CN1193031C - 一种三聚氰胺缩合产物和含磷酸的盐 - Google Patents
一种三聚氰胺缩合产物和含磷酸的盐 Download PDFInfo
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- CN1193031C CN1193031C CNB018043569A CN01804356A CN1193031C CN 1193031 C CN1193031 C CN 1193031C CN B018043569 A CNB018043569 A CN B018043569A CN 01804356 A CN01804356 A CN 01804356A CN 1193031 C CN1193031 C CN 1193031C
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- Prior art keywords
- acid
- salt
- compound
- condensation product
- melamine condensation
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- 239000002253 acid Substances 0.000 title claims abstract description 33
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 20
- 239000007859 condensation product Substances 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 9
- 239000011574 phosphorus Substances 0.000 title abstract description 9
- -1 triazine compound Chemical class 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 39
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 claims description 25
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 8
- 150000007518 monoprotic acids Chemical class 0.000 claims description 5
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 13
- 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 description 9
- 150000001408 amides Chemical class 0.000 description 7
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000012745 toughening agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 5
- 125000003003 spiro group Chemical group 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229920002903 fire-safe polymer Polymers 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 230000001698 pyrogenic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 2
- ASFAFOSQXBRFMV-LJQANCHMSA-N 3-n-(2-benzyl-1,3-dihydroxypropan-2-yl)-1-n-[(1r)-1-(4-fluorophenyl)ethyl]-5-[methyl(methylsulfonyl)amino]benzene-1,3-dicarboxamide Chemical compound N([C@H](C)C=1C=CC(F)=CC=1)C(=O)C(C=1)=CC(N(C)S(C)(=O)=O)=CC=1C(=O)NC(CO)(CO)CC1=CC=CC=C1 ASFAFOSQXBRFMV-LJQANCHMSA-N 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 2
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 1
- CSSLZLQDGHKFLE-UHFFFAOYSA-N 1-hydroxy-1$l^{5}-phospholane 1-oxide Chemical compound OP1(=O)CCCC1 CSSLZLQDGHKFLE-UHFFFAOYSA-N 0.000 description 1
- CDDGCGLADRPTQZ-UHFFFAOYSA-N 1-hydroxy-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound OP1(=O)CCC=C1 CDDGCGLADRPTQZ-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 101000905241 Mus musculus Heart- and neural crest derivatives-expressed protein 1 Proteins 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UIFYLQRSDQQZKW-UHFFFAOYSA-N P(O)(O)=O.P(O)(O)=O.OCC(CO)(CO)CO Chemical class P(O)(O)=O.P(O)(O)=O.OCC(CO)(CO)CO UIFYLQRSDQQZKW-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- GWLJTAJEHRYMCA-UHFFFAOYSA-N phospholane Chemical compound C1CCPC1 GWLJTAJEHRYMCA-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 125000001918 phosphonic acid ester group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
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Abstract
一种三聚氰胺缩合产物和含磷酸的盐,该含磷酸是一种含磷的一元酸。以及一种制备三聚氰胺缩合产物的含磷盐的方法,其中把一种三嗪化合物与一种含磷的一元酸一起加热到250-400℃的温度。
Description
本发明涉及一种三聚氰胺缩合产物和含磷酸的盐及其制备方法和作为阻燃剂在阻燃的聚合物组合物中的用途。
三聚氰胺缩合产物和含磷化合物的混合物用于阻燃的聚合物组合物是已知的,见NL-B-1006525。该专利描述了一种阻燃的聚酯组合物,其中用一种含氮的化合物与一种含磷的化合物形成防火的组合物。NL-B-1006525的聚合物组合物的缺点是含磷的化合物与含氮的化合物必须分开制备。作为NL-B-1006525中的含氮化合物,特别使用了蜜白胺。然而,制备几乎纯粹的蜜白胺的方法是一种难以实施并且在经济上吸引力很小的多步法。在第一步中,使用三聚氰胺和一种催化剂形成一种蜜白胺和相关的催化剂的盐,从这种盐出发,经过多个后续步骤得到几乎纯粹的蜜白胺。在该文献中提到的已知催化剂是氯化锌和磺酸例如对甲苯磺酸。
本发明的目的是提供一种基于三聚氰胺缩合产物和含磷化合物的阻燃剂,这种阻燃剂可以以经济的方式在单工艺步骤中制得。具体地说,本发明的目的是基于蜜白胺和含磷化合物,以经济的方式在单工艺步骤中制备一种阻燃剂。
已经发现,在使用一种含磷一元酸作为含磷酸的情况下,通过制备一种三聚氰胺缩合产物和一种含磷酸的含磷盐,可以实现这个目的。优选使用蜜白胺作为三聚氰胺缩合产物。
可用于本发明的含磷一元酸是含有至少一个磷酸、膦酸或次膦酸基团并且只带有一个酸当量的化合物。
只带有一个酸当量的磷酸、膦酸或次膦酸基团的例子有可以用通式(I)表示的磷酸酯基、可以用通式(II)表示的烷基膦酸酯基和可以用通式(III)表示的次膦酸:
(R1O-)(R2O-)-P(=O)-OH (I)
(R3O-)R4P(=O)-OH (II)
R5R6P(=O)-OH (III)
其中R1-R6(包括R6)代表取代的或未取代的烷基、芳基、环烷基、
芳烷基或烷芳基取代基。
优选使用包含式(II)和/或式(III)基团的化合物。合适的式(III)的次膦酸的例子有乙基甲基次膦酸、二乙基次膦酸、取代的或未取代的1-羟基二氢-2,5-二氧杂-1-磷杂环戊烷(1-hydroxydihydrophospholoxide)、取代的或未取代的1-羟基氧化磷杂环戊烷(1-hydroxyphospholane oxide)和二膦酸。二膦酸是带有两个膦酸根的化合物。合适的式(II)的膦酸酯的例子有甲基膦酸的甲酯、乙酯和丙酯。
含磷的一元酸和含氮化合物的含磷盐包含至少50-95摩尔%的三聚氰胺缩合产物,特别是蜜白胺。
在EP-A363,321中描述了一种膦酸三聚氰胺盐或膦酸二(三聚氰胺)盐,并且把它们用作聚合物组合物中的阻燃剂。这些盐的缺点是它们包含三聚氰胺,在加工成聚合物组合物的过程中三聚氰胺能发生升华。在EP-A363,321中描述的制备这些盐的方法不能用于三聚氰胺缩合产物例如蜜白胺,因为这些盐在水中的溶解度很差。
申请人还发现,三聚氰胺缩合产物特别是蜜白胺的含磷盐的制备可以简单地通过把一种三嗪化合物与含磷的一元酸一起加热到250-400℃的温度,优选280-350℃的温度而实现。合适的三嗪化合物是三聚氰胺、三聚氰酸二酰胺和三聚氰酸一酰胺或其混合物。优选使用三聚氰胺。可以存在杂质例如脲、二氰基二酰胺、胍和脲基三聚氰胺而没有危害。
每摩尔三嗪化合物所用的含磷一元酸的数量为0.05-0.5摩尔,优选使用0.1-0.5摩尔。也可以使用铵盐或三聚氰胺盐形式的含磷一元酸。使用三聚氰胺盐时,应考虑到三聚氰胺例如蜜白胺有可能参与缩合反应。可以相应地减少计量入反应器中的三嗪化合物的数量。
可以通过把包含一种三嗪化合物和一种含磷一元酸或其三聚氰胺或铵盐的混合物加热到大约250-350℃来进行反应。优选反应在280-320℃下进行。优选反应在几乎水平的搅拌着的反应器中进行。在反应期间生成氨,可以通过用一种惰性气体例如氮气冲洗反应器来除去它。除了含磷盐或非含磷盐形式的蜜白胺外,在反应期间还可以生成少量的其它含磷盐或非含磷盐形式的三嗪缩合产物,例如蜜勒胺、氰尿酰胺和methon。也可能把一小部分含磷的一元酸转变为酸酐化合物。
如果需要的话,可以对三聚氰胺缩合产物特别是蜜白胺的含磷盐作进一步的处理。这种进一步的处理优选用水进行洗涤,使得一部分三聚氰胺和/或其它水溶性组分能够溶解并从三聚氰胺缩合产物的含磷盐中除去。
申请人还发现本发明的蜜白胺的含磷盐能够给聚合物的组合物带来阻燃性。
本发明的聚合物组合物除了含有三聚氰胺缩合产物特别是蜜白胺的含磷盐外,还含有至少一种聚合物。另外,它还含有增强剂和/或填料和/或与蜜白胺的含磷盐具有协同作用的化合物,其可以包含除本发明的阻燃化合物之外的化合物和/或阻燃组份。还可以存在常用的添加剂例如热稳定剂和紫外线稳定剂、脱模剂、流动性促进剂、增塑剂、润滑剂、分散剂、染料和/或颜料,一般来说,这些添加剂的用量应当不会对组合物的性能产生负面影响。
可以用蜜白胺的含磷盐带来阻燃性的聚合物组合物包含需要耐热的阻燃剂的聚合物,例如聚酰胺、聚酰亚胺、聚酯、聚氨酯以及这些物质的混合物和共混物。
聚酰胺的例子有从二胺和二羧酸和/或氨基羧酸或相应的内酰胺衍生得到的聚酰胺和共聚酰胺,例如聚酰胺4、聚酰胺6、聚酰胺6/6、聚酰胺4/6,部分芳烃化的(共)聚酰胺,例如基于芳香族二胺和己二酸的聚酰胺;从亚烷基二胺和间和/或对苯二甲酸衍生得到的聚酰胺及其共聚酰胺等。
聚酯的例子有从二羧酸和二醇和/或从羟基羧酸或其相应的内酯衍生得到的聚酯,例如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、聚己内酯及其共聚酯等。
优选把蜜白胺的含磷盐与聚对苯二甲酸乙二酯和/或聚对苯二甲酸丁二酯,特别是与聚对苯二甲酸丁二酯,或者与聚酰胺例如尼龙-6、尼龙6,6或尼龙4,6用于聚合物组合物中。
如果在聚合物组合物中使用增强剂和/或填料,则它们的含量在宽的范围内变化,该含量部分地由个人想达到的力学性能的水平决定。一般来说,增强剂的含量不超过聚合物组合物总重量的50%。优选地,经过强化的聚合物组合物将包含5-50wt%的增强剂,更优选包含15-45wt%的增强剂。增强剂的例子有云母、粘土、滑石、玻璃纤维、芳族聚酰胺纤维和碳纤维。可以把不同的增强剂混合。但是优选玻璃纤维。
聚合物组合物的阻燃性能可以因对蜜白胺的含磷盐具有协同作用的化合物的存在而得到加强。结果,本发明的蜜白胺的含磷盐一般可以选择更低的含量。一种具有协同作用的化合物的例子是在与或不与能促进焦化形成的催化剂混合的情况下能形成焦化的化合物。原则上,能通过由火引起焦化的形成而加强阻燃的聚合物组合物的阻燃性能的所有已知化合物都有资格作为形成焦化的化合物。例如酚树脂、环氧树脂、三聚氰胺树脂、醇酸树脂、有机硅树脂、尿烷树脂、聚苯醚、聚乙烯醇、聚(乙烯共聚乙烯基)和含有至少两个羟基的化合物。含有至少两个羟基的化合物的例子有带有至少两个羟基的醇,例如季戊四醇、双季戊四醇、三季戊四醇及其混合物。对蜜白胺的含磷盐具有协同作用的能形成焦化的化合物的浓度一般为聚合物组合物总重量的0-30wt%。
作为能促进焦化形成的催化剂,可以使用特别是钨酸的金属盐、钨与一种非金属的配酸氧化物、氧化锡的盐、氨基磺酸铵和/或其二聚体。钨酸的金属盐优选为钨酸的碱金属盐,特别是钨酸钠。应当把钨与一种非金属的配酸氧化物理解为由非金属例如硅或磷与钨形成的配酸氧化物,例如硅钨酸或磷钨酸。聚合物组合物中所用的能促进焦化形成的催化剂的量为0.1-5wt%,优选为0.1-2.5wt%。
当聚合物组合物包含一种或多种其它的阻燃组份时,本发明的蜜白胺的含磷盐的阻燃性能可以进一步得到加强。原则上所有已知的阻燃剂都有资格作为阻燃组份。这种阻燃组份的例子有锑的氧化物例如三氧化锑,其与卤素化合物结合使用;碱土金属氧化物,例如氧化锌、氧化镁;其它金属氧化物,例如氧化铝、二氧化硅、氧化铁和氧化锰;金属氢氧化物,例如氢氧化镁和氢氧化铝;纳米复合材料;粘土,例如蒙脱土和高岭土;经过处理的粘土,例如用伯铵化合物或季铵化合物或三聚氰胺或含磷的化合物处理过的粘土;含硅化合物,例如硅酸盐、有机硅化合物、芳香族有机硅化合物和硅烷;金属硼酸盐,例如水合的或非水合的硼酸锌;含硫的化合物,例如硫化锌、硫酸铵、氨基磺酸铵和硫酸三聚氰胺盐;含磷的化合物,例如磷酸酯、膦酸酯、次膦酸酯、膦、氧化膦和亚磷酸酯。磷酸酯的例子有芳族的正磷酸酯例如磷酸三(对甲苯基)酯和磷酸三(对叔丁基苯基)酯、FyrolflexRDP(AKZO-Nobel)环磷酸酯、四苯基双酚-A二磷酸酯以及上述磷酸酯的混合物。膦酸酯的例子有膦酸酯和混合的膦酸酯。膦酸酯的例子还有1,3,2-二氧杂磷杂环己烷-5,5-二甲基-2-苯氧基-2-氧化物、膦酸季戊四醇酯聚合物例如聚[3(-9)亚烷基-2,4,8,10-四氧杂-3,9-二磷杂螺[5.5]十一碳烷-3,9-二氧化物]、环膦酸酯、双环膦酸酯例如季戊四醇二膦酸酯、线型的或环状的三羟甲基丙烷和甲基膦酸的酯,例如Antiblaze1045LV(Albright&Wilson)、环状的亚新戊基季戊四醇磷酸酯。次膦酸酯(盐)的例子有次膦酸盐例如脂环族次膦酸盐和次膦酸酯。次膦酸酯(盐)的其它例子有二次膦酸、二甲基次膦酸、乙基甲基次膦酸、二乙基次膦酸以及这些酸的盐,例如铝盐和锌盐。氧化膦的例子有异丁基双(羟烷基)氧化膦和1,4-二异丁烯-2,3,5,6-四羟基-1,4-二氧化膦或1,4-二异丁烯-1,4-二磷酰基-2,3,5,6-四羟基环己烷。含磷化合物的其它例子有NH1197(Great Lakes)、NH1511(Great Lakes)、NcendX P-30(Albemarle)、Hostaflam OP550(Clariant)、HostaflamOP910(Clariant)和Cyagard RF 1204、Cyagard RF 1241和Cyagard RF 1243(Cyagard是Cytec Industries的产品)。优选使用磷酸酯、次膦酸酯和/或膦酸酯作为含磷化合物。含磷化合物的含量可以占阻燃剂混合物总重量的0-25wt%。
在阻燃剂组合物中也可以存在其它已知的化合物例如防滴剂聚四氟乙烯。
在聚合物组合物中所用的其它阻燃组份的含量可以在很宽的范围内变化,但是一般不超过蜜白胺的含磷盐的含量。
可以使用已知的常规技术例如通过在一个转鼓式混合器中把所有的或多种组份干混,然后在一种熔融混合器例如在布雷本登混合器或单-或双螺杆挤出机或捏合机中,优选在双螺杆挤出机中熔化来制备本发明的聚合物组合物。
可以把聚合物组合物的不同组份一起计量入挤出机的入口。也可以把不同组份计量入挤出机的不同部位。可将一些可以存在的组份例如染料、稳定剂、阻燃的组合物、对三嗪阻燃剂和/或其它阻燃组份具有协同作用的化合物以例如母炼胶形式加入聚合物中。
可以使用本领域技术人员已知的技术例如注模法把本发明的阻燃聚合物组合物加工成半成品或最终产品。
在下列实施例的基础上对本发明作进一步的解释:
实施例1
在一个4L的反应器中,加入400g三聚氰胺和170g乙基甲基次膦酸(CH3-)(CH3CH2-)P(=O)-OH)的混合物。在2小时内把反应器加热到290℃。通过氮气流除去形成的氨。反应混合再加热物1小时,然后冷却产物。根据HPLC的分析,产物包含67wt%的蜜白胺和1wt%的三聚氰胺。根据元素分析,产物的磷含量为9wt%,这个值对应于0.5×102摩尔%的乙基甲基次膦酸含量。
实施例2
在一个4L的反应器中,加入400g三聚氰胺和175g甲基甲氧基次膦酸(CH3-)(CH3O-)P(=O)-OH)的混合物。在2小时内把反应器加热到290℃。通过氮气流除去形成的氨。反应混合物再加热1小时,然后冷却产物。根据HPLC的分析,产物包含66wt%的蜜白胺和2wt%的三聚氰胺。根据元素分析,产物的磷含量为9wt%,这个值对应于0.5×102摩尔%的甲基甲氧基次膦酸含量。
实施例3
向一台同轴旋转双螺杆挤出机(Werner & Pfleiderer,型号ZSK30/33)中加入45份聚对苯二甲酸丁二酯、30份玻璃纤维、25份实施例1的产物。把滚筒温度设定到250℃,螺杆速率设定到200转/分钟。从得到的化合物制得厚度为1.6mm的试验棒。让制得的一组试验棒接受UL94着火点试验。着火性能类别为VO。试验棒的E-模量为10.0mPa,在每种情况下,衰坏伸长为2.0%(ISO 527/1)。
实施例4
向一台同轴旋转双螺杆挤出机(Werner & Pfleiderer,型号ZSK30/33)中加入45份聚对苯二甲酸丁二酯、30份玻璃纤维、8份Antiblaze1045(Albright&Wilson)和17份实施例1的产物。把滚筒温度设定到250℃,螺杆速率设定到200转/分钟。从得到的化合物制得厚度为1.6mm的试验棒。让制得的一组试验棒接受UL94着火点试验。着火性能类别为VO。试验棒的E-模量为10.3mPa,在每种情况下,衰坏伸长为2.1%(ISO 527/1)。
实施例5
向一台同轴旋转双螺杆挤出机(Werner & Pfleiderer,型号ZSK30/33)中加入45份聚对苯二甲酸丁二酯、30份玻璃纤维、8份乙基甲基次膦酸铝、17份实施例1的产物。把滚筒温度设定在250℃,螺杆速率设定到200转/分钟。从得到的化合物制得厚度为1.6mm的试验棒。让制得的一组试验棒接受UL94着火点试验。着火性能类别为VO。试验棒的E-模量为10.3MPa,在每种情况下,衰坏伸长为2.1%(ISO527/1)。
实施例6
向一台小型的微型挤出机(自制的)中加入75份聚对苯二甲酸丁二酯和25份实施例2的产物。把滚筒温度设定在270℃,螺杆速率设定到100转/分钟。从得到的化合物制得厚度为2.0mm的试验棒。让制得的一组试验样品接受UL94着火点试验。着火性能类别为VO。
实施例7
向一台小型的微型挤出机(自制的)中加入75份聚酰胺-6和25份实施例2的产物。把滚筒温度设定在270℃,螺杆速率设定到100转/分钟。从得到的化合物制得厚度为2.0mm的试验棒。让制得的一组试验样品接受UL94着火点试验。着火性能类别为VO。
Claims (8)
1.一种三聚氰胺缩合产物和含磷酸的盐,其特征在于:次膦酸为所述含磷酸。
2.权利要求1的盐,其特征在于:蜜白胺为所述三聚氰胺缩合产物。
3.一种包含三聚氰胺缩合产物和次膦酸的盐的聚合物组合物。
4.一种制备三聚氰胺缩合产物的含磷盐的方法,其特征在于把一种三嗪化合物与一种含磷的一元酸一起加热到250-400℃的温度。
5.权利要求4的方法,其特征在于:温度为280-350℃。
6.权利要求4的方法,其特征在于:使用三聚氰胺、三聚氰酸二酰胺和/或三聚氰酸一酰胺作为三嗪化合物。
7.权利要求6的方法,其特征在于:使用三聚氰胺作为三嗪化合物。
8.权利要求4-7任一项的方法,其特征在于:使用膦酸酯或次膦酸作为含磷的一元酸。
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NL1014232A NL1014232C2 (nl) | 2000-01-31 | 2000-01-31 | Zout van een melaminecondensatieproduct en een fosfor bevattend zuur. |
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DE10359816B4 (de) * | 2003-12-19 | 2006-11-16 | Clariant Produkte (Deutschland) Gmbh | Flammschutzmittel-Stabilisator-Kombination für Polyester und Polyamide sowie damit hergestellte Kunststoff-Formmassen |
US7452159B2 (en) * | 2004-01-14 | 2008-11-18 | Karoleen B. Alexander | Method of making a multi-layered structure for tree well skirt and sidewalks |
DE102004019716A1 (de) * | 2004-04-20 | 2005-08-04 | Ticona Gmbh | Flammenschutzmittelzusammensetzung, flammgeschützte Formmasse, Verfahren zu deren Herstellung und deren Verwendung |
US20080071013A1 (en) * | 2006-07-12 | 2008-03-20 | David Abecassis | Novel thermoplastic pelletizing technology |
BRPI0820538B1 (pt) | 2007-11-16 | 2021-08-17 | Mind-Nrg Sa | Usos de uma isoforma recombinante solúvel de neuregulina-1, e composição farmacêutica ou kit |
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CN101570518B (zh) * | 2009-06-12 | 2010-11-17 | 东华大学 | 一种膨胀型三聚氰胺次磷酸盐阻燃剂的制备方法 |
WO2011092194A1 (de) | 2010-01-27 | 2011-08-04 | Ecoatech Gmbh | N-methyl-melaminiumsalz des monomethylmethanphosphonsäureesters als flammschutzmittel |
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EP2702102A1 (de) | 2011-04-28 | 2014-03-05 | Basf Se | Flammgeschütze formmassen |
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RU2471788C1 (ru) * | 2011-07-07 | 2013-01-10 | Лев Давидович Раснецов | Способ получения цианурата меламина |
US20160281001A1 (en) | 2013-09-17 | 2016-09-29 | Thor Gmbh | Flame retardant composition |
BR112016010648B1 (pt) | 2013-11-18 | 2021-05-04 | Afton Chemical Corporation | pacote de aditivo detergente para um combustível de gasolina sem chumbo, concentrado de aditivo, composição combustível para a gasolina sem chumbo, e métodos para operar, para melhorar pelo menos um dos depósitos de válvula de admissão ou para melhorar o desempenho antidesgaste em um motor de ignição por centelha |
US9752009B2 (en) | 2015-01-26 | 2017-09-05 | Lanxess Solutions Us Inc. | Flame retardant polymer compositions comprising heat treated phosphorus compounds and melam |
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TWI263654B (en) | 2006-10-11 |
IL150693A0 (en) | 2003-02-12 |
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AU3422201A (en) | 2001-08-14 |
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US6730773B2 (en) | 2004-05-04 |
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