CN111635559A - Organic phosphide flame retardant and preparation method and application thereof - Google Patents
Organic phosphide flame retardant and preparation method and application thereof Download PDFInfo
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- CN111635559A CN111635559A CN202010474449.7A CN202010474449A CN111635559A CN 111635559 A CN111635559 A CN 111635559A CN 202010474449 A CN202010474449 A CN 202010474449A CN 111635559 A CN111635559 A CN 111635559A
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- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 96
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 alkyl phosphoric acid Chemical compound 0.000 claims abstract description 47
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920000098 polyolefin Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 229920001225 polyester resin Polymers 0.000 claims abstract description 10
- 239000004645 polyester resin Substances 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 6
- 239000004952 Polyamide Substances 0.000 claims abstract description 5
- 229920002647 polyamide Polymers 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 24
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 4
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CUJPFPXNDSIBPG-UHFFFAOYSA-N 1,3-propanediyl Chemical group [CH2]C[CH2] CUJPFPXNDSIBPG-UHFFFAOYSA-N 0.000 description 1
- JOLLRRMLUVEWDW-UHFFFAOYSA-N 2,2-dimethylpropylphosphonic acid Chemical compound CC(C)(C)CP(O)(O)=O JOLLRRMLUVEWDW-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- DNSDAPMTVRGGLR-UHFFFAOYSA-N 2-methylpropylphosphinic acid Chemical compound CC(C)CP(O)=O DNSDAPMTVRGGLR-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- GPRQVQIDIJJIHD-UHFFFAOYSA-N 2-phenylethylphosphinic acid Chemical compound OP(=O)CCC1=CC=CC=C1 GPRQVQIDIJJIHD-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SYAHRCMTOSIYQH-UHFFFAOYSA-N C1(CCCCC1)CCP(O)=O Chemical compound C1(CCCCC1)CCP(O)=O SYAHRCMTOSIYQH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical class [N].[P] YUWBVKYVJWNVLE-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
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- DRDKFCAHTAHYER-UHFFFAOYSA-N bis(2-methylpropyl)phosphinic acid Chemical compound CC(C)CP(O)(=O)CC(C)C DRDKFCAHTAHYER-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000005331 diazinyl group Chemical group N1=NC(=CC=C1)* 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NXHKQBCTZHECQF-UHFFFAOYSA-N ethyl(methyl)phosphinic acid Chemical compound CCP(C)(O)=O NXHKQBCTZHECQF-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940018564 m-phenylenediamine 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
- CAAULPUQFIIOTL-UHFFFAOYSA-L methyl phosphate(2-) Chemical compound COP([O-])([O-])=O CAAULPUQFIIOTL-UHFFFAOYSA-L 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to an organic phosphide flame retardant, a preparation method and an application thereof, wherein the organic phosphide flame retardant is prepared by reacting at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid with at least one of amino compounds and polyamino compounds at 0-400 ℃. The flame retardant has excellent flame retardant performance, can achieve UL-94V 0 in ABS particularly, and fills the blank of halogen-free flame retardance in ABS. Meanwhile, the flame retardant has wide application range, can be used alone or can be compounded with other flame retardants and synergistic flame retardants to be applied to polyester resin, polyamide, ABS resin, polystyrene resin, polyurethane, polyolefin materials, acrylic emulsion, EVA emulsion or rubber and rubber emulsion. The invention can be widely applied to the technical field of flame retardants.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to an organic phosphide flame retardant and a preparation method and application thereof.
Background
ABS is an engineering plastic with wide application, but the bromine antimony system flame retardant is still used in large area in the industry at present, and is a huge burden for environmental protection. Meanwhile, the flame-retardant ABS of the bromine-antimony system can release toxic gas hydrogen bromide after a fire disaster occurs, so that trapped people can generate toxic secondary hazard, and the escape and rescue are not facilitated.
Disclosure of Invention
The invention aims to solve the defects in the background technology and provides the organic phosphide flame retardant with no halogen, environmental protection and high flame-retardant efficiency. The organic phosphide flame retardant not only has excellent flame retardant effect in ABS, but also has flame retardant effect when being compounded with other flame retardants and synergistic flame retardants in polyester resin, polyamide, polystyrene resin, polyurethane, polyolefin materials, acrylic emulsion, EVA emulsion or rubber and rubber emulsion.
Therefore, the invention provides a preparation method of an organic phosphide flame retardant, which comprises the following steps:
dissolving at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid in water, and dissolving or dispersing the dialkyl hypophosphorous acid or the alkyl phosphoric acid and at least one of amino compound and polyamino compound in water, wherein the molar mass ratio of the total amount of dialkyl hypophosphite and alkyl phosphate to the total amount of amino is 1: (0.01-100) dropwise adding at least one water solution of dialkyl hypophosphorous acid or alkyl phosphoric acid into an amino compound, polyamino compound water solution or water dispersion, keeping the dropwise adding temperature at 0-100 ℃, stirring for 1-240 min, filtering or concentrating and drying a reaction product, and then baking in an oven at 100-400 ℃ for 10 min-10 h to obtain the organophosphorus compound flame retardant.
A method of preparing an organophosphate flame retardant, comprising the steps of:
placing at least one of an amino compound and a polyamino compound in a kneader, wherein the molar mass ratio of the total amount of dialkyl hypophosphite and alkyl phosphate to the total amount of amino is 1: (0.01-100) dropping the aqueous solution of at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid into a kneader at the speed of finishing dropping for 1-240 min, and stirring at the temperature of 10-400 ℃ until obtaining the organic phosphorus compound flame retardant of white powder, white liquid or light yellow liquid.
Preferably, the dialkylphosphinic acids, alkylphosphoric acids, have the general formula:
in the general formula (1), R1 and R2 can be the same or different, R1 and R2 are both selected from hydroxyl, C1-C6 saturated alkyl, C7-C18 aralkyl or C7-C18 alkaryl, and zero or one or more rings are formed between R1 and R2.
Preferably, the dialkylphosphinic acid is one or more of diethylhypophosphorous acid, dimethylphosphinic acid, phenylethylhypophosphorous acid, cyclohexylethylphosphinic acid, bis (2-methyl) propylhypophosphorous acid, (bis-isobutylhypophosphorous acid), methylethylhypophosphorous acid.
Preferably, the alkyl phosphoric acid is one or more of methyl phosphoric acid, ethyl phosphoric acid, phenyl phosphoric acid, n-butyl phosphonic acid, and (2, 2-dimethyl) propyl phosphonic acid.
Preferably, the amino compound or polyamino compound has the following general formula:
in the general formula (2), R3The carbon-nitrogen composite material is selected from one or more of saturated alkane groups of C1-C6, aralkyl groups of C7-C18, alkaryl groups of C7-C18, three-to seven-membered carbon nitrogen heterocyclic groups or condensed ring groups consisting of a plurality of carbon nitrogen heterocyclic rings, and z is an integer of 1-10.
Preferably, the amino compound and the polyamino compound are selected from one or more of ethylenediamine, propylenediamine, propylenetriamine, aniline, m-diphenylamine, melamine, dicyandiamide and 1, 4-butanediamine.
An organic phosphide flame retardant prepared by any one of the methods.
Preferably, the organic phosphide flame retardant has a structural formula as follows:
Or
Or
R1 and R2 in the structural formulae (3) to (5) are as defined in the general formula (1), R1 in the structural formulae (6) and (7) are as defined in the general formula (1), and R3 in the structural formulae (3) to (7) are as defined in the general formula (2).
Preferably, z is a positive integer of not less than 1 and not more than 10.
Preferably, R1, R2 is selected from at least one of hydroxyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl (neopentyl), n-hexyl, 2-hexyl, 3-hexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, cyclohexyl, octyl, heptyl, nonyl, decyl, phenyl, benzyl, phenethyl or cyclohexylethyl; r3 is one or more selected from methyl, ethyl, propyl, 1, 3-propanediyl, propanetriyl, n-butyl, isobutyl, triazinyl, diazinyl, piperazinyl, pyridyl, phenyl and naphthyl.
An organic phosphide flame retardant (hereinafter HRY) can be independently applied to polyester resin, polyamide, polyurethane, ABS resin, polystyrene resin, polyolefin material or rubber to obtain a corresponding polymer with excellent flame retardance, and can also be applied after being compounded with nitrogen series, silicon series, phosphorus nitrogen series, aluminum hydroxide or magnesium hydroxide and other synergistic flame retardants. Wherein, the polyester resin is selected from PET, PBT, TPEE, etc., the polyurethane is selected from TPU, thermosetting polyurethane, etc., the ABS resin is selected from high butadiene content ABS, high acrylonitrile content ABS, high styrene content ABS, high impact ABS, etc., the polystyrene resin is selected from atactic polystyrene, syndiotactic polystyrene resin, etc., the polyolefin material is selected from polypropylene, polyethylene, polyvinyl alcohol, polyvinyl acetate, SEBS and the combination thereof, SBS and the combination thereof, PP, PE, etc., and the rubber is selected from EPDM, butyl rubber, natural rubber, butadiene rubber, cis-isoprene rubber, etc. The addition proportion of the organic phosphide flame retardant is 0.01 to 80 percent of the total raw material mass percentage.
The invention provides an organic phosphide flame retardant and a preparation method and application thereof, and the organic phosphide flame retardant has the following beneficial effects:
(1) the invention firstly makes at least one of dialkyl hypophosphorous acid and alkyl phosphoric acid react with aqueous solution or turbid solution of at least one of amino compound and polyamino compound, and then transfers the reaction product into an oven with the temperature of 100-400 ℃ for secondary reaction after filtration or concentration, so as to obtain the organic phosphide flame retardant HRY, or makes at least one of dialkyl hypophosphorous acid and alkyl phosphoric acid react with at least one of amino compound and polyamino compound at the temperature of 100-400 ℃ by a kneader, so as to obtain the organic phosphide. Wherein the content of the amino salt containing dialkyl phosphinic acid or alkyl phosphonic acid is 0 to 99.99 percent, and the content of the amino salt containing dialkyl phosphinic acid amide or alkyl phosphonic acid amide is 0.01 to 100 percent.
(2) The organic phosphide flame retardant is dialkyl phosphate or a composition of alkyl phosphate and a phosphoramide compound thereof. The flame retardant has better flame retardant effect than diethyl aluminum hypophosphite in engineering plastics. The product can be applied to polyester resin, polyurethane, polyolefin materials, ABS and polyamide to obtain more excellent flame retardance than dialkyl hypophosphite; particularly in the field of ABS, the flame retardant has excellent flame retardant property.
(3) The organic phosphide flame retardant has a wider application range, brings convenience to formulation design of enterprises, and reduces research and development cost.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as described in the claims.
Example 1
Dissolving 122g of diethyl hypophosphorous acid in 500g of water to obtain a diethyl hypophosphorous acid solution, and dissolving 42g of melamine in 500g of water to obtain a mixed solution; and (3) dropwise adding the diethyl hypophosphorous acid solution into the mixed solution to react to obtain a turbid solution, continuing stirring for 240min after the dropwise adding is finished, controlling the whole reaction temperature at 80 ℃, finally filtering, washing and drying the obtained turbid solution, and placing the dried product into a 100 ℃ oven to be baked for 4h to obtain the HRY flame retardant.
Example 2
Dissolving 122g of diethyl hypophosphorous acid in 500g of water to obtain a diethyl hypophosphorous acid solution, and dissolving 54g of m-phenylenediamine in 500g of water to obtain a mixed solution; and (3) dropwise adding the diethyl hypophosphorous acid solution into the mixed solution to react to obtain a turbid solution, continuously stirring for 1min after dropwise adding is finished, controlling the whole reaction temperature at 100 ℃, filtering, washing and drying the obtained turbid solution, and baking the dried product in a baking oven with a nitrogen atmosphere at 400 ℃ for 1h to obtain the HRY flame retardant.
Example 3
Dissolving 732g of ethyl phosphoric acid in 2000g of water to obtain an ethyl phosphoric acid solution, dissolving 74g of propane diamine in 100g of water to obtain a mixed solution, dropwise adding the mixed solution into the ethyl phosphoric acid solution, keeping the whole process at 0 ℃, continuing stirring for 1h after the dropwise adding is finished, then carrying out distillation concentration, drying, and placing the dried product in an oven at 250 ℃ for baking for 10h to obtain the HRY flame retardant.
Example 4
840g of dicyandiamide is placed in a kneader at 10 ℃, 2440g of diethylhypophosphorous acid is dissolved in 732g of water and is dripped into the kneader at the speed of dripping off for 150min, the kneading is continued until no water vapor is discharged, at this time, the temperature of the kneader is raised to 350 ℃, the kneading is continued for 2h, and the HRY flame retardant is obtained after discharging.
Example 5
704g of 1, 4-butanediamine was placed in a 100 ℃ kneader, 1952g of diethylphosphinic acid were dissolved in 732g of water and added dropwise to the kneader at the end of 240min, kneading was continued until no water vapor was evolved, at which point the kneader temperature was again raised to 400 ℃ and kneading was continued for 4h, discharging was carried out to obtain the HRY flame retardant.
Example 6
756g of melamine is placed in a kneader at 150 ℃, 732g of diethylhypophosphorous acid is dissolved in 732g of water and added dropwise into the kneader at the speed of dropping for 1min, and the kneading is continued until no water vapor is discharged, at this time, the temperature of the kneader is raised to 400 ℃, the kneading is continued for 2h, and the HRY flame retardant is obtained after discharging.
And (3) comparing experimental effects:
taking example 2 as an example, HRY prepared in example 2 is added into different polyester resins, polyurethane, ABS resin, polystyrene resin, polyolefin materials or rubber, and the flame retardant property is tested.
Test 1 group
Uniformly mixing 60g of PBT, 30g of HRY and 10g of ADP, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to be 240-260 ℃, then using an extrusion suite to extrude and draw strips, and granulating to obtain the flame-retardant PBT, wherein the flame-retardant PBT is not yellowed and has the flame-retardant property of UL-94-V0.
Test 2 groups
Uniformly mixing 60g of PET, 35g of HRY, 10g of ADP and 5g of MCA, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to be 240-260 ℃, then using an extrusion suite for extrusion and drawing strips, and granulating to obtain the flame-retardant PET, wherein the flame-retardant PET has the flame-retardant property of UL-94-V0.
Test 3 groups
Uniformly mixing 60g of PE, 20g of HRY, 10g of MCA and 10g of ADP, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to be 140-160 ℃, then using an extrusion suite for extrusion and drawing strips, and granulating to obtain the flame-retardant PE, wherein the flame-retardant PE has the flame-retardant property of UL-94-V0.
Test 4 groups
Uniformly mixing 70g of ABS, 20g of HRY and 10g of MPP, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to be 180-200 ℃, then extruding a brace by using an extrusion suite, and granulating to obtain the flame-retardant ABS, wherein the flame-retardant ABS has the flame-retardant characteristic of UL-94-V0.
Test 5 groups
Uniformly mixing 70g of TPU, 15g of HRY, 10g of MPP and 5g of ADP, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to 160-180 ℃, then using an extrusion suite for extrusion and drawing strips, and granulating to obtain the flame-retardant TPU, wherein the flame-retardant TPU has the flame-retardant property of UL-94-V0.
Test 6 groups
Uniformly mixing 75g of ABS, 15g of HRY and 10g of MPP, putting the mixture into a torque rheometer for mixing, controlling the temperature of the torque rheometer to be 180-200 ℃, then extruding a brace by using an extrusion suite, and granulating to obtain the flame-retardant ABS, wherein the flame-retardant ABS has the flame-retardant characteristic of UL-94-V0.
Comparative group 1
After 70g of ABS, 20g of ADP and 10g of MPP are uniformly mixed, the mixture is put into a torque rheometer for mixing, the temperature of the torque rheometer is controlled to be 180-200 ℃, then a brace is extruded by using an extrusion suite, and granulation is carried out, so that the flame-retardant ABS is obtained, and the flame-retardant ABS only has the flame-retardant characteristic of UL-94-V2 and can not achieve the flame-retardant effect of UL-94-V0.
Comparative group 2
After 75g of ABS, 15g of ADP and 10g of MPP are uniformly mixed, the mixture is put into a torque rheometer for mixing, the temperature of the torque rheometer is controlled to be 180-200 ℃, then a brace is extruded by using an extrusion suite, and granulation is carried out, so that the flame-retardant ABS is obtained, and the flame-retardant TPU only has the flame-retardant characteristic of UL-94-HB and can not achieve the flame-retardant effect of UL-94-V0.
TABLE 1 comparison of experimental data
| Flame-retardant effect | |
| Test 1 group | UL-94-V0 |
| Test 2 groups | UL-94-V0 |
| Test 3 groups | UL-94-V0 |
| Test 4 groups | UL-94-V0 |
| Test 5 groups | UL-94-V0 |
| Test 6 groups | UL-94-V0 |
| Comparative group 1 | UL-94-V2 |
| Comparative group 2 | UL-94-HB |
The experimental results show that:
the organic phosphide flame retardant prepared by the invention is applied to polyolefin materials, polyurethane, polyester resin or rubber, and the flame retardant effect of the polyolefin materials, the polyurethane, ABS resin, polyester resin or rubber is obviously improved, so that the flame retardant effect of PBT, PET, EPDM, PE and TPU reaches the level of UL-94-V0. Under the condition of consistent flame retardant adding amount, compared with the HRY/MPP compound system, the ADP/MPP compound system has the advantages that the ABS flame retardant effect of the ADP/MPP compound system can only reach the UL-94-V2 or UL-94-HB level, and the HRY/MPP compound system can reach UL 94-V0.
In conclusion, the flame retardant effect of the polyolefin material compounded with HRY and MPP, polyurethane, ABS resin, polyester resin or rubber is excellent, particularly the flame retardant effect in ABS is far better than that of the polyolefin material compounded with ADP and ADP to compound MPP, and the flame retardant property of the flame retardant is still excellent under the condition of reducing the addition ratio of the flame retardant, so that the production cost of enterprises is greatly reduced.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the organic phosphide flame retardant is characterized by comprising the following steps:
dissolving at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid in water, and dissolving or dispersing the dialkyl hypophosphorous acid or the alkyl phosphoric acid and at least one of amino compound and polyamino compound in water, wherein the molar mass ratio of the total amount of dialkyl hypophosphite and alkyl phosphate to the total amount of amino is 1: (0.01-100) dropwise adding at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid water solution into an amino compound, polyamino compound water solution or water dispersion, keeping the dropwise adding temperature at 0-100 ℃, stirring for 1-240 min, filtering or concentrating and drying a reaction product, and then baking in an oven at 100-400 ℃ for 10min to 10h to obtain the organophosphorus compound flame retardant.
2. The preparation method of the organic phosphide flame retardant is characterized by comprising the following steps:
placing at least one of an amino compound and a polyamino compound in a kneader, wherein the molar mass ratio of the total amount of dialkyl hypophosphite and alkyl phosphate to the total amount of amino is 1: (0.01-100) dropping the aqueous solution of at least one of dialkyl hypophosphorous acid or alkyl phosphoric acid into a kneader at the speed of finishing dropping for 1-240 min, and stirring at the temperature of 10-400 ℃ until obtaining the organic phosphorus compound flame retardant of white powder, white liquid or light yellow liquid.
3. The method of producing an organophosphate flame retardant according to claim 1 or 2, wherein the dialkylphosphinic acid or alkylphosphoric acid has the following general formula:
in the general formula (1), R1 and R2 can be the same or different, R1 and R2 are both selected from hydroxyl, C1-C6 saturated alkyl, C7-C18 aralkyl or C7-C18 alkaryl, and zero or one or more rings are formed between R1 and R2.
4. The method for producing an organophosphate flame retardant according to claim 1 or 2, wherein the amino compound or polyamino compound has the following general formula:
in the general formula (2), R3The carbon-nitrogen composite material is selected from one or more of saturated alkane groups of C1-C6, aralkyl groups of C7-C18, alkaryl groups of C7-C18, three-to seven-membered carbon-nitrogen heterocyclic groups or condensed ring groups consisting of a plurality of carbon-nitrogen heterocyclic groups, and z is an integer of 1-10.
5. An organophosphate flame retardant prepared by the method of any one of claims 1 to 4.
6. An organophosphate flame retardant according to claim 5, wherein the organophosphate flame retardant has the formula:
or
Or
Or
Or
R1 and R2 in the structural formulae (3) to (5) are as defined in the general formula (1), R1 in the structural formulae (6) and (7) are as defined in the general formula (1), and R3 and z in the structural formulae (3) to (7) are as defined in the general formula (2).
7. The application of the organic phosphide flame retardant is characterized in that the organic phosphide flame retardant disclosed by any one of claims 1 to 6 can be used alone or combined with other flame retardants and synergistic flame retardants in polyester resin, polyamide, ABS resin, polystyrene resin, polyurethane, polyolefin materials, acrylic emulsion, EVA emulsion or rubber and rubber emulsion.
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