中に混入し得る芳香族リン酸モノエステルの存在はそれらの性能の劣化をもたらすので、本発明難燃剤中への芳香族リン酸モノエステルの混入量は少ないほど好ましい。すなわち、本発明難燃剤中の芳香族リン酸モノエステルの含有量は1重量%以下であることが好ましく、特に0.1重量%以下であることがより好ましく、さらには0重量%であることが最も好ましい。
In the present invention, in terms of moisture resistance and water resistance, which are essential and most important performances of the cyclic amine salt of the present invention, the presence of an aromatic phosphate monoester that can be mixed in the cyclic amine salt causes deterioration of the performance. Therefore, the smaller the amount of the aromatic phosphate monoester mixed in the flame retardant of the present invention, the better. That is, the content of the aromatic phosphoric acid monoester in the flame retardant of the present invention is preferably 1% by weight or less, more preferably 0.1% by weight or less, and further preferably 0% by weight. Is most preferred.
なお、芳香族リン酸モノエステルとA成分である芳香族リン酸ジエステルとは、例えばLC/MS、或いはGC/MSを測定することによって、その存在比を調べることができる。また、31P-NMRを測定することによって、ジエステル体のケミカルシフトがδ-12~-10ppm程度、モノエステル体のケミカルシフトがδ-3~-4ppm程度であることから容易に確認することができる。
In addition, the abundance ratio of the aromatic phosphoric acid monoester and the aromatic phosphoric acid diester as the component A can be examined by measuring, for example, LC / MS or GC / MS. Further, by measuring 31 P-NMR, it can be easily confirmed that the chemical shift of the diester is about δ-12 to -10 ppm and the chemical shift of the monoester is about δ-3 to -4 ppm. it can.
また、本発明難燃剤では、本発明環状アミン塩のほか、公知の難燃剤で配合されている添加剤が含まれていても良い。
In addition, the flame retardant of the present invention may contain additives blended with known flame retardants in addition to the cyclic amine salt of the present invention.
特に、本発明難燃剤では、リン酸塩類(C成分)を好適に用いることができる。リン酸塩類のみを難燃剤として使用しても、難燃性、耐湿性、及びブルーミング耐性を同時に獲得することは非常に困難であるが、本発明環状アミン塩とリン酸塩類を同時に含有させることによって、難燃性及び耐湿性を高度に強化する以外にも、ブルーミング現象をより効果的に防止できるという効果を得ることができる。前述のように、従来技術の難燃剤では、リン酸塩類は基本的に合成樹脂とは混ざりにくく分散安定化しにくい。これらの難燃剤成分が樹脂中に良好に分散されていないと、難燃性樹脂の成形性、耐衝撃性等の諸物性が低下してしまい、さらに容易にブリードアウトすることが多い。これに対し、本発明では、本発明環状アミン塩がリン酸塩類に対して合成樹脂中において分散安定化剤及び/又は相溶化剤としても機能する点において、従来技術よりも優位に立つものである。
In particular, phosphates (C component) can be preferably used in the flame retardant of the present invention. Even if only phosphates are used as flame retardants, it is very difficult to simultaneously acquire flame retardancy, moisture resistance, and blooming resistance. However, the cyclic amine salt of the present invention and phosphates should be contained at the same time. Thus, in addition to highly enhancing the flame retardancy and moisture resistance, it is possible to obtain an effect of more effectively preventing the blooming phenomenon. As described above, in the conventional flame retardant, phosphates are basically difficult to mix with the synthetic resin and difficult to stabilize. If these flame retardant components are not well dispersed in the resin, various physical properties such as moldability and impact resistance of the flame retardant resin are deteriorated, and more often bleed out. In contrast, in the present invention, the cyclic amine salt of the present invention is superior to the prior art in that it functions as a dispersion stabilizer and / or a compatibilizer in the synthetic resin with respect to phosphates. is there.
前記リン酸塩類としては、特に限定されないが、例えば1)ポリリン酸アンモニウム等の無機縮合リン酸アンモニウム塩、2)被覆されたポリリン酸アンモニウム等の無機縮合リン酸アンモニウム塩、3)リン酸、ピロリン酸又は縮合リン酸とトリアジン誘導体とからなる有機塩類等の少なくとも1種を挙げることができる。
Although it does not specifically limit as said phosphates, For example, 1) Inorganic condensed ammonium phosphate salts, such as ammonium polyphosphate, 2) Inorganic condensed ammonium phosphate salts, such as coated ammonium polyphosphate, 3) Phosphoric acid, pyrroline Examples thereof include at least one of organic salts composed of an acid or condensed phosphoric acid and a triazine derivative.
前記C成分の1)ポリリン酸アンモニウム等の無機縮合リン酸アンモニウム塩としては、市販品の例として、製品名「エクソリットAP422」、「エクソリットAP700」(いずれもクラリアント社製)、製品名「テラージュS-10」、「テラージュS-20」(いずれもチッソ(株)社製)、製品名「スミセーフP」(住友化学工業社製)等が挙げられる。
Examples of commercially available products of inorganic condensed ammonium phosphates such as C component 1) inorganic condensed ammonium phosphate such as ammonium polyphosphate include product names “Exorit AP422”, “Exorit AP700” (both manufactured by Clariant), and product names “Terrage S”. -10 "," Terrage S-20 "(all manufactured by Chisso Corporation), and the product name" Sumisafe P "(manufactured by Sumitomo Chemical Co., Ltd.).
前記C成分の2)被覆されたポリリン酸アンモニウム等の無機縮合リン酸アンモニウム塩は、吸湿によって容易に加水分解されるポリリン酸アンモニウム塩の有する欠点を補うために、熱硬化樹脂でマイクロカプセル化したり、メラミン架橋によって被覆等の表面処理を行ったり、また界面活性剤、シリコン化合物等によって顆粒の表面処理を行ったものである。これらの市販品の例として、製品名「エクソリットAP462」(クラリアント社製)、製品名「テラージュC-30」、「テラージュC-60」、「テラージュC-70」、「テラージュC-80」(いずれもチッソ(株)社製)等が挙げられる。
2) The coated inorganic condensed ammonium phosphate salt such as ammonium polyphosphate coated with component C may be microencapsulated with a thermosetting resin to compensate for the disadvantages of the ammonium polyphosphate salt that is easily hydrolyzed by moisture absorption. Further, surface treatment such as coating is performed by melamine cross-linking, and surface treatment of granules is performed by a surfactant, a silicon compound, or the like. Examples of these commercially available products are product names “Exorit AP462” (manufactured by Clariant), product names “Terrage C-30”, “Terrage C-60”, “Terrage C-70”, “Terrage C-80” ( All of them are manufactured by Chisso Corporation).
前記C成分の3)リン酸、ピロリン酸、若しくは縮合リン酸と、トリアジン誘導体からなるアミンとからなる有機塩類としては、具体的にはメラミン、グアナミン、メチルグアナミン、エチルグアナミン、ベンゾグアナミン、ベンジルグアナミン、グアナジン、グアニジン、2,4-ジアミノ-6-モルホリノ-1,3,5-トリアジン、2,4-ジアミノ-6-チオモルホリノ-1,3,5-トリアジン等のトリアジン誘導体のリン酸塩、ピロリン酸塩、3分子以上リン酸が縮合したポリリン酸塩が挙げられる。
Specific examples of organic salts composed of 3) phosphoric acid, pyrophosphoric acid or condensed phosphoric acid of the C component and an amine composed of a triazine derivative include melamine, guanamine, methylguanamine, ethylguanamine, benzoguanamine, benzylguanamine, Guanidine, guanidine, phosphates of triazine derivatives such as 2,4-diamino-6-morpholino-1,3,5-triazine, 2,4-diamino-6-thiomorpholino-1,3,5-triazine, pyrroline An acid salt, and a polyphosphate condensed with three or more molecules of phosphoric acid.
本発明難燃剤において、本発明環状アミン塩のほか、C成分のうち、少なくとも1種のリン酸塩類を含む難燃剤組成物を種々の樹脂成分に混合することにより、合成樹脂組成物等を高度に難燃化することができる。
In the flame retardant of the present invention, in addition to the cyclic amine salt of the present invention, a flame retardant composition containing at least one phosphate among the C components is mixed with various resin components to make a synthetic resin composition and the like highly advanced. Can be flame retardant.
本発明難燃剤は、チャー形成型のリン・窒素系難燃剤であるが、代表的なチャー形成形難燃剤である赤燐、ポリリン酸アミン塩、大部分のリン酸エステル類、及びトリアジン誘導体は水分に対して大きな影響を受けやすい。つまり、難燃剤として致命的な欠陥となるリン系化合物の特徴、例えば、赤燐に由来するフォスフィン(PH3)ガスの発生、ポリリン酸アミン塩に由来するブルーミング現象の発生、リン酸エステルの加水分解に由来する着色、アミン(窒素)系分解ガスの発生、樹脂の着色や分子量低下等の欠陥は、ほとんどが吸湿による水分及び水分由来の活性ラジカル等が原因となっているという問題がある。
The flame retardant of the present invention is a char-forming phosphorus / nitrogen flame retardant, but typical char-forming flame retardants include red phosphorus, polyphosphate amine salts, most phosphate esters, and triazine derivatives. Susceptible to moisture. That is, characteristics of phosphorus compounds that are fatal defects as flame retardants, such as generation of phosphine (PH 3 ) gas derived from red phosphorus, occurrence of blooming phenomenon derived from polyphosphate amine salt, hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitrogen) -based decomposition gas, resin coloring and molecular weight reduction are caused by moisture caused by moisture absorption and active radicals derived from moisture.
すなわち、チャー形成形のリン系難燃剤として実用上最も重要とされる性能は、合成樹脂に高度な難燃性を付与しつつ、同時に高度に耐吸湿性を備えることによりある。
That is, the most important performance in practical use as a char-forming phosphorus-based flame retardant is to impart high flame resistance to the synthetic resin and at the same time have high moisture absorption resistance.
また、チャー形成形のリン系難燃剤のほとんどは、一般的に樹脂相溶性が悪いので、例えば極性の低いポリオレフィン樹脂に添加しても樹脂中に均一に安定的に分散し続けることはないので、難燃剤の樹脂表面への移行や樹脂の機械的物性の極端な低下を引き起こすという問題がある。
In addition, most of the char-forming phosphorus flame retardants generally have poor resin compatibility. For example, even when added to polyolefin resins with low polarity, they do not continue to disperse uniformly and stably in the resin. There is a problem that the flame retardant is transferred to the resin surface and the mechanical properties of the resin are extremely lowered.
リン酸エステル類からなる一部の難燃剤では、樹脂相溶性の優れたものも存在するが、融点及び熱分解開始温度が低い液体のものがほとんどであるために可塑性が強すぎて成形性を低下させることがあり、また成形品に対して高度な難燃性を付与することができないことが多い。
Some flame retardants composed of phosphate esters have excellent resin compatibility, but most liquids have a low melting point and low thermal decomposition starting temperature, so the plasticity is too strong and the moldability is low. In many cases, the flame retardancy may be lowered, and high flame retardancy may not be imparted to the molded product.
本発明環状アミン塩は単独でも非吸湿性難燃剤であるが、より難燃性を強化するために吸湿性をもつC成分を同時に添加した場合においても、本発明環状アミン塩が樹脂中でC成分を安定的に分散又は相溶化させることができる一種の保護緩衝剤の役割をするので、吸湿性を抑え、なおかつ、難燃剤組成物の樹脂中での分散均一性を維持することにより、成形品表面への移行性、ブルーミング現象、あるいは成形品の表面荒れを同時に抑えることができる。
The cyclic amine salt of the present invention alone is a non-hygroscopic flame retardant, but the cyclic amine salt of the present invention is also contained in the resin even when a C component having hygroscopicity is added at the same time in order to further enhance the flame retardancy. Since it acts as a kind of protective buffer that can stably disperse or compatibilize the components, it suppresses hygroscopicity and also maintains dispersion uniformity in the resin of the flame retardant composition. Transferability to the product surface, blooming phenomenon, or surface roughness of the molded product can be suppressed at the same time.
2.本発明難燃剤を含む難燃性樹脂組成物(本発明組成物)
(1)難燃性樹脂組成物
本発明は、本発明難燃剤及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して本発明環状アミン塩1~100重量部を含む難燃性樹脂組成物を包含する。 2. Flame retardant resin composition containing the flame retardant of the present invention (the composition of the present invention)
(1) Flame Retardant Resin Composition The present invention is a resin composition comprising the flame retardant of the present invention and a resin component, and comprises 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. Includes flammable resin composition.
(1)難燃性樹脂組成物
本発明は、本発明難燃剤及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して本発明環状アミン塩1~100重量部を含む難燃性樹脂組成物を包含する。 2. Flame retardant resin composition containing the flame retardant of the present invention (the composition of the present invention)
(1) Flame Retardant Resin Composition The present invention is a resin composition comprising the flame retardant of the present invention and a resin component, and comprises 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. Includes flammable resin composition.
樹脂成分としては、特に制限されるものではなく、例えば公知の合成樹脂から選択することができる。より具体的には、ポリオレフィン系樹脂、ポリスチレン系樹脂、ポリビニル系樹脂、ポリアミド系樹脂、ポリ意味時計樹脂、ポリエステル系樹脂、ポリエーテル系樹脂、ポリカーボネート系樹脂、ポリアセタール系樹脂、ポリエーテル・エーテルケトン樹脂、ポリフエニレン・スルフイド樹脂、ポリアミド・イミド樹脂、ポリエーテル・スルフォン樹脂、ポリスルフォン樹脂、ポリメチル・ペンテン樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、ポリウレタン樹脂、フェノール樹脂等の熱可塑性樹脂や熱硬化性樹脂のホモポリマーあるいはコポリマーの単独又はそれらの組み合わせによる樹脂アロイ類等が挙げられる。
The resin component is not particularly limited, and can be selected from, for example, known synthetic resins. More specifically, polyolefin resins, polystyrene resins, polyvinyl resins, polyamide resins, poly-meaning clock resins, polyester resins, polyether resins, polycarbonate resins, polyacetal resins, polyether ether ketone resins. , Thermoplastic resins such as polyphenylene / sulfide resin, polyamide / imide resin, polyether / sulfone resin, polysulfone resin, polymethyl / pentene resin, urea resin, melamine resin, epoxy resin, polyurethane resin, phenol resin, etc. And resin alloys by homopolymers or copolymers alone or in combination thereof.
本発明組成物において好適なポリオレフィン系樹脂としては、エチレン、プロピレン、1-ブテン、4-メチル-1-ペンテン、1-ヘキセン、1-オクテン等のα-オレフィンの単独重合体、前記のα―オレフィン同士のランダムあるいはブロック共重合体の単体及び混合物等の樹脂、さらにこれと酢酸ビニル又は無水マレイン酸が共重合された樹脂等のポリオレフィン系樹脂が好適に使用することができる。より具体的には、プロピレン単独重合体、プロピレン-エチレンランダム共重合体、プロピレン-エチレンブロック共重合体、プロピレン-エチレン-ブテン共重合体等のようなポリプロピレン系樹脂、低密度エチレン単独重合体、高密度エチレン単独重合体、エチレン-α-オレフィンランダム共重合体、エチレン-酢酸ビニル共重合体、エチレン-エチルアクリレート共重合体のようなポリエチレン系樹脂等が挙げられる。また、本発明において難燃性樹脂組成物の物性を改良するために、必要に応じて、ポリエチレン系合成ゴム、ポリオレフィン系合成ゴム等を配合することもできる。
Suitable polyolefin resins in the composition of the present invention include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above α- Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used. More specifically, polypropylene resins such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer, low density ethylene homopolymer, Examples thereof include polyethylene resins such as high-density ethylene homopolymer, ethylene-α-olefin random copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. Further, in the present invention, in order to improve the physical properties of the flame retardant resin composition, a polyethylene-based synthetic rubber, a polyolefin-based synthetic rubber, or the like can be blended as necessary.
ポリスチレン系樹脂としては、例えばポリスチレン、アクリロニトリル-スチレン共重合体、アクリロニトリル-ブタジエン-スチレン共重合体等が挙げられる。
Examples of the polystyrene resin include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.
ポリビニル系樹脂としては、例えばアルキルアクリレート、アルキルメタクリレート、酢酸ビニル、ビニルアルコール等のようなビニル単量体の単独重合体のほか、これらのビニル単量体と前述のα-オレフィンとの共重合体等を挙げることができる。
Examples of the polyvinyl resin include homopolymers of vinyl monomers such as alkyl acrylates, alkyl methacrylates, vinyl acetate, vinyl alcohol and the like, and copolymers of these vinyl monomers and the aforementioned α-olefins. Etc.
ポリアミド系樹脂としては、例えばポリアミド6、ポリアミド6・6、ポリアミド11、ポリアミド12、ポリアミド6・3、ポリアミド6・4、ポリアミド4・6、ポリアミド6・10等が挙げられる。
Examples of the polyamide-based resin include polyamide 6, polyamide 6 • 6, polyamide 11, polyamide 12, polyamide 6 • 3, polyamide 6 • 4, polyamide 4 • 6, polyamide 6 • 10, and the like.
ポリエステル系樹脂としては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリ(1,4-シキロヘキサンジメチレンテレフタレート)等が挙げられる。
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate), and the like.
ポリエーテル系樹脂としては、例えばポリフェニレンエーテル、ポリエチレンエーテル等が挙げられる。
Examples of polyether resins include polyphenylene ether and polyethylene ether.
ポリカーボネート系樹脂としては、例えば芳香族ポリカーボネート、脂肪族ポリカーボネート、脂肪族-芳香族ポリカーボネート等が挙げられる。一般的には2,2-ビス(4-ヒドロキシフェニル)アルカン系、ビス(4-ヒドロキシフェニル)エーテル系、ビス(4-ヒドロキシフェニル)スルホン系、ビス(4-ヒドロキシフェニル)スルフィド系等のビスフェノール類からなる重合物又は共重合物が挙げられる。
Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, bisphenol such as 2,2-bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, etc. Polymers or copolymers consisting of the above are mentioned.
また、本発明組成物における樹脂成分としては、上述の各系の樹脂類のほかにも、2種以上の樹脂成分を適当な相溶化剤の共存下又は非共存下に混練して製造されたアロイ樹脂も含まれる。アロイ樹脂としては、例えばポリプロピレン/ポリアミド、ポリプロピレン/ポリブチレンテレフタレート、アクリロニトリル・ブタジエン・スチレン共重合体/ポリブチレンテレフタレート、アクリロニトリル・ブタジエン・スチレン共重合体/ポリアミド、ポリカーボネート/アクリロニトリル・ブタジエン・スチレン共重合体、ポリカーボネート/ポリメチルメタクリレート、ポリカーボネート/ポリアミド、ポリカーボネート/ポリエチレンテレフタレート、ポリカーボネート/ポリブチレンテレフタレート等が挙げられる。
Further, as the resin component in the composition of the present invention, in addition to the above-mentioned resins, two or more types of resin components were kneaded in the presence or absence of an appropriate compatibilizer. Alloy resins are also included. Examples of alloy resins include polypropylene / polyamide, polypropylene / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polyamide, and polycarbonate / acrylonitrile / butadiene / styrene copolymer. Polycarbonate / polymethyl methacrylate, polycarbonate / polyamide, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, and the like.
さらに、樹脂成分として、前記した合成樹脂の変性物、例えば合成樹脂を不飽和カルボン酸類(例えば、アクリル酸、メタクリル酸、マレイン酸、フマル酸、無水マレイン酸、無水イタコン酸等)又はシロキサン等によりグラフトさせて得られる変性物も用いることができる。
Further, as a resin component, a modified product of the above-described synthetic resin, for example, a synthetic resin is obtained by unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.) A modified product obtained by grafting can also be used.
上記の樹脂成分の中でも、より汎用性が高く、安価で、かつ、各種物性のバランスを取りやすい成形品が得られるという見地より、特にポリオレフィン系樹脂と本発明難燃剤との組み合わせがより好ましい。特に、ポリプロピレン単独重合体、エチレン-プロピレンランダム共重合体及びエチレン-プロピレンブロック共重合体の少なくとも1種と本発明難燃剤とを含む難燃性樹脂組成物は、成形性、耐熱性、耐吸湿性及び特に高度な難燃性に関し、従来にない特に優れた性能を発揮できるのでより好ましい。
Among the above resin components, the combination of the polyolefin resin and the flame retardant of the present invention is particularly preferred from the viewpoint that a molded product having higher versatility, lower cost, and balance of various physical properties can be obtained. In particular, a flame retardant resin composition containing at least one of a polypropylene homopolymer, an ethylene-propylene random copolymer, and an ethylene-propylene block copolymer and the flame retardant of the present invention has moldability, heat resistance, and moisture absorption resistance. With regard to the properties and particularly high flame retardancy, it is more preferable because it can exhibit particularly excellent performance that has not been achieved in the past.
本発明組成物においては、本発明環状アミン塩の配合割合について特に制限はなく、各種物性及び難燃性を保持する程度の配合量を添加すれば良い。このなかでも特に混練安定性及び成形性を保ちつつ、さらには成形品に対して耐湿性及び高度な難燃性を与えるには、樹脂成分100重量部に対して本発明環状アミン塩1~100重量部を配合すれば良く、さらに好ましくは10重量部~50重量部を配合すれば良い。本発明難燃剤の配合割合が1重量部を下回ると難燃性が不十分となることがある一方、100重量部を超えると樹脂本来のもつ特性が得られなくなるおそれがある。
In the composition of the present invention, the blending ratio of the cyclic amine salt of the present invention is not particularly limited, and a blending amount sufficient to maintain various physical properties and flame retardancy may be added. Among these, the cyclic amine salts 1 to 100 of the present invention are added to 100 parts by weight of the resin component in order to keep the kneading stability and moldability, and to give the molded article moisture resistance and high flame retardancy. What is necessary is just to mix | blend a weight part, and what is necessary is just to mix | blend 10 to 50 weight part more preferably. If the blending ratio of the flame retardant of the present invention is less than 1 part by weight, the flame retardancy may be insufficient. On the other hand, if it exceeds 100 parts by weight, the inherent properties of the resin may not be obtained.
また、本発明環状アミン塩に加えて、前記C成分をさらに添加することにより、本発明組成物の特徴であるチャー形成能に対して、発泡による炭化促進効果(アミン、トリアジン、メラミン等のリン酸塩等)が相乗的に起こることにより、より高度な難燃性を獲得することが可能となる。
In addition to the cyclic amine salt of the present invention, by further adding the component C, the char forming ability characteristic of the composition of the present invention is enhanced by the effect of promoting carbonization by foaming (phosphorus such as amine, triazine and melamine). As a result of the synergistic occurrence of acid salts, etc., it becomes possible to obtain higher flame retardancy.
本発明における難燃剤組成物及び樹脂成分を含む樹脂組成物においては、その配合割合として樹脂成分100重量部に対して本発明環状アミン塩を1~50重量部、当該C成分を1~50重量部とすることが好ましく、特に本発明環状アミン塩を10~30重量部、当該C成分を10~30重量部とすることがより好ましい。
In the resin composition containing the flame retardant composition and the resin component in the present invention, the blending ratio is 1 to 50 parts by weight of the cyclic amine salt of the present invention and 1 to 50 parts by weight of the C component with respect to 100 parts by weight of the resin component. The cyclic amine salt of the present invention is preferably 10 to 30 parts by weight, and the C component is more preferably 10 to 30 parts by weight.
本発明組成物には、上記成分のほかに、本発明の効果を妨げない範囲内において、必要に応じて公知又は市販の添加剤を適宜配合することができる。例示すると、フェノール系化合物、ホスフィン系化合物、チオエーテル系化合物等の酸化防止剤、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチレート系化合物、ヒンダードアミン系化合物等の紫外線吸収剤又は耐光剤;カチオン系化合物、アニオン系化合物、ノニオン系化合物、両性化合物、金属酸化物、π系導電性高分子化合物、カーボン等の帯電防止剤及び導電剤;脂肪酸、脂肪酸アミド、脂肪酸エステル、脂肪酸金属塩等の滑剤;ベンジリデンソルビトール系化合物等の核剤;タルク、炭酸カルシウム、硫酸バリウム、マイカ、ガラス繊維、ガラスビーズ、低融点ガラス等の充填剤のほか、金属不活性化剤、着色剤、ブルーミング防止剤、表面改質剤、アンチブロッキング剤、防曇剤、粘着剤、ガス吸着剤、鮮度保持剤、酵素、消臭剤、香料等が挙げられる。
In addition to the above components, the composition of the present invention can be appropriately blended with known or commercially available additives as necessary within the range not impeding the effects of the present invention. Illustrative examples are antioxidants such as phenol compounds, phosphine compounds, thioether compounds, UV absorbers or light stabilizers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, hindered amine compounds; cationic compounds, anions Compounds, nonionic compounds, amphoteric compounds, metal oxides, π-based conductive polymer compounds, carbon and other antistatic agents and conductive agents; fatty acids, fatty acid amides, fatty acid esters, fatty acid metal salts and other lubricants; benzylidene sorbitols Nucleating agents such as compounds; in addition to fillers such as talc, calcium carbonate, barium sulfate, mica, glass fiber, glass beads, low melting glass, metal deactivators, colorants, antiblooming agents, surface modifiers, Anti-blocking agent, anti-fogging agent, adhesive, gas adsorbent, freshness preservation Agents, enzymes, deodorants, fragrances, and the like.
また、本発明組成物のドリップコントロール剤として、フィブリル形成能を持つポリテトラフルオロエチレン含有混合粒子粉体を添加することもできる。フィブリル形成能を有するポリテトラフルオロエチレン含有混合粒子粉体を添加することにより、難燃性樹脂組成物の燃焼性試験、特にUL規格の垂直燃焼試験(UL94V)において、燃焼時の試験片のドリップ防止性能をより高めることができる。
Also, as the drip control agent of the composition of the present invention, polytetrafluoroethylene-containing mixed particle powder having fibril forming ability can be added. Addition of polytetrafluoroethylene-containing mixed particle powder having fibril-forming ability enables drip of test pieces during combustion in a flammability test of a flame retardant resin composition, particularly in a UL standard vertical combustion test (UL94V) The prevention performance can be further increased.
フィブリル形成能を有するポリテトラフルオロエチレン含有混合粒子粉体としては、例えばポリテトラフルオロエチレン、テトラフルオロエチレン系共重合体等が挙げられるが、好ましくはポリテトラフルオロエチレン(PTFE)である。
Examples of the polytetrafluoroethylene-containing mixed particle powder having a fibril-forming ability include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer, and polytetrafluoroethylene (PTFE) is preferable.
この場合、前記粉体の平均粒径は限定的ではないが、通常0.1~1000μm程度とすれば良い。また、その添加量は所望のドリップ防止性能等に応じて適宜設定できるが、一般的には樹脂成分100重量部に対して0.01~10重量部程度とすることが好ましい。
In this case, the average particle size of the powder is not limited, but it is usually about 0.1 to 1000 μm. The addition amount can be appropriately set according to the desired drip prevention performance and the like, but is generally preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component.
(2)難燃性樹脂組成物の製造方法
本発明組成物は、上記各成分を均一に混合することにより得ることができる。好ましくは、上記各成分を溶融混練することによって製造することができる。その場合の混練順序も特に限定されず、各々を同時に混合しても良いし、あるいは数種類を予め混合し、残りを後から混合しても良い。 (2) Method for Producing Flame Retardant Resin Composition The composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can manufacture by melt-kneading said each component. The kneading order in that case is not particularly limited, either may be mixed at the same time, or several types may be mixed in advance and the rest may be mixed later.
本発明組成物は、上記各成分を均一に混合することにより得ることができる。好ましくは、上記各成分を溶融混練することによって製造することができる。その場合の混練順序も特に限定されず、各々を同時に混合しても良いし、あるいは数種類を予め混合し、残りを後から混合しても良い。 (2) Method for Producing Flame Retardant Resin Composition The composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can manufacture by melt-kneading said each component. The kneading order in that case is not particularly limited, either may be mixed at the same time, or several types may be mixed in advance and the rest may be mixed later.
混合方法としては限定的でなく、例えばタンブラー式V型ブレンダー、ヘンシェルミキサー、リボンミキサー等の高速撹拌機、単軸、二軸連続混練機、ロールミキサー等の装置を単独で又は組み合わせて用いる方法が採用できる。
The mixing method is not limited. For example, a high-speed stirrer such as a tumbler type V-type blender, a Henschel mixer, or a ribbon mixer, a single-screw or twin-screw continuous kneader, or a method that uses a roll mixer alone or in combination. Can be adopted.
本発明では、さらに予め数種をマスターバッチとして合成樹脂と高濃度の組成物を作成し、その後さらに樹脂と混合希釈し、所定の樹脂組成物を得ることもできる。
In the present invention, a synthetic resin and a high-concentration composition can be prepared using several types of master batches in advance, and then further mixed and diluted with the resin to obtain a predetermined resin composition.
(3)難燃性樹脂組成物の使用
本発明組成物は、優れた難燃性を達成するとともに、ブリードが効果的に抑制できるため、成形品として好適に用いることができる。すなわち、本発明の難燃性樹脂組成物は、成形品の製造のための樹脂組成物として好適に用いることができる。これにより、難燃性に優れた成形品を提供することができる。 (3) Use of flame retardant resin composition The composition of the present invention achieves excellent flame retardancy and can effectively suppress bleed, and therefore can be suitably used as a molded product. That is, the flame retardant resin composition of the present invention can be suitably used as a resin composition for producing a molded product. Thereby, the molded article excellent in the flame retardance can be provided.
本発明組成物は、優れた難燃性を達成するとともに、ブリードが効果的に抑制できるため、成形品として好適に用いることができる。すなわち、本発明の難燃性樹脂組成物は、成形品の製造のための樹脂組成物として好適に用いることができる。これにより、難燃性に優れた成形品を提供することができる。 (3) Use of flame retardant resin composition The composition of the present invention achieves excellent flame retardancy and can effectively suppress bleed, and therefore can be suitably used as a molded product. That is, the flame retardant resin composition of the present invention can be suitably used as a resin composition for producing a molded product. Thereby, the molded article excellent in the flame retardance can be provided.
3.成形品
本発明は、本発明の難燃性樹脂組成物を成形してなる難燃性樹脂成形品も包含する。 3. Molded Article The present invention includes a flame retardant resin molded article obtained by molding the flame retardant resin composition of the present invention.
本発明は、本発明の難燃性樹脂組成物を成形してなる難燃性樹脂成形品も包含する。 3. Molded Article The present invention includes a flame retardant resin molded article obtained by molding the flame retardant resin composition of the present invention.
成形方法は特に制限がなく、例えば射出成形、押出成形等の公知の成形方法が使用できる。例えば、押出成形機による方法、一度シートを作成し、これを真空成形、プレス成形等の二次加工による方法、射出成形機による方法等が挙げられるが、本発明では汎用性が高いという点で特に射出成形が好ましい。
The molding method is not particularly limited, and known molding methods such as injection molding and extrusion molding can be used. For example, a method using an extrusion molding machine, a sheet once prepared, a method using secondary processing such as vacuum molding and press molding, a method using an injection molding machine, and the like can be mentioned, but the present invention is highly versatile. In particular, injection molding is preferred.
射出成形においても、通常のコールドランナー方式の射出成形法だけではなく、ランナーレスを可能にするホットランナー方式によって成形品を製造することができる。さらには、例えばガスアシスト射出成形、射出圧縮成形、超高速射出成形等を採用することもできる。
Also in injection molding, a molded product can be manufactured not only by a normal cold runner injection molding method but also by a hot runner method that enables runnerless operation. Furthermore, for example, gas assist injection molding, injection compression molding, ultra-high speed injection molding, or the like can be employed.
本発明の難燃性樹脂組成物からなる成形品としては、家電製品、OA製品、自動車分野等における難燃性を必要とされる用途に適用することができる。具体的には、電線・ケーブル等の絶縁被覆材料又は各種電気部品、メーターボックス、ランプハウジング、コルゲートチューブ、電線被覆材、バッテリー部品等の各種自動車、船舶、航空機部品、洗面台部品、便器部品、風呂場部品、床暖房部品、照明器具、エアコン等の各種住宅設備部品、屋根材、天井材、壁材、床材等各種建築材料、テレビ、ラジオ、録画・録音機器、洗濯機、冷蔵庫、掃除機、炊飯器、照明機器等の家庭電化製品等の用途に好適に用いられる。
The molded article made of the flame-retardant resin composition of the present invention can be applied to uses that require flame retardancy in home appliances, OA products, automobile fields, and the like. Specifically, insulation coating materials such as electric wires and cables or various electric parts, meter boxes, lamp housings, corrugated tubes, electric wire coating materials, various automobiles such as battery parts, ships, aircraft parts, wash basin parts, toilet parts, Various bathroom equipment parts, floor heating parts, lighting fixtures, various housing equipment parts such as air conditioners, roofing materials, ceiling materials, wall materials, flooring materials, TVs, radios, recording / recording equipment, washing machines, refrigerators, cleaning It is suitably used for home appliances such as a machine, rice cooker, and lighting equipment.
以下、本発明を実施例及び比較例を挙げて詳細に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.
なお、下記の合成例等において得られた各々の化合物の諸物性は次のようにして測定した。
In addition, various physical properties of each compound obtained in the following synthesis examples were measured as follows.
(1)純度
FID検出器付ガスクロマトグラフィー(GC-2010:島津製作所(株)製)及びフォトダイオードアレイ(PDA)3次元UV検出器付高速液体クロマトグラフィー(アライアンスHPLCシステム:
ウォーターズ社製)にて純度の確認を行った。
(2)融点
全自動融点測定装置(FP-62:メトラートレド社製)にて融点の測定を行った。
(3)元素分析
元素分析計(EA1110:CEインスツルメンツ社製)にて炭素、水素及び窒素を、マイクロウェーブ試料分解装置(ETHOS1:マイルストーンゼネラル社製)で湿式分解後に高周波結合プラズマ発光分析装置(ICP-OES、720ES:バリアン社製)にてリンを、それぞれの化合物について元素分析を行った。
(4)構造解析
赤外吸収分析装置(FT-IR、FT-720堀場製作所(株)製)、質量分析計付ガスクロマトグラフィー(GCMS-QP2010Plus:島津製作所(株)製)、300MHz核磁気共鳴吸収分析装置(JNM-AL300:日本電子(株)製)による水素核磁気共鳴(1H-NMR)スペクトル及びリン核磁気共鳴(31P-NMR)スペクトルより、各々の化合物の構造同定を行った。 (1) Purity Gas chromatography with FID detector (GC-2010: manufactured by Shimadzu Corporation) and high performance liquid chromatography with photodiode array (PDA) three-dimensional UV detector (Alliance HPLC system:
Purity was confirmed with Waters).
(2) Melting point The melting point was measured with a fully automatic melting point measurement apparatus (FP-62: manufactured by METTLER TOLEDO).
(3) Elemental analysis High-frequency coupled plasma emission spectrometer (EA1110: manufactured by CE Instruments) after wet decomposition of carbon, hydrogen, and nitrogen with a microwave sample decomposition apparatus (ETHOS1: manufactured by Milestone General) ( ICP-OES, 720ES (manufactured by Varian, Inc.) was subjected to elemental analysis of phosphorus and each compound.
(4) Structural analysis Infrared absorption analyzer (FT-IR, FT-720, manufactured by Horiba, Ltd.), gas chromatography with mass spectrometer (GCMS-QP2010Plus: manufactured by Shimadzu Corporation), 300 MHz nuclear magnetic resonance The structure of each compound was identified from the hydrogen nuclear magnetic resonance ( 1 H-NMR) spectrum and phosphorus nuclear magnetic resonance ( 31 P-NMR) spectrum obtained by an absorption analyzer (JNM-AL300: manufactured by JEOL Ltd.). .
FID検出器付ガスクロマトグラフィー(GC-2010:島津製作所(株)製)及びフォトダイオードアレイ(PDA)3次元UV検出器付高速液体クロマトグラフィー(アライアンスHPLCシステム:
ウォーターズ社製)にて純度の確認を行った。
(2)融点
全自動融点測定装置(FP-62:メトラートレド社製)にて融点の測定を行った。
(3)元素分析
元素分析計(EA1110:CEインスツルメンツ社製)にて炭素、水素及び窒素を、マイクロウェーブ試料分解装置(ETHOS1:マイルストーンゼネラル社製)で湿式分解後に高周波結合プラズマ発光分析装置(ICP-OES、720ES:バリアン社製)にてリンを、それぞれの化合物について元素分析を行った。
(4)構造解析
赤外吸収分析装置(FT-IR、FT-720堀場製作所(株)製)、質量分析計付ガスクロマトグラフィー(GCMS-QP2010Plus:島津製作所(株)製)、300MHz核磁気共鳴吸収分析装置(JNM-AL300:日本電子(株)製)による水素核磁気共鳴(1H-NMR)スペクトル及びリン核磁気共鳴(31P-NMR)スペクトルより、各々の化合物の構造同定を行った。 (1) Purity Gas chromatography with FID detector (GC-2010: manufactured by Shimadzu Corporation) and high performance liquid chromatography with photodiode array (PDA) three-dimensional UV detector (Alliance HPLC system:
Purity was confirmed with Waters).
(2) Melting point The melting point was measured with a fully automatic melting point measurement apparatus (FP-62: manufactured by METTLER TOLEDO).
(3) Elemental analysis High-frequency coupled plasma emission spectrometer (EA1110: manufactured by CE Instruments) after wet decomposition of carbon, hydrogen, and nitrogen with a microwave sample decomposition apparatus (ETHOS1: manufactured by Milestone General) ( ICP-OES, 720ES (manufactured by Varian, Inc.) was subjected to elemental analysis of phosphorus and each compound.
(4) Structural analysis Infrared absorption analyzer (FT-IR, FT-720, manufactured by Horiba, Ltd.), gas chromatography with mass spectrometer (GCMS-QP2010Plus: manufactured by Shimadzu Corporation), 300 MHz nuclear magnetic resonance The structure of each compound was identified from the hydrogen nuclear magnetic resonance ( 1 H-NMR) spectrum and phosphorus nuclear magnetic resonance ( 31 P-NMR) spectrum obtained by an absorption analyzer (JNM-AL300: manufactured by JEOL Ltd.). .
<合成例1>
1.ジフェニルヒドロゲンホスフェートピペラジン塩(DPHPP)の合成
1.1 ジフェニルクロロホスフェート(DPCP)の合成
コンデンサー、側管付滴下漏斗及び温度計を備えた撹拌装置付4ツ口フラスコに、フェノール94.1g(1.0mol)、オキシ塩化リン76.67g(0.5mol)及びトルエン700gを投入し、側管付滴下漏斗にはトリエチルアミン106.25g(1.05mol)を投入した。コンデンサーの上端に塩化カルシウム管を取り付けて空気中の水分が反応系内に混入しないようにした後、フラスコを恒温水槽にて30℃に保ちながら窒素雰囲気下で撹拌を開始した。撹拌開始後、滴下漏斗よりトリエチルアミンを2時間かけて反応生成物の温度が40℃を超えないように滴下させた。滴下終了後より1時間の反応熟成の後に、反応生成物をサンプリングしてGC/MSを測定したところ、得られた微黄色透明液体の反応中間体の純度は98%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z268)、反応生成物として上記式(17)で示されるジフェニルクロロホスフェート(DPCP:Mw
268.63)が得られたことが確認できた。 <Synthesis Example 1>
1. Synthesis of diphenyl hydrogen phosphate piperazine salt (DPHPP) 1.1 Synthesis of diphenyl chlorophosphate (DPCP)
A 4-neck flask with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer was charged with 94.1 g (1.0 mol) of phenol, 76.67 g (0.5 mol) of phosphorus oxychloride and 700 g of toluene, The dropping funnel with a side tube was charged with 106.25 g (1.05 mol) of triethylamine. A calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and stirring was then started in a nitrogen atmosphere while maintaining the flask at 30 ° C. in a constant temperature water bath. After the start of stirring, triethylamine was dropped from the dropping funnel over 2 hours so that the temperature of the reaction product did not exceed 40 ° C. After the reaction ripening for 1 hour from the end of the dropwise addition, the reaction product was sampled and GC / MS was measured. As a result, the purity of the obtained reaction intermediate of the slightly yellow transparent liquid was 98% or more. From the molecular ion peak of the spectrum (M + : m / z 268), diphenylchlorophosphate (DPCP: Mw) represented by the above formula (17) as a reaction product was obtained.
268.63) was obtained.
1.ジフェニルヒドロゲンホスフェートピペラジン塩(DPHPP)の合成
1.1 ジフェニルクロロホスフェート(DPCP)の合成
268.63)が得られたことが確認できた。 <Synthesis Example 1>
1. Synthesis of diphenyl hydrogen phosphate piperazine salt (DPHPP) 1.1 Synthesis of diphenyl chlorophosphate (DPCP)
268.63) was obtained.
1.2 ジフェニルヒドロゲンホスフェート(DPHP)の合成
前記1.1より、反応物中に含まれる原料のフェノールが、完全に消失しているのをGC/MSで確認した後、フラスコを恒温水槽にて20℃まで冷却し、フラスコに水140gを投入後30分撹拌した。撹拌終了後、反応液を30分静置して有機層と水層に分層させて水層を抜き出した。フラスコをマントルヒーターにて徐々に加熱しながらフラスコ内の反応液の温度が120℃に達するまで反応液中のトルエンを留去した。トルエンの留去量が560gになったところで一旦加熱を停止し、反応物を80℃になるまで冷却した後、水140gを投入して再加熱し、トルエンと水との共沸によりトルエンを反応系中から除去しながら、還流することによって同時にジフェニルヒドロゲンホスフェート(DPHP)の加水分解を2時間かけて行った。これを室温まで冷却した後、酢酸エチル300gをフラスコに投入して撹拌した後、再分層させて水層を抜き出した。有機層を水で洗浄した後、有機層中の反応生成物をサンプリングして反応中間体の純度を確認したところ、純度は99%以上(HPLC)であった。この反応生成物を完全に減圧下で乾燥させると、融点69℃の白色固体となった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた反応生成物が上記式(18)で示されるジフェニルヒドロゲンホスフェート(DPHP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 7.11-7.23(4H,m)、7.29-7.40(6H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -11.31 1.2 Synthesis of diphenylhydrogen phosphate (DPHP)
From 1.1 above, after confirming by GC / MS that the raw material phenol contained in the reaction had completely disappeared, the flask was cooled to 20 ° C. in a constant temperature water bath, and 140 g of water was added to the flask. The mixture was stirred for 30 minutes after the addition. After completion of the stirring, the reaction solution was allowed to stand for 30 minutes to be separated into an organic layer and an aqueous layer, and the aqueous layer was extracted. While gradually heating the flask with a mantle heater, toluene in the reaction solution was distilled off until the temperature of the reaction solution in the flask reached 120 ° C. When the amount of toluene distilled out reached 560 g, heating was temporarily stopped and the reaction product was cooled to 80 ° C., then 140 g of water was added and reheated, and toluene was reacted by azeotropy of toluene and water. While removing from the system, diphenylhydrogen phosphate (DPHP) was simultaneously hydrolyzed over 2 hours by refluxing. After cooling this to room temperature, 300 g of ethyl acetate was added to the flask and stirred, and then the layers were separated and the aqueous layer was extracted. After the organic layer was washed with water, the reaction product in the organic layer was sampled to confirm the purity of the reaction intermediate. As a result, the purity was 99% or higher (HPLC). When this reaction product was completely dried under reduced pressure, it became a white solid having a melting point of 69 ° C. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained reaction product was diphenyl hydrogen phosphate (DPHP) represented by the above formula (18).
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 7.11-7.23 (4H, m), 7.29-7.40 (6H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -11.31
1H-NMR(300MHz,DMSO-d6):δ/ppm 7.11-7.23(4H,m)、7.29-7.40(6H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -11.31 1.2 Synthesis of diphenylhydrogen phosphate (DPHP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 7.11-7.23 (4H, m), 7.29-7.40 (6H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -11.31
1.3 ジフェニルヒドロゲンホスフェートピペラジン塩(DPHPP)の合成
前記1.2に続いて、反応生成物であるジフェニルヒドロゲンホスフェート(DPHP)を含む有機層にメタノール1000gを加えて溶解させて、側管付滴下漏斗にメタノール200gに溶解させた無水ピペラジン21.5g(0.25mol)溶液を投入した。反応液を撹拌しながら2時間かけてピペラジン溶液を滴下すると、白色固体が析出した。この白色固体をメタノール/水(2/1,wt)で再結晶することにより、117.1g(0.20mol,収率80%)の白色結晶粉体が得られた。この白色結晶粉体の融点は202.2℃であった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた反応生成物が上記式(19)で示されるジフェニルヒドロゲンホスフェートピペラジン塩(DPHPP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 3.23(8H,s)、6.96-7.01(4H,m)、7.11-7.14(8H,m)、7.20-7.27(8H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.54
元素分析C28H32N2O8P2(Mw586.51)として、
計算値: C,57.34; H,5.50; N,4.78; P,10.56
実測値: C,57.13; H,5.52; N,4.77; P,10.54 1.3 Synthesis of diphenylhydrogen phosphate piperazine salt (DPHPP)
Following 1.2, 1000 g of methanol was added to the organic layer containing the reaction product diphenyl hydrogen phosphate (DPHP) and dissolved, and anhydrous piperazine 21.20 dissolved in 200 g of methanol in a dropping funnel with a side tube. 5 g (0.25 mol) solution was added. When the piperazine solution was added dropwise over 2 hours while stirring the reaction solution, a white solid was precipitated. The white solid was recrystallized from methanol / water (2/1, wt) to obtain 117.1 g (0.20 mol, yield 80%) of white crystal powder. The melting point of this white crystal powder was 202.2 ° C. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted to a diphenyl hydrogen phosphate piperazine salt represented by the above formula (19) ( DHPPP).
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 3.23 (8H, s), 6.96-7.01 (4H, m), 7.11-7.14 (8H, m), 7.20-7.27 (8H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.54
As elemental analysis C 28 H 32 N 2 O 8 P 2 (Mw 586.51),
Calculated: C, 57.34; H, 5.50; N, 4.78; P, 10.56
Found: C, 57.13; H, 5.52; N, 4.77; P, 10.54
1H-NMR(300MHz,DMSO-d6):δ/ppm 3.23(8H,s)、6.96-7.01(4H,m)、7.11-7.14(8H,m)、7.20-7.27(8H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.54
元素分析C28H32N2O8P2(Mw586.51)として、
計算値: C,57.34; H,5.50; N,4.78; P,10.56
実測値: C,57.13; H,5.52; N,4.77; P,10.54 1.3 Synthesis of diphenylhydrogen phosphate piperazine salt (DPHPP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 3.23 (8H, s), 6.96-7.01 (4H, m), 7.11-7.14 (8H, m), 7.20-7.27 (8H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.54
As elemental analysis C 28 H 32 N 2 O 8 P 2 (Mw 586.51),
Calculated: C, 57.34; H, 5.50; N, 4.78; P, 10.56
Found: C, 57.13; H, 5.52; N, 4.77; P, 10.54
<合成例2>
2.ジ-p-トリルヒドロゲンホスフェートピペラジン塩(DTHPP)の合成
2.1 ジ-p-トリルクロロホスフェート(DTCP)の合成
前記1.1のフェノールの代わりに、p-クレゾール108.14g(1.0mol)を用い、前記1.1と同様の操作を行うことにより、反応生成物をサンプリングしてGC/MSを測定したところ、得られた微黄色透明液体の反応生成物の純度は98%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z296)、反応生成物として上記式(20)で示されるジフェニルクロロホスフェート(DPCP:Mw
296.69)が得られたことが確認できた。 <Synthesis Example 2>
2. Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP) 2.1 Synthesis of di-p-tolyl chlorophosphate (DTCP)
Using 108.14 g (1.0 mol) of p-cresol in place of the phenol of 1.1, the reaction product was sampled and GC / MS was measured by performing the same operation as 1.1. However, the purity of the reaction product of the obtained pale yellow transparent liquid is 98% or more, and from the molecular ion peak of the GC / MS spectrum (M + : m / z 296), the reaction product is represented by the above formula (20). Diphenylchlorophosphate (DPCP: Mw)
296.69) was obtained.
2.ジ-p-トリルヒドロゲンホスフェートピペラジン塩(DTHPP)の合成
2.1 ジ-p-トリルクロロホスフェート(DTCP)の合成
296.69)が得られたことが確認できた。 <Synthesis Example 2>
2. Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP) 2.1 Synthesis of di-p-tolyl chlorophosphate (DTCP)
296.69) was obtained.
2.2 ジ-p-トリルヒドロゲンホスフェート(DTHP)の合成
前記2.1に示された工程に続いて、前記1.2と同様の操作を行い、得られた反応物をサンプリングして反応生成物の純度を確認したところ、純度は99%以上(HPLC)であった。この反応生成物を完全に減圧下で乾燥させると、融点79℃の白色固体となった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた反応生成物が上記式(21)で示されるジ-p-トリルヒドロゲンホスフェート(DPHP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.25(6H,s)、7.03-7.08(4H,m)、7.12-7.17(4H,m).
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.91 2.2 Synthesis of di-p-tolyl hydrogen phosphate (DTHP)
Subsequent to the step shown in 2.1, the same operation as in 1.2 was performed, and the obtained reaction product was sampled to confirm the purity of the reaction product. As a result, the purity was 99% or higher (HPLC )Met. When this reaction product was completely dried under reduced pressure, it became a white solid having a melting point of 79 ° C. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained reaction product was di-p-tolyl hydrogen phosphate (DPHP) represented by the above formula (21). It was.
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.25 (6H, s), 7.03-7.08 (4H, m), 7.12-7.17 (4H, m).
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.91
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.25(6H,s)、7.03-7.08(4H,m)、7.12-7.17(4H,m).
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.91 2.2 Synthesis of di-p-tolyl hydrogen phosphate (DTHP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.25 (6H, s), 7.03-7.08 (4H, m), 7.12-7.17 (4H, m).
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.91
2.3 ジ-p-トリルヒドロゲンホスフェートピペラジン塩(DTHPP)の合成
前記2.2に示された工程に続いて、前記1.3と同様の操作を行うことにより、112.5g(0.18mol,収率70%)の白色結晶粉体が得られた。この白色結晶粉体の融点は206.2℃であった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた反応生成物が上記式(22)で示されるジ-p-トリルヒドロゲンホスフェートピペラジン塩(DTHPP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.21(12H,s)、3.21(8H,s)、6.98-7.05(16H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -9.97
元素分析C32H40N2O8P2(Mw 642.62)として、
計算値: C,59.81; H,6.27; N,4.36; P,9.64
実測値: C,59.43; H,6.08; N,4.32; P,9.63 2.3 Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP)
Subsequent to the step shown in 2.2, the same operation as in 1.3 was performed to obtain 112.5 g (0.18 mol, yield 70%) of white crystalline powder. The melting point of this white crystal powder was 206.2 ° C. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted into di-p-tolyl hydrogen represented by the above formula (22). It was confirmed to be phosphate piperazine salt (DTHPP).
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.21 (12H, s), 3.21 (8H, s), 6.98-7.05 (16H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97
As Elemental Analysis C 32 H 40 N 2 O 8 P 2 (Mw 642.62),
Calculated: C, 59.81; H, 6.27; N, 4.36; P, 9.64
Found: C, 59.43; H, 6.08; N, 4.32; P, 9.63
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.21(12H,s)、3.21(8H,s)、6.98-7.05(16H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -9.97
元素分析C32H40N2O8P2(Mw 642.62)として、
計算値: C,59.81; H,6.27; N,4.36; P,9.64
実測値: C,59.43; H,6.08; N,4.32; P,9.63 2.3 Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.21 (12H, s), 3.21 (8H, s), 6.98-7.05 (16H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97
As Elemental Analysis C 32 H 40 N 2 O 8 P 2 (Mw 642.62),
Calculated: C, 59.81; H, 6.27; N, 4.36; P, 9.64
Found: C, 59.43; H, 6.08; N, 4.32; P, 9.63
<合成例3>
3.ジ-2,6-キシレニルヒドロゲンホスフェートピペラジン塩(DTHPP)の合成
3.1 ジ-2,6-キシレニルクロロホスフェート(DXCP)の合成
前記1.1のフェノールの代わりに、2,6-キシレノール122.16g(1.0mol)を用い、前記1.1と同様の操作を行うことにより、反応生成物をサンプリングしてGC/MSを測定したところ、得られた微黄色透明液体の反応生成物の純度は99%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z324)、反応生成物として上記式(23)で示されるジ-2,6-キシレニルクロロホスフェート(DXCP:Mw
324.74)が得られたことが確認できた。 <Synthesis Example 3>
3. Synthesis of di-2,6- xylenyl hydrogen phosphate piperazine salt (DTHPP) 3.1 Synthesis of di-2,6-xylenyl chlorophosphate (DXCP)
In place of the phenol of 1.1, 122.16 g (1.0 mol) of 2,6-xylenol was used and the same operation as in 1.1 was performed. As a result, the purity of the reaction product of the slightly yellow transparent liquid obtained was 99% or more. From the molecular ion peak of the GC / MS spectrum (M + : m / z 324), the reaction product represented by the above formula (23 Di-2,6-xylenylchlorophosphate (DXCP: Mw)
324.74) was obtained.
3.ジ-2,6-キシレニルヒドロゲンホスフェートピペラジン塩(DTHPP)の合成
3.1 ジ-2,6-キシレニルクロロホスフェート(DXCP)の合成
324.74)が得られたことが確認できた。 <Synthesis Example 3>
3. Synthesis of di-2,6- xylenyl hydrogen phosphate piperazine salt (DTHPP) 3.1 Synthesis of di-2,6-xylenyl chlorophosphate (DXCP)
324.74) was obtained.
3.2 ジ-2,6-キシレニルヒドロゲンホスフェート(DTHP)の合成
前記3.1に示された工程に続いて、前記1.2と同様の操作を行い、得られた反応生成物をサンプリングして反応生成物の純度を確認したところ、純度は98%以上(HPLC)であった。この反応生成物を完全に減圧下で乾燥させると、融点140.4℃の白色固体となった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた反応生成物が上記式(24)で示されるジ-2,6-キシレニルヒドロゲンホスフェート(DXHP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.27(12H,s)、6.95-7.06(6H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -9.97 3.2 Synthesis of di-2,6-xylenyl hydrogen phosphate (DTHP)
Subsequent to the step shown in 3.1, the same operation as in 1.2 was performed, and the purity of the reaction product was confirmed by sampling the obtained reaction product. The purity was 98% or more ( HPLC). When this reaction product was completely dried under reduced pressure, it became a white solid with a melting point of 140.4 ° C. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, the obtained reaction product is di-2,6-xylenyl hydrogen phosphate (DXHP) represented by the above formula (24). I was able to confirm.
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.27 (12H, s), 6.95-7.06 (6H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.27(12H,s)、6.95-7.06(6H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -9.97 3.2 Synthesis of di-2,6-xylenyl hydrogen phosphate (DTHP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.27 (12H, s), 6.95-7.06 (6H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97
3.3 ジ-2,6-キシレニルヒドロゲンホスフェートピペラジン塩(DXHPP)の合成
前記3.2に示された工程に続いて、前記1.3と同様の操作を行うことにより、108.3g(0.16mol,収率62%)の白色結晶粉体が得られた。この白色結晶粉体の融点は224.2℃であった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた反応生成物が上記式(25)で示されるジ-2,6-キシレニルヒドロゲンホスフェートピペラジン塩(DXHPP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.28(24H,s)、2.97(8H,s)、6.81-6.85(4H,m)、6.93-6.95(12H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -8.49
元素分析C36H48N2O8P2(Mw 698.72)として、
計算値: C,61.88; H,6.92; N,4.01; P,8.87
実測値: C,61.63; H,6.85; N,3.98; P,8.81 3.3 Synthesis of di-2,6-xylenyl hydrogen phosphate piperazine salt (DXHPP)
Subsequent to the step shown in 3.2, the same operation as in 1.3 was performed to obtain 108.3 g (0.16 mol, yield 62%) of white crystalline powder. The melting point of this white crystal powder was 224.2 ° C. In addition, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted to the di-2,6-xyx represented by the above formula (25). It was confirmed that it was a rhenyl hydrogen phosphate piperazine salt (DXHPP).
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.28 (24H, s), 2.97 (8H, s), 6.81-6.85 (4H, m), 6.93- 6.95 (12H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −8.49
As Elemental Analysis C 36 H 48 N 2 O 8 P 2 (Mw 698.72),
Calculated values: C, 61.88; H, 6.92; N, 4.01; P, 8.87
Found: C, 61.63; H, 6.85; N, 3.98; P, 8.81
1H-NMR(300MHz,DMSO-d6):δ/ppm 2.28(24H,s)、2.97(8H,s)、6.81-6.85(4H,m)、6.93-6.95(12H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -8.49
元素分析C36H48N2O8P2(Mw 698.72)として、
計算値: C,61.88; H,6.92; N,4.01; P,8.87
実測値: C,61.63; H,6.85; N,3.98; P,8.81 3.3 Synthesis of di-2,6-xylenyl hydrogen phosphate piperazine salt (DXHPP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 2.28 (24H, s), 2.97 (8H, s), 6.81-6.85 (4H, m), 6.93- 6.95 (12H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm −8.49
As Elemental Analysis C 36 H 48 N 2 O 8 P 2 (Mw 698.72),
Calculated values: C, 61.88; H, 6.92; N, 4.01; P, 8.87
Found: C, 61.63; H, 6.85; N, 3.98; P, 8.81
<合成例4>
4.ジ-4-t-ブチルヒドロゲンホスフェートピペラジン塩(DBHPP)の合成
4.1 ジ-4-t-ブチルクロロホスフェート(DBCP)の合成
前記1.1のフェノールの代わりに、4-t-ブチルフェノール150.22g(1.0mol)を用い、前記1.1と同様の操作を行うことにより、反応生成物をサンプリングしてGC/MSを測定したところ、得られた黄色固体の反応生成物の純度は97%以上であり、融点は101.0℃であった。また、GC/MSスペクトルの分子イオンピークより(M+:m/z380)、反応生成物として上記式(26)で示されるジ-4-t-ブチルクロロホスフェート(DXCP:Mw 380.85)が得られたことが確認できた。
<Synthesis Example 4>
4). Synthesis of di-4-t-butyl hydrogen phosphate piperazine salt (DBHPP) 4.1 Synthesis of di-4-t-butyl chlorophosphate (DBCP)
Using 150.22 g (1.0 mol) of 4-t-butylphenol in place of the phenol of 1.1, the reaction product was sampled by performing the same operation as in 1.1, and GC / MS was determined. As a result, the purity of the obtained yellow solid reaction product was 97% or more, and the melting point was 101.0 ° C. Further, from the molecular ion peak of the GC / MS spectrum (M + : m / z 380), di-4-t-butylchlorophosphate (DXCP: Mw 380.85) represented by the above formula (26) was obtained as a reaction product. It was confirmed that it was obtained.
4.ジ-4-t-ブチルヒドロゲンホスフェートピペラジン塩(DBHPP)の合成
4.1 ジ-4-t-ブチルクロロホスフェート(DBCP)の合成
4). Synthesis of di-4-t-butyl hydrogen phosphate piperazine salt (DBHPP) 4.1 Synthesis of di-4-t-butyl chlorophosphate (DBCP)
4.2 ジ-4-t-ブチルヒドロゲンホスフェート(DBHP)の合成
前記4.1に示された工程に続いて、前記1.2と同様の操作を行い、得られた反応生成物をサンプリングして反応生成物の純度を確認したところ、純度は98%以上(HPLC)であった。この反応生成物を完全に減圧下で乾燥させると、融点137.4℃の淡赤褐色固体となった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた反応生成物が上記式(27)で示されるジ-4-t-ブチルヒドロゲンホスフェート(DBHP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 1.26(18H,s)、7.08-7.11(4H,m)、7.35-7.38(4H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.88 4.2 Synthesis of di-4-tert-butyl hydrogen phosphate (DBHP)
Subsequent to the step shown in 4.1, the same operation as in 1.2 was performed, and the reaction product obtained was sampled to confirm the purity of the reaction product. As a result, the purity was 98% or more ( HPLC). When this reaction product was completely dried under reduced pressure, a light reddish brown solid with a melting point of 137.4 ° C. was obtained. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was found that the obtained reaction product was di-4-tert-butyl hydrogen phosphate (DBHP) represented by the above formula (27). It could be confirmed.
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 1.26 (18H, s), 7.08-7.11 (4H, m), 7.35-7.38 (4H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.88
1H-NMR(300MHz,DMSO-d6):δ/ppm 1.26(18H,s)、7.08-7.11(4H,m)、7.35-7.38(4H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.88 4.2 Synthesis of di-4-tert-butyl hydrogen phosphate (DBHP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 1.26 (18H, s), 7.08-7.11 (4H, m), 7.35-7.38 (4H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.88
4.3 ジ-4-t-ブチルヒドロゲンホスフェートピペラジン塩(DBHPP)の合成
前記4.2に示された工程に続いて、前記1.3と同様の操作を行うことにより、162.2g(0.20mol,収率80%)の淡黄白色結晶粉体が得られた。この白色結晶粉体の融点は252.1℃であった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた反応生成物が上記式(28)で示されるジ-4-t-ブチルヒドロゲンホスフェートピペラジン塩(DXHPP)であることが確認できた。
1H-NMR(300MHz,DMSO-d6):δ/ppm 1.23(36H,s)、3.18(8H,s)、7.02-7.05(8H,m)、7.20-7.24(8H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.04
元素分析C44H64N2O8P2(Mw 810.94)として、
計算値: C,65.17; H,7.95; N,3.45; P,7.64
実測値: C,65.30; H,7.89; N,3.47; P,7.61 4.3 Synthesis of di-4-tert-butylhydrogen phosphate piperazine salt (DBHPP)
Subsequent to the step shown in 4.2, the same operation as in 1.3 was performed to obtain 162.2 g (0.20 mol, yield 80%) of pale yellowish white crystalline powder. . The melting point of this white crystal powder was 252.1 ° C. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was di-4-t-butyl represented by the above formula (28). It was confirmed that it was hydrogen phosphate piperazine salt (DXHPP).
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 1.23 (36H, s), 3.18 (8H, s), 7.02-7.05 (8H, m), 7.20- 7.24 (8H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.04
As elemental analysis C 44 H 64 N 2 O 8 P 2 (Mw 810.94),
Calculated values: C, 65.17; H, 7.95; N, 3.45; P, 7.64
Found: C, 65.30; H, 7.89; N, 3.47; P, 7.61
1H-NMR(300MHz,DMSO-d6):δ/ppm 1.23(36H,s)、3.18(8H,s)、7.02-7.05(8H,m)、7.20-7.24(8H,m)
31P-NMR(109MHz,DMSO-d6):δ/ppm -10.04
元素分析C44H64N2O8P2(Mw 810.94)として、
計算値: C,65.17; H,7.95; N,3.45; P,7.64
実測値: C,65.30; H,7.89; N,3.47; P,7.61 4.3 Synthesis of di-4-tert-butylhydrogen phosphate piperazine salt (DBHPP)
1 H-NMR (300 MHz, DMSO-d6): δ / ppm 1.23 (36H, s), 3.18 (8H, s), 7.02-7.05 (8H, m), 7.20- 7.24 (8H, m)
31 P-NMR (109 MHz, DMSO-d6): δ / ppm -10.04
As elemental analysis C 44 H 64 N 2 O 8 P 2 (Mw 810.94),
Calculated values: C, 65.17; H, 7.95; N, 3.45; P, 7.64
Found: C, 65.30; H, 7.89; N, 3.47; P, 7.61
<比較例1>
5.フェニルジヒドロゲンホスフェートピペラジン塩(PDHPP)の合成
5.1フェニルジクロロホスフェート(PDCP)の合成
コンデンサー及び温度計を備えた撹拌装置付4ツ口フラスコに、フェノール94.11g(1.00mol)、オキシ塩化リン459.99g(3.00mol)及び塩化亜鉛2.73g(0.02mol)を投入した。コンデンサーの上端に塩化カルシウム管を取り付けて空気中の水分が反応系内に混入しないようにした後、窒素雰囲気下で撹拌を開始し、マントルヒーターにて徐々に昇温させた。反応中は塩化水素ガスが発生するので、突沸しないように5時間かけて80℃まで加熱した。その後、反応生成物中にフェノールのピークが消失していることをGC及びHPLCで確認し、フラスコを減圧して反応生成物の蒸留精製を行った。減圧蒸留は反応生成物中の過剰なオキシ塩化リンを留去するために、留去温度34~100℃、真空度50Torrにて蒸留を行い、291gのオキシ塩化リン(回収率95%)を得た。この反応生成物をさらに留去温度118~120℃、真空度6Torrにて蒸留を行い、159.92g(0.76mol:収率75.8%)の無色透明液体を得た。得られた化合物の純度は99%以上(GC)であり、沸点は243℃/760Torrであった。この化合物のGC/MSスペクトルの分子イオンピークより(M+:m/z210)、得られた化合物は上記式(29)で示されるフェニルジクロロホスフェート(PDCP:Mw
210.98)であることが確認できた。 <Comparative Example 1>
5. Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP) 5.1 Synthesis of phenyl dichlorophosphate (PDCP)
94.11 g (1.00 mol) of phenol, 459.99 g (3.00 mol) of phosphorus oxychloride and 2.73 g (0.02 mol) of zinc chloride are charged into a four-necked flask equipped with a stirrer and equipped with a condenser and a thermometer. did. A calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and then stirring was started in a nitrogen atmosphere and the temperature was gradually raised with a mantle heater. Since hydrogen chloride gas was generated during the reaction, it was heated to 80 ° C. over 5 hours so as not to bump. Thereafter, it was confirmed by GC and HPLC that the phenol peak had disappeared in the reaction product, and the reaction product was distilled and purified under reduced pressure. Distillation under reduced pressure was performed at a distillation temperature of 34 to 100 ° C. and a degree of vacuum of 50 Torr to distill off excess phosphorus oxychloride in the reaction product to obtain 291 g of phosphorus oxychloride (recovery rate 95%). It was. The reaction product was further distilled at a distillation temperature of 118 to 120 ° C. and a degree of vacuum of 6 Torr to obtain 159.92 g (0.76 mol: yield 75.8%) of a colorless transparent liquid. The purity of the obtained compound was 99% or more (GC), and the boiling point was 243 ° C./760 Torr. From the molecular ion peak of the GC / MS spectrum of this compound (M + : m / z 210), the obtained compound was converted to phenyldichlorophosphate (PDCP: Mw) represented by the above formula (29).
209.98).
5.フェニルジヒドロゲンホスフェートピペラジン塩(PDHPP)の合成
5.1フェニルジクロロホスフェート(PDCP)の合成
210.98)であることが確認できた。 <Comparative Example 1>
5. Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP) 5.1 Synthesis of phenyl dichlorophosphate (PDCP)
209.98).
5.2 フェニルジヒドロゲンホスフェート(PDHP)の合成
コンデンサー及び温度計を備えた撹拌装置付4ツ口フラスコに、フェニルジクロロホスフェート159.92g(0.76mol)及び水341.1g(18.95mol)を投入した。撹拌開始後5時間加熱還流し、GCにてフェニルジクロロホスフェートのピークが消失していることを確認した後、反応液をエバポレータにて濃縮乾固して赤色粘凋液体を得た。この粘凋体をジクロロメタンでトリチュレーションを行うことにより固体を析出させた。この固体をジクロロメタンで洗浄及び乾燥することにより、110.85g(0.64mol:収率84.0%)の淡褐白色個体を得た。得られた化合物の純度は99%以上(HPLC)であり、融点は100.0℃であった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた化合物は上記式(30)で示されるフェニルジヒドロゲンホスフェート(PDHP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 6.86-6.89(3H,m)、7.03-7.08(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -4.10 5.2 Synthesis of phenyl dihydrogen phosphate (PDHP)
In a four-necked flask equipped with a stirrer and equipped with a condenser and a thermometer, 159.92 g (0.76 mol) of phenyldichlorophosphate and 341.1 g (18.95 mol) of water were charged. After stirring, the mixture was heated to reflux for 5 hours. After confirming that the peak of phenyldichlorophosphate had disappeared by GC, the reaction solution was concentrated to dryness with an evaporator to obtain a red viscous liquid. The viscose was triturated with dichloromethane to precipitate a solid. This solid was washed with dichloromethane and dried to obtain 110.85 g (0.64 mol: yield 84.0%) of a pale brown white solid. The purity of the obtained compound was 99% or higher (HPLC), and the melting point was 100.0 ° C. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained compound was phenyl dihydrogen phosphate (PDHP) represented by the above formula (30).
1 H-NMR (300 MHz, D 2 O): δ / ppm 6.86-6.89 (3H, m), 7.03-7.08 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm -4.10
1H-NMR(300MHz,D2O):δ/ppm 6.86-6.89(3H,m)、7.03-7.08(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -4.10 5.2 Synthesis of phenyl dihydrogen phosphate (PDHP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 6.86-6.89 (3H, m), 7.03-7.08 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm -4.10
5.3 フェニルジヒドロゲンホスフェートピペラジン塩(PDHPP)の合成
コンデンサー、側管付滴下漏斗及び温度計を備えた撹拌装置付4ツ口フラスコに、フェニルジヒドロゲンホスフェート110.85g(0.64mol)及びメタノール998gを投入した。側管付滴下漏斗には、あらかじめメタノール494gに溶解させたピペラジン86.14g(0.64mol)を投入した。撹拌開始後、室温にて1時間かけて滴下漏斗よりピペラジン溶液を滴下させ、滴下終了後に1時間さらに撹拌を続けたところ、白色綿状生成物が析出した。この生成物をメタノールで洗浄後、乾燥することにより157.41g(0.60mol:収率95.0%)の白色固体を得た。得られた化合物の純度は99%以上(HPLC)であるが、明確な融点を示さなかった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた化合物が上記式(31)で示されるフェニルジヒドロゲンホスフェートピペラジン塩(PDHPP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 3.19-3.20(8H,m)、7.01-7.10(3H,m)、7.23-7.29(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -1.51
元素分析C10H17N2O4P(Fw 260.23)として、
計算値: C,46.15; H,6.58; N,10.77; P,11.90
実測値: C,45.91; H,6.33; N,10.61; P,11.85 5.3 Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP)
110.85 g (0.64 mol) of phenyl dihydrogen phosphate and 998 g of methanol were charged into a four-necked flask equipped with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer. To the dropping funnel with a side tube, 86.14 g (0.64 mol) of piperazine previously dissolved in 494 g of methanol was added. After the start of stirring, the piperazine solution was dropped from the dropping funnel over 1 hour at room temperature, and further stirring was continued for 1 hour after completion of the dropping, whereby a white cotton-like product was precipitated. This product was washed with methanol and dried to obtain 157.41 g (0.60 mol: yield 95.0%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted to phenyl dihydrogen phosphate piperazine salt (PDHPP) represented by the above formula (31). It was confirmed that.
1 H-NMR (300 MHz, D 2 O): δ / ppm 3.19-3.20 (8H, m), 7.01-7.10 (3H, m), 7.23-7.29 (2H , M)
31 P-NMR (109 MHz, D 2 O): δ / ppm −1.51
As Elemental Analysis C 10 H 17 N 2 O 4 P (Fw 260.23),
Calculated: C, 46.15; H, 6.58; N, 10.77; P, 11.90
Found: C, 45.91; H, 6.33; N, 10.61; P, 11.85
1H-NMR(300MHz,D2O):δ/ppm 3.19-3.20(8H,m)、7.01-7.10(3H,m)、7.23-7.29(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -1.51
元素分析C10H17N2O4P(Fw 260.23)として、
計算値: C,46.15; H,6.58; N,10.77; P,11.90
実測値: C,45.91; H,6.33; N,10.61; P,11.85 5.3 Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 3.19-3.20 (8H, m), 7.01-7.10 (3H, m), 7.23-7.29 (2H , M)
31 P-NMR (109 MHz, D 2 O): δ / ppm −1.51
As Elemental Analysis C 10 H 17 N 2 O 4 P (Fw 260.23),
Calculated: C, 46.15; H, 6.58; N, 10.77; P, 11.90
Found: C, 45.91; H, 6.33; N, 10.61; P, 11.85
<比較例2>
6.p-トリルジヒドロゲンホスフェートピペラジン塩(TDHPP)の合成
6.1 p-トリルジクロロホスフェート(TDCP)の合成
前記5.1のフェノールの代わりに、p-クレゾール108.14g(1.0mol)を用い、前記5.1と同様の操作を行うことにより、174.16gの黄色透明液体(0.77mol:収率77.4%)を得た。この化合物のGC/MSを測定したところ、得られた化合物の純度は98%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z224)、上記式(32)で示されるフェニルジクロロホスフェート(TDCP:Mw
223.96)が得られたことが確認できた。 <Comparative Example 2>
6). Synthesis of p-tolyl dihydrogen phosphate piperazine salt (TDHPP) 6.1 Synthesis of p-tolyl dichlorophosphate (TDCP)
By using 108.14 g (1.0 mol) of p-cresol in place of the phenol of 5.1, the same operation as in 5.1 was performed to obtain 174.16 g of a yellow transparent liquid (0.77 mol: yield). Rate 77.4%). When GC / MS of this compound was measured, the purity of the obtained compound was 98% or more, and it was represented by the above formula (32) from the molecular ion peak of the GC / MS spectrum (M + : m / z 224). Phenyldichlorophosphate (TDCP: Mw
223.96) was obtained.
6.p-トリルジヒドロゲンホスフェートピペラジン塩(TDHPP)の合成
6.1 p-トリルジクロロホスフェート(TDCP)の合成
223.96)が得られたことが確認できた。 <Comparative Example 2>
6). Synthesis of p-tolyl dihydrogen phosphate piperazine salt (TDHPP) 6.1 Synthesis of p-tolyl dichlorophosphate (TDCP)
223.96) was obtained.
6.2 p-トリルジヒドロゲンホスフェート(TDHP)の合成
前記6.1に示された工程に続いて、前記5.2と同様の操作を行ったところ、116.48g(0.62mol:収率80.0%)の白色個体(融点98.7℃)を得た。得られた化合物の純度を確認したところ、純度は98%以上(HPLC)であった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた化合物が上記式(33)で示されるp-トリルジヒドロゲンホスフェート(TDHP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 2.05(3H,s)、6.84-6.87(2H,m)、6.95-6.98(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.89 6.2 Synthesis of p-tolyl dihydrogen phosphate (TDHP)
Subsequent to the step shown in 6.1, the same operation as in 5.2 was performed. As a result, 116.48 g (0.62 mol: yield 80.0%) of a white solid (melting point: 98.7 ° C. ) When the purity of the obtained compound was confirmed, the purity was 98% or higher (HPLC). From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained compound was p-tolyl dihydrogen phosphate (TDHP) represented by the above formula (33).
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.05 (3H, s), 6.84-6.87 (2H, m), 6.95-6.98 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.89
1H-NMR(300MHz,D2O):δ/ppm 2.05(3H,s)、6.84-6.87(2H,m)、6.95-6.98(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.89 6.2 Synthesis of p-tolyl dihydrogen phosphate (TDHP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.05 (3H, s), 6.84-6.87 (2H, m), 6.95-6.98 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.89
6.3 p-トリルジヒドロゲンホスフェートピペラジン塩(TDHPP)の合成
前記6.2に示された工程に続いて、前記5.3と同様の操作を行うことにより、152.83g(0.56mol,収率90.0%)の白色個体が得られた。得られた化合物の純度は99%以上(HPLC)であるが、明確な融点を示さなかった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた化合物が上記式(34)で示されるp-トリルジヒドロゲンホスフェートピペラジン塩(TDHPP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 2.15(3H,s)、3.19(8H,s)、6.94-6.96(2H,m)、7.03-7.06(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -0.87
元素分析C11H19N2O4P(Fw 274.25)として、
計算値: C,48.17; H,6.98; N,10.21; P,11.29
実測値: C,48.00; H,7.06; N,10.21; P,11.21 6.3 Synthesis of p-tolyldihydrogen phosphate piperazine salt (TDHPP)
Subsequent to the step shown in 6.2, the same operation as in 5.3 was performed to obtain 152.83 g (0.56 mol, yield 90.0%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted into p-tolyl dihydrogen phosphate piperazine salt represented by the above formula (34) ( TDHPP) was confirmed.
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.15 (3H, s), 3.19 (8H, s), 6.94-6.96 (2H, m), 7.03- 7.06 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm −0.87
As Elemental Analysis C 11 H 19 N 2 O 4 P (Fw 274.25),
Calculated: C, 48.17; H, 6.98; N, 10.21; P, 11.29
Found: C, 48.00; H, 7.06; N, 10.21; P, 11.21
1H-NMR(300MHz,D2O):δ/ppm 2.15(3H,s)、3.19(8H,s)、6.94-6.96(2H,m)、7.03-7.06(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -0.87
元素分析C11H19N2O4P(Fw 274.25)として、
計算値: C,48.17; H,6.98; N,10.21; P,11.29
実測値: C,48.00; H,7.06; N,10.21; P,11.21 6.3 Synthesis of p-tolyldihydrogen phosphate piperazine salt (TDHPP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.15 (3H, s), 3.19 (8H, s), 6.94-6.96 (2H, m), 7.03- 7.06 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm −0.87
As Elemental Analysis C 11 H 19 N 2 O 4 P (Fw 274.25),
Calculated: C, 48.17; H, 6.98; N, 10.21; P, 11.29
Found: C, 48.00; H, 7.06; N, 10.21; P, 11.21
<比較例3>
7.2,6-キシレニルジヒドロゲンホスフェートピペラジン塩(XDHPP)の合成
7.1 2,6-キシレニルジクロロホスフェート(XDCP)の合成
前記5.1のフェノールの代わりに、2,6-キシレノール122.16g(1.0mol)を用い、前記5.1と同様の操作を行うことにより、239.04gの褐色液体(1.0mol:収率100%)を得た。この化合物のGC/MSを測定したところ、得られた化合物の純度は95%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z238)、上記式(35)で示される2,6-キシレニルジクロロホスフェート(XDCP:Mw
237.97)が得られたことが確認できた。 <Comparative Example 3>
7. Synthesis of 2,6- Xylenyl Dihydrogen Phosphate Piperazine Salt (XDHPP) 7.1 Synthesis of 2,6-Xylenyl Dichlorophosphate (XDCP)
By using 122.16 g (1.0 mol) of 2,6-xylenol in place of the phenol of 5.1, the same operation as in 5.1 was performed to obtain 239.04 g of a brown liquid (1.0 mol: Yield 100%). When GC / MS of this compound was measured, the purity of the obtained compound was 95% or more, and it was represented by the above formula (35) from the molecular ion peak of the GC / MS spectrum (M + : m / z 238). 2,6-Xylenyldichlorophosphate (XDCP: Mw
237.97) was obtained.
7.2,6-キシレニルジヒドロゲンホスフェートピペラジン塩(XDHPP)の合成
7.1 2,6-キシレニルジクロロホスフェート(XDCP)の合成
237.97)が得られたことが確認できた。 <Comparative Example 3>
7. Synthesis of 2,6- Xylenyl Dihydrogen Phosphate Piperazine Salt (XDHPP) 7.1 Synthesis of 2,6-Xylenyl Dichlorophosphate (XDCP)
237.97) was obtained.
7.2 2,6-キシレニルジヒドロゲンホスフェート(XDHP)の合成
前記7.1に示された工程に続いて、前記5.2と同様の操作を行ったところ、87.93g(0.44mol:収率43.5%)の白色個体(融点139.0℃)を得た。得られた化合物の純度を確認したところ、純度は98%以上(HPLC)であった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた化合物が上記式(36)で示される2,6-キシレニルジヒドロゲンホスフェート(XDHP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 2.16(6H,s)、6.84-6.89(1H,m)、6.94-6.96(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.83 7.2 Synthesis of 2,6-xylenyl dihydrogen phosphate (XDHP)
Subsequent to the process shown in 7.1, the same operation as in 5.2 was performed. As a result, 87.93 g (0.44 mol: yield 43.5%) of a white solid (melting point: 139.0 ° C. ) When the purity of the obtained compound was confirmed, the purity was 98% or higher (HPLC). From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained compound was 2,6-xylenyl dihydrogen phosphate (XDHP) represented by the above formula (36). It was.
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.16 (6H, s), 6.84-6.89 (1H, m), 6.94-6.96 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.83
1H-NMR(300MHz,D2O):δ/ppm 2.16(6H,s)、6.84-6.89(1H,m)、6.94-6.96(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.83 7.2 Synthesis of 2,6-xylenyl dihydrogen phosphate (XDHP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.16 (6H, s), 6.84-6.89 (1H, m), 6.94-6.96 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.83
7.3 2,6-キシレニルジヒドロゲンホスフェートピペラジン塩(XDHPP)の合成
前記7.2に示された工程に続いて、前記5.3と同様の操作を行うことにより、111.23g(0.39mol,収率88.7%)の白色個体が得られた。得られた化合物の純度は99%以上(HPLC)であるが、明確な融点を示さなかった。この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた化合物が上記式(37)で示される2,6-キシレニルジヒドロゲンホスフェートピペラジン塩(XDHPP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 2.17(6H,s)、3.09(8H,s)、6.80-6.84(1H,m)、6.91-6.94(2H,m)
31P-NMR(109MHz,D2O):δ/ -1.75
元素分析C12H21N2O4P(Fw 288.28)として、
計算値: C,50.00; H,7.34; N,9.72; P,10.74
実測値: C,49.91; H,7.29; N,9.69; P,10.61 7.3 Synthesis of 2,6-xylenyl dihydrogen phosphate piperazine salt (XDHPP)
Subsequent to the step shown in 7.2, the same operation as in 5.3 was performed to obtain 111.23 g (0.39 mol, yield 88.7%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was 2,6-xylenyl dihydrogen phosphate piperazine represented by the above formula (37). It was confirmed to be a salt (XDHPP).
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.17 (6H, s), 3.09 (8H, s), 6.80-6.84 (1H, m), 6.91- 6.94 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / -1.75
As Elemental Analysis C 12 H 21 N 2 O 4 P (Fw 288.28),
Calculated values: C, 50.00; H, 7.34; N, 9.72; P, 10.74
Found: C, 49.91; H, 7.29; N, 9.69; P, 10.61
1H-NMR(300MHz,D2O):δ/ppm 2.17(6H,s)、3.09(8H,s)、6.80-6.84(1H,m)、6.91-6.94(2H,m)
31P-NMR(109MHz,D2O):δ/ -1.75
元素分析C12H21N2O4P(Fw 288.28)として、
計算値: C,50.00; H,7.34; N,9.72; P,10.74
実測値: C,49.91; H,7.29; N,9.69; P,10.61 7.3 Synthesis of 2,6-xylenyl dihydrogen phosphate piperazine salt (XDHPP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 2.17 (6H, s), 3.09 (8H, s), 6.80-6.84 (1H, m), 6.91- 6.94 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / -1.75
As Elemental Analysis C 12 H 21 N 2 O 4 P (Fw 288.28),
Calculated values: C, 50.00; H, 7.34; N, 9.72; P, 10.74
Found: C, 49.91; H, 7.29; N, 9.69; P, 10.61
<比較例4>
8.4-t-ブチルジヒドロゲンホスフェートピペラジン塩(BDHPP)の合成
8.1 4-t-ブチルジクロロホスフェート(BDCP)の合成
前記5.1のフェノールの代わりに、4-t-ブチルフェノール150.22g(1.0mol)を用い、前記5.1と同様の操作を行うことにより、267.09gの褐色液体(1.0mol:収率100%)を得た。この化合物のGC/MSを測定したところ、得られた化合物の純度は95%以上であり、GC/MSスペクトルの分子イオンピークより(M+:m/z266)、上記式(38)で示される4-t-ブチルジクロロホスフェート(BDCP:Mw
266.00)が得られたことが確認できた。 <Comparative example 4>
8. Synthesis of 4-t -butyl dihydrogen phosphate piperazine salt (BDHPP) 8.1 Synthesis of 4-t-butyl dichlorophosphate (BDCP)
By using 150.22 g (1.0 mol) of 4-t-butylphenol instead of the phenol of 5.1, the same operation as in 5.1 was performed, whereby 267.09 g of a brown liquid (1.0 mol: Yield 100%). When GC / MS of this compound was measured, the purity of the obtained compound was 95% or more, and it was represented by the above formula (38) from the molecular ion peak of the GC / MS spectrum (M + : m / z 266). 4-t-butyldichlorophosphate (BDCP: Mw
266.00) was obtained.
8.4-t-ブチルジヒドロゲンホスフェートピペラジン塩(BDHPP)の合成
8.1 4-t-ブチルジクロロホスフェート(BDCP)の合成
266.00)が得られたことが確認できた。 <Comparative example 4>
8. Synthesis of 4-t -butyl dihydrogen phosphate piperazine salt (BDHPP) 8.1 Synthesis of 4-t-butyl dichlorophosphate (BDCP)
266.00) was obtained.
8.2 4-t-ブチルジヒドロゲンホスフェート(BDHP)の合成
前記8.1に示された工程に続いて、前記5.2と同様の操作を行ったところ、115.56g(0.5mol:収率50.2%)の黄色個体(融点96.2℃)を得た。得られた化合物の純度を確認したところ、純度は97%以上(HPLC)であった。この化合物の1H-NMR測定及び31P-NMR測定の結果より、得られた化合物が上記式(39)で示される4-t-ブチルジヒドロゲンホスフェート(XDHP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 1.14(9H,s)、6.97-7.02(2H,m)、7.29-7.34(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.73 8.2 Synthesis of 4-tert-butyl dihydrogen phosphate (BDHP)
Subsequent to the step shown in 8.1, the same operation as in 5.2 was performed. As a result, 115.56 g (0.5 mol: yield 50.2%) of a yellow solid (melting point: 96.2 ° C. ) When the purity of the obtained compound was confirmed, the purity was 97% or higher (HPLC). From the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, it was confirmed that the obtained compound was 4-t-butyldihydrogen phosphate (XDHP) represented by the above formula (39).
1 H-NMR (300 MHz, D 2 O): δ / ppm 1.14 (9H, s), 6.97-7.02 (2H, m), 7.29-7.34 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.73
1H-NMR(300MHz,D2O):δ/ppm 1.14(9H,s)、6.97-7.02(2H,m)、7.29-7.34(2H,m).
31P-NMR(109MHz,D2O):δ/ppm -3.73 8.2 Synthesis of 4-tert-butyl dihydrogen phosphate (BDHP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 1.14 (9H, s), 6.97-7.02 (2H, m), 7.29-7.34 (2H, m).
31 P-NMR (109 MHz, D 2 O): δ / ppm −3.73
8.3 4-t-ブチルジヒドロゲンホスフェートピペラジン塩(BDHPP)の合成
前記8.2に示された工程に続いて、前記5.3と同様の操作を行うことにより、135.14g(0.43mol,収率85.1%)の白色個体が得られた。得られた化合物の純度は99%以上(HPLC)であるが、明確な融点を示さなかった。また、この化合物の1H-NMR測定及び31P-NMR測定の結果、さらに下記の元素分析の結果より、得られた化合物が上記式(40)で示される4-t-ブチルジヒドロゲンホスフェートピペラジン塩(BDHPP)であることが確認できた。
1H-NMR(300MHz,D2O):δ/ppm 1.19(9H,s)、3.15(8H,s)、7.03-7.06(2H,m)、7.33-7.36(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -1.48
元素分析C14H25N2O4P(Fw 316.33)として、
計算値: C,53.16; H,7.97; N,8.86; P,9.79
実測値: C,52.81; H,7.78; N,8.93; P,9.71 8.3 Synthesis of 4-t-butyl dihydrogen phosphate piperazine salt (BDHPP)
Subsequent to the step shown in 8.2, the same operation as in 5.3 was performed to obtain 135.14 g (0.43 mol, yield 85.1%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of 1 H-NMR measurement and 31 P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted to 4-t-butyldihydrogen phosphate piperazine represented by the above formula (40). It was confirmed to be a salt (BDHPP).
1 H-NMR (300 MHz, D 2 O): δ / ppm 1.19 (9H, s), 3.15 (8H, s), 7.03-7.06 (2H, m), 7.33- 7.36 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm −1.48
As elemental analysis C 14 H 25 N 2 O 4 P (Fw 316.33),
Calculated: C, 53.16; H, 7.97; N, 8.86; P, 9.79.
Found: C, 52.81; H, 7.78; N, 8.93; P, 9.71
1H-NMR(300MHz,D2O):δ/ppm 1.19(9H,s)、3.15(8H,s)、7.03-7.06(2H,m)、7.33-7.36(2H,m)
31P-NMR(109MHz,D2O):δ/ppm -1.48
元素分析C14H25N2O4P(Fw 316.33)として、
計算値: C,53.16; H,7.97; N,8.86; P,9.79
実測値: C,52.81; H,7.78; N,8.93; P,9.71 8.3 Synthesis of 4-t-butyl dihydrogen phosphate piperazine salt (BDHPP)
1 H-NMR (300 MHz, D 2 O): δ / ppm 1.19 (9H, s), 3.15 (8H, s), 7.03-7.06 (2H, m), 7.33- 7.36 (2H, m)
31 P-NMR (109 MHz, D 2 O): δ / ppm −1.48
As elemental analysis C 14 H 25 N 2 O 4 P (Fw 316.33),
Calculated: C, 53.16; H, 7.97; N, 8.86; P, 9.79.
Found: C, 52.81; H, 7.78; N, 8.93; P, 9.71
2.難燃性合成樹脂組成物の調製
前記の各合成例で得られた環状アミン塩を用いて難燃性合成樹脂組成物を調製した。難燃性合成樹脂組成物を構成する成分は、合成樹脂、及び難燃剤からなり、下記にそれぞれの成分を示す。この下記成分を表1及び表2に記載してある配合割合(重量部)に従って、各成分をドライブレンドした後、2軸押出機にて溶融混合して押出混練し、ストランドをカットしてペレット状難燃性樹脂組成物を得た。2軸押出機としては、(株)神戸製鋼所製の2軸押出機「KTX30型」(スクリュウ径30mm、L/D=37、ベント付き)を用いた。 2. Preparation of flame retardant synthetic resin composition A flame retardant synthetic resin composition was prepared using the cyclic amine salt obtained in each of the above synthesis examples. The component which comprises a flame-retardant synthetic resin composition consists of a synthetic resin and a flame retardant, and shows each component below. The following components were dry blended according to the blending ratio (parts by weight) described in Tables 1 and 2, and then melt-mixed and extruded and kneaded in a twin-screw extruder, cut into strands, and pellets. A flame retardant resin composition was obtained. As the twin screw extruder, a twin screw extruder “KTX30 type” (screw diameter 30 mm, L / D = 37, with vent) manufactured by Kobe Steel, Ltd. was used.
前記の各合成例で得られた環状アミン塩を用いて難燃性合成樹脂組成物を調製した。難燃性合成樹脂組成物を構成する成分は、合成樹脂、及び難燃剤からなり、下記にそれぞれの成分を示す。この下記成分を表1及び表2に記載してある配合割合(重量部)に従って、各成分をドライブレンドした後、2軸押出機にて溶融混合して押出混練し、ストランドをカットしてペレット状難燃性樹脂組成物を得た。2軸押出機としては、(株)神戸製鋼所製の2軸押出機「KTX30型」(スクリュウ径30mm、L/D=37、ベント付き)を用いた。 2. Preparation of flame retardant synthetic resin composition A flame retardant synthetic resin composition was prepared using the cyclic amine salt obtained in each of the above synthesis examples. The component which comprises a flame-retardant synthetic resin composition consists of a synthetic resin and a flame retardant, and shows each component below. The following components were dry blended according to the blending ratio (parts by weight) described in Tables 1 and 2, and then melt-mixed and extruded and kneaded in a twin-screw extruder, cut into strands, and pellets. A flame retardant resin composition was obtained. As the twin screw extruder, a twin screw extruder “KTX30 type” (screw diameter 30 mm, L / D = 37, with vent) manufactured by Kobe Steel, Ltd. was used.
(1)合成樹脂
住友ノーブレンAY564(住友化学(株)製、PP)
(2)難燃剤
DPHPP:ジフェニルヒドロゲンホスフェートピペラジン塩
DTHPP:ジ-p-トリルヒドロゲンホスフェートピペラジン塩
DXHPP:ジ-2,5-キシレニルヒドロゲンホスフェートピペラジン塩
BDHPP:ジ-4-t-ブチルフェニルヒドロゲンホスフェートピペラジン塩
PDHPP:フェニルジヒドロゲンホスフェートピペラジン塩
TDHPP:p-トリルジヒドロゲンホスフェートピペラジン塩
XDHPP:2,5-キシレニルジヒドロゲンホスフェートピペラジン塩
BDHPP:4-t-ブチルフェニルジヒドロゲンホスフェート ピペラジン塩
APP:エクソリットAP422(クラリアント社製 ポリリン酸アンモニウム)
cAPP:エクソリットAP462(クラリアント社製 メラミン被覆ポリリン酸アンモニウム) (1) Synthetic resin Sumitomo Nobrene AY564 (manufactured by Sumitomo Chemical Co., Ltd., PP)
(2) Flame retardant DPHPP: Diphenyl hydrogen phosphate piperazine salt DTHPP: Di-p-tolyl hydrogen phosphate piperazine salt DXHPP: Di-2,5-xylenyl hydrogen phosphate piperazine salt BDHPP: Di-4-t-butyl Phenyl hydrogen phosphate piperazine salt PDHPP: Phenyl dihydrogen phosphate piperazine salt TDHPP: p-tolyl dihydrogen phosphate piperazine salt XDHPP: 2,5-xylenyl dihydrogen phosphate piperazine salt BDHPP: 4-t-butylphenyl dihydrogen phosphate piperazine Salt APP: Exolit AP422 (Ammonium polyphosphate manufactured by Clariant)
cAPP: Exorit AP462 (Melamine-coated ammonium polyphosphate manufactured by Clariant)
住友ノーブレンAY564(住友化学(株)製、PP)
(2)難燃剤
DPHPP:ジフェニルヒドロゲンホスフェートピペラジン塩
DTHPP:ジ-p-トリルヒドロゲンホスフェートピペラジン塩
DXHPP:ジ-2,5-キシレニルヒドロゲンホスフェートピペラジン塩
BDHPP:ジ-4-t-ブチルフェニルヒドロゲンホスフェートピペラジン塩
PDHPP:フェニルジヒドロゲンホスフェートピペラジン塩
TDHPP:p-トリルジヒドロゲンホスフェートピペラジン塩
XDHPP:2,5-キシレニルジヒドロゲンホスフェートピペラジン塩
BDHPP:4-t-ブチルフェニルジヒドロゲンホスフェート ピペラジン塩
APP:エクソリットAP422(クラリアント社製 ポリリン酸アンモニウム)
cAPP:エクソリットAP462(クラリアント社製 メラミン被覆ポリリン酸アンモニウム) (1) Synthetic resin Sumitomo Nobrene AY564 (manufactured by Sumitomo Chemical Co., Ltd., PP)
(2) Flame retardant DPHPP: Diphenyl hydrogen phosphate piperazine salt DTHPP: Di-p-tolyl hydrogen phosphate piperazine salt DXHPP: Di-2,5-xylenyl hydrogen phosphate piperazine salt BDHPP: Di-4-t-butyl Phenyl hydrogen phosphate piperazine salt PDHPP: Phenyl dihydrogen phosphate piperazine salt TDHPP: p-tolyl dihydrogen phosphate piperazine salt XDHPP: 2,5-xylenyl dihydrogen phosphate piperazine salt BDHPP: 4-t-butylphenyl dihydrogen phosphate piperazine Salt APP: Exolit AP422 (Ammonium polyphosphate manufactured by Clariant)
cAPP: Exorit AP462 (Melamine-coated ammonium polyphosphate manufactured by Clariant)
3.難燃性樹脂組成物の成形品の評価
前述で得られた難燃性合成樹脂組成物を用いて射出成形法により成形品を作製した。射出成形は、日精樹脂工業(株)製射出成形機「FE80S型」(型締圧80トン)を使用した。射出成形して種々の試験片を得た後、それらの試験片を23℃、50%RHの条件で48時間状態調整処理してから、それぞれ初期燃焼性評価、耐湿性評価及びブリード評価を行った。さらに、耐湿性試験後に再度燃焼性評価を行った。それらの結果を表1及び表2に示す。 3. Evaluation of molded product of flame retardant resin composition A molded product was produced by an injection molding method using the flame retardant synthetic resin composition obtained above. For injection molding, an injection molding machine “FE80S type” manufactured by Nissei Plastic Industry Co., Ltd. (clamping pressure: 80 tons) was used. After obtaining various test pieces by injection molding, the test pieces were conditioned for 48 hours at 23 ° C. and 50% RH, and then subjected to initial flammability evaluation, moisture resistance evaluation and bleed evaluation, respectively. It was. Further, the flammability evaluation was performed again after the moisture resistance test. The results are shown in Tables 1 and 2.
前述で得られた難燃性合成樹脂組成物を用いて射出成形法により成形品を作製した。射出成形は、日精樹脂工業(株)製射出成形機「FE80S型」(型締圧80トン)を使用した。射出成形して種々の試験片を得た後、それらの試験片を23℃、50%RHの条件で48時間状態調整処理してから、それぞれ初期燃焼性評価、耐湿性評価及びブリード評価を行った。さらに、耐湿性試験後に再度燃焼性評価を行った。それらの結果を表1及び表2に示す。 3. Evaluation of molded product of flame retardant resin composition A molded product was produced by an injection molding method using the flame retardant synthetic resin composition obtained above. For injection molding, an injection molding machine “FE80S type” manufactured by Nissei Plastic Industry Co., Ltd. (clamping pressure: 80 tons) was used. After obtaining various test pieces by injection molding, the test pieces were conditioned for 48 hours at 23 ° C. and 50% RH, and then subjected to initial flammability evaluation, moisture resistance evaluation and bleed evaluation, respectively. It was. Further, the flammability evaluation was performed again after the moisture resistance test. The results are shown in Tables 1 and 2.
なお、これらの評価方法は、具体的には以下の方法によって行った。
(1)燃焼性
燃焼性の評価は、UL94垂直燃焼試験法に準拠して、1.6mm(1/16inch)厚及び0.8mm(1/32inch)厚UL試験片を作成して燃焼試験を行った。UL94垂直燃焼試験の結果は、「V-0」、「V-1」、「V-2」、「不可」の4段階評価を行った。
(2)ブリード試験
2mm/3mm厚の黒色平板試験片(カーボンブラック1phr添加)を作成後に150℃、7日間加熱し、その後に試験片について23℃、50%Rhの条件で48時間のエージング処理を施した後、試験片表面への難燃剤等の染み出しの有無を目視観察した。なお、耐湿性試験の結果は、「○(染み出しが全くみられない)」、「△(若干の染み出しがみられる)」、「×(著しい染み出しがみられるか、もしくはブルーミングがみられる)」、「××(著しい染み出しがみられるか、もしくはブルーミングがみられ、なおかつ、試験片に亀裂がみられる)の4段階で評価を行った。
(3)耐湿性試験
1.6mm(1/16inch)厚及び0.8mm(1/32inch)厚のUL試験片を作成後に60℃、90%Rhの条件で30日間高湿度状態処理を施し、その後試験片について23℃、50%Rhの条件で48時間のエージング処理を施した後、試験片表面への難燃剤等の染み出しの有無を目視観察した。なお、耐湿性試験の結果は、「○(染み出しが全くみられない)」、「△(若干の染み出しがみられる)」、「×(著しい染み出しがみられるか、もしくはブルーミングがみられる)」の3段階で評価を行った。 In addition, these evaluation methods were specifically performed by the following methods.
(1) Flammability Evaluation of flammability is based on the UL94 vertical combustion test method, and 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness UL test pieces are prepared and a combustion test is performed. went. As a result of the UL94 vertical combustion test, a four-level evaluation of “V-0”, “V-1”, “V-2”, and “impossible” was performed.
(2) Bleed test A black flat plate test piece (with 1 phr of carbon black added) having a thickness of 2 mm / 3 mm was prepared and heated at 150 ° C. for 7 days, and then the test piece was aged for 48 hours at 23 ° C. and 50% Rh. Then, the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). The evaluation was made in four stages: “XX” (remarkable exudation or blooming was observed, and cracks were observed in the test piece).
(3) Moisture resistance test After preparing a UL test piece of 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness, it was subjected to a high humidity state treatment for 30 days at 60 ° C. and 90% Rh, Thereafter, the test piece was subjected to an aging treatment for 48 hours under the conditions of 23 ° C. and 50% Rh, and then the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). It was evaluated in three stages.
(1)燃焼性
燃焼性の評価は、UL94垂直燃焼試験法に準拠して、1.6mm(1/16inch)厚及び0.8mm(1/32inch)厚UL試験片を作成して燃焼試験を行った。UL94垂直燃焼試験の結果は、「V-0」、「V-1」、「V-2」、「不可」の4段階評価を行った。
(2)ブリード試験
2mm/3mm厚の黒色平板試験片(カーボンブラック1phr添加)を作成後に150℃、7日間加熱し、その後に試験片について23℃、50%Rhの条件で48時間のエージング処理を施した後、試験片表面への難燃剤等の染み出しの有無を目視観察した。なお、耐湿性試験の結果は、「○(染み出しが全くみられない)」、「△(若干の染み出しがみられる)」、「×(著しい染み出しがみられるか、もしくはブルーミングがみられる)」、「××(著しい染み出しがみられるか、もしくはブルーミングがみられ、なおかつ、試験片に亀裂がみられる)の4段階で評価を行った。
(3)耐湿性試験
1.6mm(1/16inch)厚及び0.8mm(1/32inch)厚のUL試験片を作成後に60℃、90%Rhの条件で30日間高湿度状態処理を施し、その後試験片について23℃、50%Rhの条件で48時間のエージング処理を施した後、試験片表面への難燃剤等の染み出しの有無を目視観察した。なお、耐湿性試験の結果は、「○(染み出しが全くみられない)」、「△(若干の染み出しがみられる)」、「×(著しい染み出しがみられるか、もしくはブルーミングがみられる)」の3段階で評価を行った。 In addition, these evaluation methods were specifically performed by the following methods.
(1) Flammability Evaluation of flammability is based on the UL94 vertical combustion test method, and 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness UL test pieces are prepared and a combustion test is performed. went. As a result of the UL94 vertical combustion test, a four-level evaluation of “V-0”, “V-1”, “V-2”, and “impossible” was performed.
(2) Bleed test A black flat plate test piece (with 1 phr of carbon black added) having a thickness of 2 mm / 3 mm was prepared and heated at 150 ° C. for 7 days, and then the test piece was aged for 48 hours at 23 ° C. and 50% Rh. Then, the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). The evaluation was made in four stages: “XX” (remarkable exudation or blooming was observed, and cracks were observed in the test piece).
(3) Moisture resistance test After preparing a UL test piece of 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness, it was subjected to a high humidity state treatment for 30 days at 60 ° C. and 90% Rh, Thereafter, the test piece was subjected to an aging treatment for 48 hours under the conditions of 23 ° C. and 50% Rh, and then the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). It was evaluated in three stages.
難燃剤としてポリリン酸アンモニウム及び被覆ポリリン酸アンモニウムを単独で使用した場合には、難燃性、耐湿性、及びブリード耐性のすべてが実用上不十分であり、特にポリリン酸アンモニウムを単独使用した場合では、ブリード試験において試験片の亀裂発生が多数認められた(比較例5、6)。
When ammonium polyphosphate and coated ammonium polyphosphate are used alone as a flame retardant, flame retardancy, moisture resistance, and bleed resistance are all insufficient for practical use, especially when ammonium polyphosphate is used alone. In the bleed test, many cracks were observed in the test pieces (Comparative Examples 5 and 6).
また、難燃剤として芳香族リン酸モノエステルピペラジン塩を用いた場合は、若干のブリード耐性が上がるものの、耐湿性及び難燃性についてはポリリン酸アンモニウムとほぼ同様の結果であり、吸湿性が高いため、実用上使用に耐え得るものではないことが確認された(比較例1~4)。
In addition, when aromatic phosphate monoester piperazine salt is used as a flame retardant, the bleed resistance is slightly increased, but the moisture resistance and flame resistance are almost the same as those of ammonium polyphosphate, and the hygroscopicity is high. Therefore, it was confirmed that it was not practically usable (Comparative Examples 1 to 4).
これに対し、難燃剤として芳香族リン酸ジエステルピペラジン塩を単独使用した場合には、ポリリン酸アンモニウムと同等の難燃性を付与できる上、さらに高度な耐湿性及びブリード耐性が付与されていることが確認された(実施例1~4)。
On the other hand, when an aromatic phosphate diester piperazine salt is used alone as a flame retardant, flame retardancy equivalent to that of ammonium polyphosphate can be imparted, and further high moisture resistance and bleed resistance are imparted. Was confirmed (Examples 1 to 4).
一方、難燃剤として、ポリリン酸アンモニウム又は被覆ポリリン酸アンモニウムと芳香族リン酸エステル類(モノエステル、ジエステル)のピペラジン塩とを併用した場合、比較的少量の添加でも高度な難燃性を獲得することができた(実施例5~10、比較例7~14)。
On the other hand, when flame retardant is used in combination with ammonium polyphosphate or coated polyphosphate and piperazine salt of aromatic phosphate ester (monoester, diester), high flame retardancy can be achieved even with relatively small amount of addition. (Examples 5 to 10, Comparative Examples 7 to 14).
しかしながら、このうちポリリン酸アンモニウム又は被覆ポリリン酸アンモニウムと芳香族リン酸モノエステルピペラジン塩とを併用した場合、いずれの場合においても成形後初期では高度な難燃性が付与されているものの、高湿度下における経時劣化に伴って外観不良及び難燃性の低下を引き起こした(比較例7~12)。それに比べて、芳香族リン酸ジエステルピペラジン塩を併用する場合には、高度な難燃性に加えて、高耐湿性、さらに高ブリード耐性を発揮できることが確認された(実施例5~10)。
However, among them, when ammonium polyphosphate or coated ammonium polyphosphate and an aromatic phosphate monoester piperazine salt are used in combination, in any case, high flame retardancy is imparted at the initial stage after molding, but high humidity Along with the deterioration with time, the appearance deteriorated and the flame retardancy decreased (Comparative Examples 7 to 12). In comparison, it was confirmed that when the aromatic phosphate diester piperazine salt is used in combination, in addition to high flame retardancy, it can exhibit high moisture resistance and high bleed resistance (Examples 5 to 10).
但し、芳香族リン酸ジエステルピペラジン塩と被覆ポリリン酸アンモニウムの併用においては、若干被覆ポリリン酸アンモニウムの分散性に劣り、ブリード試験後にわずかに斑点模様がみられることがあるが、耐湿性試験後のUL94V試験では依然としてV-0ないしV-2の難燃性能を維持していた(実施例6、8)。
However, in the combined use of aromatic phosphate diester piperazine salt and coated ammonium polyphosphate, the dispersibility of the coated ammonium polyphosphate is slightly inferior, and a slight spot pattern may be seen after the bleed test, but after the moisture resistance test In the UL94V test, the flame retardancy performance of V-0 to V-2 was still maintained (Examples 6 and 8).
また、芳香族リン酸ジエステル、芳香族リン酸モノエステル及びポリリン酸アンモニウムを併用した場合においては、芳香族リン酸モノエステルの高い吸湿性によって、芳香族リン酸ジエステルのもつ耐湿性及びブリード耐性が阻害された(比較例13~14)。
In addition, when the aromatic phosphate diester, aromatic phosphate monoester and ammonium polyphosphate are used in combination, the aromatic phosphate diester has high moisture absorption, so that the aromatic phosphate diester has moisture resistance and bleed resistance. Inhibited (Comparative Examples 13 to 14).
Claims (10)
- 1)アニオン成分である芳香族リン酸ジエステル及び2)カチオン成分である環状アミンから構成される芳香族リン酸ジエステルの環状アミン塩を含む難燃剤組成物であって、当該環状アミン塩が下記一般式(I)
で表される、環状アミン塩を含む難燃剤組成物。 A flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I)
The flame retardant composition containing cyclic amine salt represented by these. - 当該芳香族リン酸ジエステルの環状アミン塩において、
下記一般式(II)
で表されるA成分と、
下記一般式(III)
で表されるB成分との構成比率が、イオン当量比でA成分/B成分=0.8/1.0~1.0/1.2である、請求項1に記載の難燃剤組成物。 In the cyclic amine salt of the aromatic phosphoric diester,
The following general formula (II)
A component represented by
The following general formula (III)
2. The flame retardant composition according to claim 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component = 0.8 / 1.0 to 1.0 / 1.2. . - 芳香族リン酸モノエステルの含有量が難燃剤組成物中1重量%以下である、請求項1に記載の難燃剤組成物。 The flame retardant composition according to claim 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition.
- リン酸塩類の少なくとも1種をさらに含む、請求項1に記載の難燃剤組成物。 The flame retardant composition according to claim 1, further comprising at least one phosphate.
- 請求項1に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~100重量部を含む難燃性樹脂組成物。 A resin composition comprising the flame retardant composition according to claim 1 and a resin component, wherein the flame retardant composition comprises 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component. Resin composition.
- 請求項4に記載の難燃剤組成物及び樹脂成分を含む樹脂組成物であって、樹脂成分100重量部に対して当該芳香族リン酸ジエステルの環状アミン塩1~50重量部、当該リン酸塩類1~50重量部を含む難燃性樹脂組成物。 A resin composition comprising the flame retardant composition according to claim 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates A flame retardant resin composition comprising 1 to 50 parts by weight.
- 当該樹脂成分がポリオレフィン系樹脂である、請求項5又は6に記載の難燃剤樹脂組成物。 The flame retardant resin composition according to claim 5 or 6, wherein the resin component is a polyolefin resin.
- 請求項5~7のいずれかに記載の難燃性樹脂組成物を成形してなる難燃性樹脂成形品。 A flame retardant resin molded product obtained by molding the flame retardant resin composition according to any one of claims 5 to 7.
- 電気・電子部品、OA機器部品、家電機器部品、自動車用部品又は機器機構部品に用いられる、請求項8に記載の難燃性樹脂成形品。 The flame-retardant resin molded product according to claim 8, which is used for electric / electronic parts, OA equipment parts, home appliance parts, automotive parts or equipment mechanism parts.
- 下記一般式(I)
で表される芳香族リン酸ジエステルの環状アミン塩を製造する方法であって、
(1)下記一般式(IV)
で表される化合物を、アミンの存在下においてオキシハロゲン化リンと反応させることにより、
下記一般式(V)
で表される含ハロゲン芳香族リン酸エステル酸誘導体を合成する工程、
(2)当該含ハロゲン芳香族リン酸エステル酸誘導体を加水分解させることにより、
下記一般式(II)
で表される芳香族リン酸ジエステルを合成する工程、
(3)当該芳香族リン酸ジエステルに対し、下記一般式(VI)
で表される化合物を添加することによって、前記一般式(I)で表される化合物を合成する工程
を含む、芳香族リン酸ジエステルの環状アミン塩の製造方法。 The following general formula (I)
A process for producing a cyclic amine salt of an aromatic phosphoric diester represented by
(1) The following general formula (IV)
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)
A step of synthesizing a halogen-containing aromatic phosphate ester derivative represented by:
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)
A step of synthesizing an aromatic phosphate diester represented by:
(3) For the aromatic phosphoric acid diester, the following general formula (VI)
A method for producing a cyclic amine salt of an aromatic phosphoric diester, comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-165395 | 2010-07-22 | ||
JP2010165395A JP2012025840A (en) | 2010-07-22 | 2010-07-22 | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012011519A1 true WO2012011519A1 (en) | 2012-01-26 |
Family
ID=45496937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/066534 WO2012011519A1 (en) | 2010-07-22 | 2011-07-21 | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2012025840A (en) |
TW (1) | TW201209143A (en) |
WO (1) | WO2012011519A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013118728A1 (en) | 2012-02-09 | 2013-08-15 | ユニバーサル製缶株式会社 | Can production device |
JP5243653B1 (en) * | 2012-09-26 | 2013-07-24 | 株式会社フジクラ | Flame-retardant resin composition and molded body using the same |
CN104804039A (en) * | 2015-04-07 | 2015-07-29 | 上海大学 | Synthesis method for organic phosphorus based flame retardant metabolite |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB675779A (en) * | 1949-12-08 | 1952-07-16 | Roche Products Ltd | A process for the manufacture of substituted phosphorus oxyacids |
JPH01143881A (en) * | 1987-11-27 | 1989-06-06 | Lion Corp | Production of phosphoric acid diester |
JPH10175985A (en) * | 1996-12-17 | 1998-06-30 | Tosoh Corp | Nitrogen-containing organic phosphoric acid compound and flame-retardant resin composition compounding the same |
JP2002080633A (en) * | 2000-09-08 | 2002-03-19 | Tokuyama Corp | Flame retardant |
JP2004115796A (en) * | 2002-09-25 | 2004-04-15 | Clariant Gmbh | Flame-retardant thermosetting material |
JP2005120021A (en) * | 2003-10-16 | 2005-05-12 | Asahi Denka Kogyo Kk | High-purity piperazine pyrophosphate and method for producing the same |
-
2010
- 2010-07-22 JP JP2010165395A patent/JP2012025840A/en active Pending
-
2011
- 2011-07-18 TW TW100125287A patent/TW201209143A/en unknown
- 2011-07-21 WO PCT/JP2011/066534 patent/WO2012011519A1/en active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB675779A (en) * | 1949-12-08 | 1952-07-16 | Roche Products Ltd | A process for the manufacture of substituted phosphorus oxyacids |
JPH01143881A (en) * | 1987-11-27 | 1989-06-06 | Lion Corp | Production of phosphoric acid diester |
JPH10175985A (en) * | 1996-12-17 | 1998-06-30 | Tosoh Corp | Nitrogen-containing organic phosphoric acid compound and flame-retardant resin composition compounding the same |
JP2002080633A (en) * | 2000-09-08 | 2002-03-19 | Tokuyama Corp | Flame retardant |
JP2004115796A (en) * | 2002-09-25 | 2004-04-15 | Clariant Gmbh | Flame-retardant thermosetting material |
JP2005120021A (en) * | 2003-10-16 | 2005-05-12 | Asahi Denka Kogyo Kk | High-purity piperazine pyrophosphate and method for producing the same |
Non-Patent Citations (1)
Title |
---|
BAKER, ROBERT J. ET AL.: "A Study of the Reactivity of Secondary Phosphanes with Radical Sources: A New Dehydrocoupling Reaction", HELVETICA CHIMICA ACTA, vol. 93, no. 6, 15 June 2010 (2010-06-15), pages 1081 - 1085 * |
Also Published As
Publication number | Publication date |
---|---|
TW201209143A (en) | 2012-03-01 |
JP2012025840A (en) | 2012-02-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101416843B1 (en) | Oligomeric bis-phosphate flame retardants and compositions containing the same | |
JP7244085B2 (en) | FLAME RETARDANT COMPOSITION AND FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION CONTAINING THE FLAME RETARDANT COMPOSITION | |
TWI761486B (en) | Flame retardant composition and flame retardant synthetic resin composition containing the same | |
JP5823135B2 (en) | Flame retardant resin composition | |
KR20150130896A (en) | Spiro bisphosphite based compound and uses of the same | |
EP3176212B1 (en) | Flame-retardant resin composition and article molded from same | |
EP3950885A1 (en) | Flame-retardant composition and flame-retardant synthetic resin composition | |
WO2012011519A1 (en) | Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition | |
JPH10182875A (en) | Flame-retardant thermoplastic resin composition improved in resistances to moisture and heat | |
WO1997041173A1 (en) | Flame retardant composition for polymers | |
US5102932A (en) | Flame retardants for polymers | |
ITMI941088A1 (en) | NEW POLI (PENTAERITRIL DIPHOSPHONATE) AND ITS USE IN SELF-EXTINGUISHING THERMOPLASTIC POLYMERIC COMPOSITIONS | |
JP7323749B2 (en) | Flame retardant and its preparation process | |
JP7431436B2 (en) | Flame-retardant polypropylene resin composition | |
KR101411008B1 (en) | Novel phosphorus compound, method for preparing thereof and flame retardant thermoplastic resin composition containing the same | |
KR102687495B1 (en) | Flame retardants and their manufacturing processes | |
JP4152011B2 (en) | Phosphate ester compounds | |
KR100448419B1 (en) | Mono(2,2,6,6-tetramethyl piperidyl) diaryl phosphate compounds having improved fire retardancy and thermal resistance and low tarnishing, preparation method thereof, and resin composition comprising the same | |
KR20240110985A (en) | Flame retardant and preparation process thereof | |
JP2020109150A (en) | Flame retardant composition, flame retardant resin composition using the same, molded article, and method for producing molded article | |
JP3899569B2 (en) | Flame retardant polyolefin resin composition | |
JP2020105465A (en) | Flame retardant composition, flame retardant resin composition using the same, molded article, and method for producing molded article | |
CN113966359A (en) | Additive composition | |
TW201932541A (en) | Composition and fire-retardant resin composition | |
JP2018065758A (en) | Compound, and flame retardant and flame-retardant resin composition which employ that compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11809689 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11809689 Country of ref document: EP Kind code of ref document: A1 |