CN102850392A - Organic rare earth metal phosphinate or polymer thereof, and preparation method and application thereof - Google Patents
Organic rare earth metal phosphinate or polymer thereof, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102850392A CN102850392A CN2012101868224A CN201210186822A CN102850392A CN 102850392 A CN102850392 A CN 102850392A CN 2012101868224 A CN2012101868224 A CN 2012101868224A CN 201210186822 A CN201210186822 A CN 201210186822A CN 102850392 A CN102850392 A CN 102850392A
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- CN
- China
- Prior art keywords
- rare earth
- earth metal
- polymkeric substance
- phospho acid
- metal salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 rare earth metal phosphinate Chemical class 0.000 title claims abstract description 149
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 68
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003063 flame retardant Substances 0.000 claims abstract description 70
- 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 abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 79
- 239000000126 substance Substances 0.000 claims description 45
- 239000000206 moulding compound Substances 0.000 claims description 31
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920001059 synthetic polymer Polymers 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical group OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 239000012757 flame retardant agent Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 150000002909 rare earth metal compounds Chemical class 0.000 abstract 1
- 238000011282 treatment Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000004033 plastic Substances 0.000 description 17
- 229920003023 plastic Polymers 0.000 description 17
- 238000012545 processing Methods 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003385 sodium Chemical class 0.000 description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 150000002603 lanthanum Chemical class 0.000 description 3
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 3
- 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 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 101100235070 Mus musculus Lgalsl gene Proteins 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-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
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 239000004110 Zinc silicate Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- CKMNQZXKOURUMB-UHFFFAOYSA-N cerium dimer Chemical compound [Ce]#[Ce] CKMNQZXKOURUMB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical group C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- HVHZIOXTVVFZGV-UHFFFAOYSA-N diphosphono hydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical class NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(=O)OP(O)(O)=O HVHZIOXTVVFZGV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 229920000570 polyether Polymers 0.000 description 2
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- 229940071182 stannate Drugs 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
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- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 2
- 235000019352 zinc silicate Nutrition 0.000 description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 2
- MXAOILAHPVJWBS-UHFFFAOYSA-N 10-(azepan-1-yl)-10-oxodecanamide Chemical compound NC(=O)CCCCCCCCC(=O)N1CCCCCC1 MXAOILAHPVJWBS-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 1
- OECUQWQIGXMPAN-UHFFFAOYSA-N 6-oxo-6-pyrrolidin-1-ylhexanamide Chemical compound NC(=O)CCCCC(=O)N1CCCC1 OECUQWQIGXMPAN-UHFFFAOYSA-N 0.000 description 1
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 1
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
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- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
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- FDJZNXLKZOXHPN-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O FDJZNXLKZOXHPN-UHFFFAOYSA-N 0.000 description 1
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- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- OXIACMHTSQNJCY-UHFFFAOYSA-N bis[hydroxy(phosphonooxy)phosphoryl] hydrogen phosphate 1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(=O)OP(=O)(O)OP(=O)(O)OP(=O)(O)OP(=O)(O)O.N1=C(N)N=C(N)N=C1N OXIACMHTSQNJCY-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
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- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 description 1
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- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000012795 eco-friendly flame retardant Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWARNCMTCYKUBS-UHFFFAOYSA-N ethyl n-(ethoxycarbonylcarbamoyl)carbamate Chemical compound CCOC(=O)NC(=O)NC(=O)OCC FWARNCMTCYKUBS-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 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
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 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
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides an organic rare earth metal phosphinate or a polymer thereof, and a preparation method thereof. Rare earth metal is contained in phosphonate structures of the organic rare earth metal phosphinate or the polymer thereof. The preparation method comprises the steps that: 1, an alkali metal salt of substituted phosphinic acid or phosphinic acid polymer containing substituents R1 and R2 is dissolved in water, such that a solution is obtained; and the solution is added into a reactor containing heating and stirring devices; 2, under a heating condition, a rare earth metal compound is gradually added; stirring is continuously carried out, until a reaction is sufficiently carried out; 3, when the reaction is finished, filtering, drying, and crushing treatments are carried out, such that the organic rare earth metal phosphinate or the polymer thereof is obtained. The invention also relates to the application of the organic rare earth metal phosphinate or the polymer thereof as a flame retardant, a flame retardant composition, and a flame retardant polymer molding composition.
Description
Technical field
The present invention relates to a kind of organic secondary phosphine acid salt and its polymkeric substance, particularly relate to organic phospho acid rare earth metal salt and its polymkeric substance and preparation method thereof and application.
Background technology
Macromolecular material is take carbon and protium as the material that main long carbochain molecule forms, and has combustibility, and they have not only caused a large amount of losses when burning, simultaneously also in various degree discharge a large amount of smog and toxic gas, cause casualties.This is so that fire retardant becomes one of essential functional aid of macromolecular material.Usually, halogenated compound, particularly many bromos aromatic compound has been used as the flame-retardant additive in this base polymer.It has been generally acknowledged that when these products were lighted, the halogenated compound in these products was suppressed at the free radical gas-phase reaction that occurs in the flame.This is so that halogenated flame is used as the additive of the different types of polymers material that comprises polyester and nylon very at large.Yet at nearest approximately quindecennial, the dispute of the environmental protection of its initiation and health aspect has limited its further use, and the use of halogenated flame has been subjected to supervisory.At this moment, fire retardant industry thinks that towards research and development the direction of more eco-friendly flame-retardant additive changes under pressure.Phosphorus type flame retardant is high because of its phosphorus content, and has high flame retardant, few additive and on the little characteristics of finished product physical property impact.Phosphorus type flame retardant has fire-retardant and the plasticising dual-use function, can make fire retardant realize fully non-halogen, improve the flow processability energy in the plastic shaping and reduce to ablate, improve heat aging performance, improve heat-drawn wire, and the resistates after can suppressing to burn, be the logical substitute of halogenated flame.Most of phosphorous fire retardant promotes to provide flame retardant activity with the combination that becomes charcoal by solidifying phase reaction, polymkeric substance carbonization.These flame resistant methods obviously depend on the polymkeric substance that wherein uses this phosphorous flame-retardant additive.Therefore, concrete phosphorous structure need to be designed to be applicable to the multiple polymers type.At late 1970s and the beginning of the eighties, prepared the various salt of diaryl phospho acid, alkylaryl Hypophosporous Acid, 50 and dialkyl phosphinic acid, for example aluminium or zinc salt are for example in U.S. Patent No. 4,150,495; 4,208,321; With 4,205, illustrate in 322.These phosphinates are added among the PET or with polyethylene terephthalate copolymer and close.In the level of 10 1 20wt%, measure by the oxygen index (L0I) of unit, observe flame retardant resistance and improve.But existing fire retardant thermostability deficiency is difficult to satisfy the processing request of portioned product, such as glass fiber enhanced nylon or polyester.So fire retardant or the fire-retardant combination of inventing a kind of high thermal stability have its actual value.The outer shell structure of rare earth element uniqueness demonstrates not only abundant but also unique physics one chemical property, has determined that also its compound has a lot of peculiar functions, and this is the basis that rare-earth additive is used.
At present, the additive agent field of rare earth element successful Application has PVC with the thermo-stabilizer of calcium zinc and rare earth combination, the p crystal-type nucleater with rare earth multicomponent complex compound or rare earth and IIA family metal formation binuclear complex of PP.And in flame retardant area, rare earth element there is no the application precedent, is in conjunction with using with rare earth element and high thermal-stability bittern-free flame retardant or flame retardant combination how, is the research topic of a renewal.
Summary of the invention
Technical problem to be solved by this invention is problem fire retardant or thermostability deficiency or not environmental protection in the prior art.
For solving this technical problem, the invention provides a kind of organic phospho acid rare earth metal salt and its polymkeric substance and preparation method thereof and application.
Organic phospho acid rare earth metal salt provided by the invention or its polymkeric substance is characterized in that, combination has rare earth metal in the phosphonate structure of this organic phospho acid rare earth metal salt or its polymkeric substance.
Organic phospho acid rare earth metal salt provided by the invention or its polymkeric substance is characterized in that, represent by (I) or (II):
Wherein: R
1And R
2Be respectively the C of straight chain or branched or ring-type
1-C
6Alkyl, the preferably C of straight or branched
1-C
4Alkyl.Described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, hexyl, isohexyl, cyclohexyl or phenyl.
Re is 1/3 of lanthanide series rare-earth elements, 1/3 the implication at this place is: because Re is trivalent, thereby for each Re, have in the structure shown in three formulas (II) and three oxygen its covalency simultaneously with its covalency, in other words, the mole number of the Re in the structure shown in the formula (II) in fact only has and 1/3 of the mole number of the O of its covalency.
U is the cell-average polymkeric substance, u=1～5
Organic phospho acid rare earth metal salt provided by the invention or its polymkeric substance, it is characterized in that, the residual moisture content of this organic phospho acid rare earth metal salt or its polymkeric substance is 0.01-0.30wt%, and average particle size particle size is 0.1-1000 μ m, and volume density is 80-800g/L.
Organic phospho acid rare earth metal salt provided by the invention or its synthetic polymer method comprise step: the first step, will contain substituent R
1And R
2Replacement phosphonic acids or an alkali metal salt of its polymkeric substance be dissolved in the water and obtain solution, again this solution is joined in the reactor with heating and whipping appts second step, under heating condition, progressively add rare earth compound, continuously stirring is until fully reaction; In the 3rd step, after reaction finishes, after filtration, drying and pulverization process, obtain final product, i.e. organic phospho acid rare earth metal salt or its polymkeric substance.
Rare earth compound in the described second step is preferably in the metal oxide that contains rare earth metal, metal hydroxides, metal acetate, metal nitrate, the metal chloride any.
Rare earth element in the described rare earth compound is preferably lanthanide series rare-earth elements.
The described substituent R that contains
1And R
2Replacement phospho acid or the phosphorus content in the phospho acid polymkeric substance and the mol ratio of described rare earth compound be preferably 3: 1.
The invention provides aforesaid organic phospho acid rare earth metal salt or its polymkeric substance or arbitrarily the mixture of two or more different these organic phospho acid rare earth metal salts and/or its polymkeric substance as the application of fire retardant, flame retardant composition and flame-retardant polymer moulding compound.
Preferred organic phospho acid rare earth metal salt polymkeric substance is as the application of fire retardant in the flame-retardant polymer moulding compound.
Organic phospho acid rare earth metal salt that the present invention proposes or its polymkeric substance are as the application of flame retardant composition, the concrete grammar of this application is preferably as follows: will add additive in alkyl phosphinic acid rare-earth salts or alkyl phosphinic acid rare-earth salts polymkeric substance or its mixture, obtain flame retardant composition, wherein: the add-on of alkyl phosphinic acid rare-earth salts or alkyl phosphinic acid rare-earth salts polymkeric substance is 70wt-95wt%, and the add-on of additive is 5wt-30wt%.The average particle size particle size of flame retardant composition is 0.1-3000 μ m, is preferably 0.1-1000 μ m, more preferably 1-100 μ m.
Described additive is three (hydroxyethyl) chlorinated isocyanurates and aromatic multi-carboxy acid's oligopolymer vinegar, benzoguanamine, three (hydroxyethyl) chlorinated isocyanurates, wallantoin, glycoluril, melamine, melamine cyanurate, the urea cyanurate, Dyhard RU 100, guanidine, melamine phosphate, two melamine phosphates, five melamine triphosphates, three melamine diphosphates, four melamine triphosphates, six melamine pentaphosphates, the melamine diphosphate, the melamine tetraphosphate, the melamine pyrophosphate salt, the melamine polyphosphate, the melam polyphosphate, melem polyphosphate or mellon(e) polyphosphate, zn cpds, magnesium compound, calcium cpd, aluminum compound, in manganic compound or carbodiimide or (many) isocyanic ester any; Be preferably in three (hydroxyethyl) chlorinated isocyanurates and aromatic multi-carboxy acid's oligopolymer ester, benzoguanamine, three (hydroxyethyl) chlorinated isocyanurates, wallantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, Dyhard RU 100 or the guanidine any; Described zn cpds such as zinc oxide, zinc hydroxide, aqua oxidation zinc, zinc carbonate, zinc, zinc hydroxyl stannate, zinc silicate, zinc phosphate, zinc borate or zinc molybdate; Acid amide in described carbodiimide such as carbonyl diurethane are own.Described magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, two hydrotalcites, magnesiumcarbonate or magnesium calcium carbonate.Described calcium cpd such as calcium hydroxide, calcium oxide, hydrocalumite; Described zn cpds such as zinc oxide (such as active zinc flower), zinc hydroxide, aqua oxidation zinc, zinc carbonate (such as alkaline carbonic acid zinc, Carbon Dioxide zinc), zinc, zinc hydroxyl stannate, zinc silicate, alkaline phosphatase zinc, alkaline zinc borate, alkaline zinc molybdate or alkaline zinc sulphide.Described aluminum compound such as aluminum oxide, aluminium hydroxide, hydrargillite or aluminum phosphate.Described manganic compound such as manganese oxide, manganous hydroxide.Described tin compound such as stannic oxide.
Organic phospho acid rare earth metal salt polymkeric substance that the present invention proposes is as the application of fire retardant in the flame-retardant polymer moulding compound, concrete grammar is as follows: flame retardant composition, polymkeric substance and additive are mixed in mixing tank, heating and melting is even in the compounding associated plant, products therefrom is extruded, cooling namely gets required flame-retardant polymer moulding compound product.
The described polymkeric substance that wherein mixes is derived from diamines and dicarboxylic acid, or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, or derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone.
This polymeric amide and copolyamide such as polymeric amide-2,12, polymeric amide-4(gathers-4-Aminobutanoicacid), polymeric amide-4,6(gathers (tetramethylene adipamide), polymeric amide-6(polycaprolactam, poly-6-aminocaprolc acid) polymeric amide-6,6(gathers (N, N-hexa-methylene adipamide)), polymeric amide-6,9(gathers (hexa-methylene nonane two acid amides), polymeric amide-6,10(gathers (hexa-methylene decanediamide)), polymeric amide-6,12(gathers (hexa-methylene dodecane diamide)), polymeric amide-6/6,6(poly-(hexa-methylene hexanamide-be total to-phthalein amine in oneself)), polymeric amide-7(gathers-the 7-aminoheptylic acid), polymeric amide-7,7(gathers heptamethylene pimeloyl amine), polymeric amide-8(poly-8-amino eaprylic acid), polymeric amide-8,8(gathers eight methylene radical suberamides), polymeric amide-9(gathers-9 aminononanoic acid), polymeric amide-9,9(gathers nine methylene radical pelargonamides), polymeric amide-10(poly-10-amino capric acid), polymeric amide-10,9(gathers (decamethylene pelargonamide)), polymeric amide-10,10(gathers decamethylene certain herbaceous plants with big flowers acid amides), polyamide-11 (poly-11-amino undecanoic acid), polymeric amide-12(polylauryllactam), derived from meta-dimethylbenzene, the aromatic polyamide of diamines and hexanodioic acid; The polymeric amide (polyhexamethylene isophthaloyl amine or polyhexamethylene terephthalamide) of being made by hexamethylene-diamine and m-phthalic acid and/or terephthalic acid, if suitable, made as properties-correcting agent by elastomerics, such as poly--2,4,4-tri-methyl hexamethylene terephthalamide or poly--meta-phenylene isophthaloyl amine; Above-mentioned polymeric amide and polyolefine with olefin copolymer, and from aggressiveness, or connect with valence bond or the elastomerics of grafting; Or and polyethers, as with polyoxyethylene glycol, polypropylene glycol, or the segmented copolymer of polytetramethylene glycol; Perhaps by by EPDM or by the copolyamide of ABS modification or polymeric amide; The perhaps polymeric amide of condensation (" RIM polymeric amide system in treating processes ").
This polyester such as polyethylene terephthalate, and polybutylene terephthalate (Celanex2500, Celanex 2002, Celanese; Ultradur, BASF), poly-(Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane terephthalate), poly-hydroxybenzoate, and derived from the segmented polyetherester of the polyethers with hydroxyl end groups; And by polycarbonate or by the polyester of MBS modification.
Described compounding associated plant adopts single screw extrusion machine or multi-region screw extrusion press, and effective spiro rod length (L) of compounding associated plant is 4-200D, and D is screw diameter.
The uniform Heating temperature of described melting is 250-290 ℃ for polyethylene terephthalate, is 230-270 ℃ for polybutylene terephthalate, for polymeric amide-the 6th, and 260-290 ℃, for polymeric amide-the 6.6th, 260-290 ℃.
General remark: the production of flame retardant plastics moulding compound and plastic molded articles, processing and test
Flame retardant compositions optionally mixes with additive with polymeric aggregate, and in 230 to 260 ℃ of (GRPBT) or 260 to 280 ℃ (GRPA 66) lower addings of temperature twin screw extruder.The polymer-extruded thing of homogenize is drawn, in water-bath, cool off, and subsequently granulation.
After abundant drying, moulding compound is obtained test sample in 240 to 270 ℃ of (GRPBT) or 260 to 290 ℃ (GRPA 66) lower processing of melt temperature in injection moulding machine.For measure UL94(insurance laboratory from the test sample of the test sample used thickness 1.6mm of every kind of mixture) the burning grade. following burning grade is provided by UL94:
V-0: the time that burns away never was longer than 10 seconds, and the summation of the time that burns away when lighting for 10 times is no more than 50 seconds, does not have drippage on fire, and sample burns down fully, and sample never was longer than 30 seconds in the twilight sunset of lighting after finishing perdurability.
V-1: never be longer than 30 seconds in the time that burns away of lighting after finishing, the summation of the time that burns away when lighting for 10 times is no more than 250 seconds, and the twilight sunset of sample after lighting end never was longer than 60 seconds perdurability, and other standard is as V-0.
V-2: cotton indicator is dripped by fire. lights; Other standard is as V-1.
Unclassified (n.r.): do not satisfy burning grade V-2.
Flame-retardant polymer moulding compound of the present invention is applicable to producd fibers, and film, or moulded work are particularly useful for the Electrical and Electronic field.The present invention preferably uses flame-retardant polymer moulded work of the present invention as lamp part, such as lamp socket and lamp bracket, and plug and insertion wiring board, coil stand, for the shell of electrical condenser or contactor, and contactor, relay1 case and reverberator.
Organic Hypophosporous Acid, 50 rare-earth salts provided by the present invention has good flame retardant effect, and thermotolerance is strong; Preparation is simple, and starting material are easy to obtain, and cost is low; Compare with existing halogenated compound fire retardant, be conducive to environmental protection.
Embodiment
Further specify the present invention according to following embodiment.
Embodiment 1
Two ethyl phospho acid lanthanums synthetic: in reactor, add the two ethyl phospho acid sodium of 101.8g and the 400g aqueous solution, two ethyl phospho acid sodium structural formulas shown in general formula (I), R
1With R
2Be ethyl; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains lanthanum trichloride 57.4g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid lanthanum 116.5g (theoretical value 117.8g).
Embodiment 2
Two ethyl phospho acid lanthanums are dimeric synthetic: in reactor, add the two ethyl phospho acid sodium dimers of 91.3g and the 400g aqueous solution, two ethyl phospho acid sodium dimeric structure formulas shown in general formula (II), R
1With R
2Be ethyl; U equals 1; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains lanthanum trichloride 57.4g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid lanthanum dimer 95.5g (theoretical value 107.3g).
Embodiment 3
The preparation of two ethyl phospho acid lanthanums and two ethyl phospho acid cerium mixtures: in reactor, add the two ethyl phospho acid sodium of 101.8g and the 400g aqueous solution, two ethyl phospho acid sodium structural formulas shown in general formula (I), R
1With R
2Be ethyl; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains lanthanum trichloride 31.6g and contain cerous compounds 26.2g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid lanthanums and two ethyl phospho acid cerium mixture 114.3g (theoretical value 118.1g).
Embodiment 4
The preparation of two ethyl phospho acid lanthanum dimers and two ethyl phospho acid cerium dimer mixtures: in reactor, add the two ethyl phospho acid sodium dimers of 91.3g and the 400g aqueous solution, two ethyl phospho acid sodium dimeric structure formulas shown in general formula (II), R
1And R
2Be ethyl; U equals 1; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains lanthanum trichloride 31.6g and contain cerous compounds 26.2g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid lanthanum dimers and two ethyl phospho acid cerium dimer 93.2g (theoretical value 107.6g).
Embodiment 5
The preparation of two ethyl phospho acid samariums: in reactor, add the two ethyl phospho acid sodium of 101.8g and the 400g aqueous solution, two ethyl phospho acid sodium structural formulas shown in general formula (I), R
1With R
2Be ethyl; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains Samarium chloride 60.5g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid samarium 115.0g (theoretical value 118.1g).
Embodiment 6
The dimeric preparation of two ethyl phospho acid samarium: in reactor, add the two ethyl phospho acid sodium dimers of 91.3g and the 400g aqueous solution, two ethyl phospho acid sodium dimeric structure formulas shown in general formula (II), R
1And R
2Be ethyl; U equals 1; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains Samarium chloride 60.5g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two ethyl phospho acid samarium 97.2g (theoretical value 107.6g).
Embodiment 7
Two methyl-phosphinic acid lanthanums synthetic: in reactor, add the two methyl-phosphinic acids of 94g and the 400g aqueous solution, two methyl-phosphinic acid sodium structural formulas shown in general formula (I), R
1With R
2Be methyl; Under agitation, be warming up to 90 ℃, begin to drip the aqueous solution 248.5g that contains lanthanum trichloride 81.5g, dropwised in 1 hour, and then be incubated 1 hour; After reaction finishes, filter, washing, oven dry is pulverized, and obtains two methyl-phosphinic acid lanthanum 128.2g (theoretical value 138.7g).
Embodiment 8
General remark according to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing and test ", the mixture that will be comprised of the polybutylene terephthalate (PBT1) of the MPP of the product of the embodiment 7 of 14% weight and 6% weight and 80% weight 230 to 260 ℃ of lower compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder; After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-0 according to the classification of UL94.
Embodiment 9
General remark according to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing and test ", the mixture that will be comprised of the polybutylene terephthalate (PBT1) of the MPP of the product of the embodiment 3 of 14% weight and 6% weight and 80% weight 230 to 260 ℃ of lower compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder; After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-1 according to the classification of UL94.
Embodiment 10
General remark according to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing and test ", will by the MPP of the product of the embodiment 4 of 14% weight and 6% weight and mixture that 80% weight polybutylene terephthalate (PBT1) forms in twin screw extruder 230 to 260 ℃ of lower compoundings, obtain the flame-retardant polymer moulding compound.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-1 according to the classification of UL94.
Embodiment 11
General remark according to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing and test ", the mixture that will be comprised of the MPP of the weight OP1230 of the product of the embodiment 1 of 8% weight and 6% and 6% weight and 50% weight polybutylene terephthalate (PBT2) and 30% weight glass 230 to 260 ℃ of lower compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-0 according to the classification of UL94.
Embodiment 12
According to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, the mixture that will be comprised of the MPP of the OP1230 of the product of the embodiment 2 of 8% weight and 6% weight and 6% weight and 50% weight polybutylene terephthalate (PBT2) and 30% weight glass 230 to 260 ℃ of lower compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-0 according to the classification of UL94.
Embodiment 13
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, will be by the product of the embodiment 1 of 6% weight and the fire retardant OP1230 of 6% weight, 5% weight melamine polyphosphate, 1% weight zinc borate, 52% weight polyamide PA66, the mixture that forms with 30% weight glass fiber 260 to 280 ℃ of lower compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 260 to 300 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-0 according to the classification of UL94.
Embodiment 14
General remark according to above-mentioned " production of flame retardant plastics moulding compound and plastic molded articles; processing and test ", will be by the product of the embodiment 5 of 14% weight and the MPP(melamine pyrophosphate of 6% weight) and the mixture that forms of the polybutylene terephthalate (PBT1) of 80% weight in twin screw extruder 230 to 260 ℃ of lower compoundings, obtain the flame-retardant polymer moulding compound; After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of lower processing of melt temperature in injection moulding machine.Test sample is V-1 according to the classification of UL94.
The embodiment application result sees Table two
The used chemical of table one
| Melamine pyrophosphate MPP | Ciba M200 |
| Polybutylene terephthalate (PBT1) | Celanex2300GV 1/30 (containing 30% glass) |
| Polybutylene terephthalate (PBT2) | GE307 |
| Two ethyl phospho acid sodium | Press CN 1660857A preparation |
| Two ethyl phospho acid sodium dimers | Press CN 101906117A (embodiment 1) preparation |
| Fire retardant OP1230 | Clariant company produces |
| Glass | HP3786(3.2MM) Taiwan BiCheng Co., Ltd |
| Nylon 66PA66 | BASF A3 |
| Zinc borate ZB | Lucky blue or green chemical industry |
| Lanthanum trichloride | Chemical Reagent Co., Ltd., Sinopharm Group |
| Cerous compounds | Chemical Reagent Co., Ltd., Sinopharm Group |
| Samarium chloride | Chemical Reagent Co., Ltd., Sinopharm Group |
| Two methyl-phosphinic acids | Chemical Reagent Co., Ltd., Sinopharm Group |
Table two embodiment application result
| Embodiment | 8 | 9 | 10 | 11 | 12 | 13 | 14 |
| Embodiment 1 product | 8 | 6 | |||||
| Embodiment 2 products | 8 | ||||||
| Embodiment 3 products | 14 | ||||||
| Embodiment 4 products | 14 | ||||||
| Embodiment 5 products | 14 | ||||||
| Embodiment 7 products | 14 | ||||||
| OP1230 | 6 | 6 | 6 | ||||
| ZB | 1 | ||||||
| MPP | 6 | 6 | 6 | 6 | 6 | 5 | 6 |
| PBT1 | 80 | 80 | 80 |
| PBT2 | 50 | 50 | 50 | ||||
| Glass | 30 | 30 | 30 | 30 | |||
| PA6,6 | 52 | ||||||
| The UL94 classification | V-0 | V-1 | V-1 | V-0 | V-0 | V-0 | V-1 |
Claims (16)
1. an organic phospho acid rare earth metal salt or its polymkeric substance is characterized in that, in the phosphonate structure of this organic phospho acid rare earth metal salt or its polymkeric substance rare earth metal are arranged.
2. organic phospho acid rare earth metal salt according to claim 1 or its polymkeric substance is characterized in that, represent by (I) or (II):
Wherein: R
1And R
2Be respectively the C of straight chain or branched or ring-type
1-C
6Alkyl,
Re is 1/3 of lanthanide series rare-earth elements,
U is the cell-average polymkeric substance, u=1～5.
3. organic phospho acid rare earth metal salt according to claim 2 or its polymkeric substance is characterized in that described alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, hexyl, isohexyl, cyclohexyl or phenyl.
4. organic phospho acid rare earth metal salt according to claim 2 or its polymkeric substance is characterized in that described alkyl is the C of straight or branched
1-C
4Alkyl.
5. organic phospho acid rare earth metal salt according to claim 1 or its polymkeric substance, it is characterized in that, the residual moisture content of this organic Hypophosporous Acid, 50 rare earth metal salt or its polymkeric substance is 0.01-0.30wt%, and average particle size particle size is 0.1-1000 μ m, and volume density is 80-800g/L.
6. organic phospho acid rare earth metal salt claimed in claim 2 or its synthetic polymer method is characterized in that, may further comprise the steps:
The first step will contain substituent R
1And R
2Replacement phospho acid or an alkali metal salt of phospho acid polymkeric substance be dissolved in the water and obtain solution, again this solution is joined in the reactor with heating and whipping appts;
Second step under heating condition, progressively adds rare earth compound, and continuously stirring is until fully reaction;
In the 3rd step, after reaction finishes, after filtration, drying and pulverization process, obtain described organic phospho acid rare earth metal salt or its polymkeric substance.
7. organic phospho acid rare earth metal salt according to claim 6 or its synthetic polymer method, it is characterized in that, described rare earth compound be in the metal oxide that contains rare earth metal, metal hydroxides, metal acetate, metal nitrate, the metal chloride any.
8. organic phospho acid rare earth metal salt according to claim 6 or its synthetic polymer method is characterized in that, the rare earth element in the described rare earth compound is lanthanide series rare-earth elements, and described basic metal is sodium or potassium.
9. organic phospho acid rare earth metal salt according to claim 6 or its synthetic polymer method is characterized in that, the described substituent R that contains
1And R
2The replacement phospho acid or the mol ratio of the phosphorus content in the phospho acid polymkeric substance and described rare earth compound be 3: 1.
Organic phospho acid rare earth metal salt as claimed in claim 1 or its polymkeric substance or arbitrarily the mixture of two or more different these organic phospho acid rare earth metal salts and/or its polymkeric substance as the application of fire retardant, flame retardant composition and flame-retardant polymer moulding compound.
11. application according to claim 10, it is characterized in that, the concrete grammar of described application is as follows: add additive in organic phospho acid rare earth metal salt or its polymkeric substance or in the mixture of arbitrarily two or more different these organic phospho acid rare earth metal salts and/or its polymkeric substance, obtain described flame retardant composition, the average particle size particle size of obtained flame-retardant agent composition is 0.1-3000 μ m.
12. application according to claim 11 is characterized in that, described additive is melamine phosphate, two melamine phosphates, melamine pyrophosphate salt, melamine polyphosphate, any one in the alkyl Hypophosporous Acid, 50 or any two or more mixture.
13. application according to claim 10, it is characterized in that, when described organic secondary phosphine acid salt or its polymkeric substance are used for the flame-retardant polymer moulding compound, concrete grammar is as follows: flame retardant composition, polymkeric substance and additive are mixed in mixing tank, heating and melting is even in the compounding associated plant, products therefrom is extruded, and cooling obtains described flame-retardant polymer moulding compound.
14. application according to claim 13 is characterized in that described polymkeric substance is derived from diamines and dicarboxylic acid, or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, or derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone.
15. according to right 13 described application, it is characterized in that described compounding associated plant adopts single screw extrusion machine or multi-region screw extrusion press, effective spiro rod length of compounding associated plant is 4-200D, D is screw diameter.
16. application according to claim 13, it is characterized in that, the uniform Heating temperature of described melting, it is 250-290 ℃ for polyethylene terephthalate, it is 230-270 ℃ for polybutylene terephthalate, for polymeric amide-the 6th, 260-290 ℃, for polymeric amide-the 6.6th, 260-290 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475706A (en) * | 2009-01-22 | 2009-07-08 | 广东华南精细化工研究院有限公司 | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof |
| CN102086401A (en) * | 2009-12-04 | 2011-06-08 | 中国科学院大连化学物理研究所 | Organic aluminum phosphate fire retardant and preparation method and use thereof |
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| CN101475706A (en) * | 2009-01-22 | 2009-07-08 | 广东华南精细化工研究院有限公司 | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof |
| CN102086401A (en) * | 2009-12-04 | 2011-06-08 | 中国科学院大连化学物理研究所 | Organic aluminum phosphate fire retardant and preparation method and use thereof |
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| Title |
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| AFONIN, E. G.，ET AL.: "Synthesis and investigation of rare earth element bis(chloromethyl)phosphinates", 《ZHURNAL OBSHCHEI KHIMII》, vol. 61, no. 4, 31 December 1991 (1991-12-31), pages 790 - 5, XP008118133 * |
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| CN105017311A (en) * | 2015-07-08 | 2015-11-04 | 广东华南精细化工研究院有限公司 | Rare earth phenylethyl phosphinate, and synthesis method and application thereof |
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