CN111848681B - Metal coordination intumescent flame retardant and preparation method thereof - Google Patents
Metal coordination intumescent flame retardant and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 88
- 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 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- -1 o-phenylenediamine compound Chemical class 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 39
- 239000007787 solid Substances 0.000 description 19
- 238000003760 magnetic stirring Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LLYCMZGLHLKPPU-UHFFFAOYSA-N perbromic acid Chemical compound OBr(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
-
- 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
A metal coordination intumescent flame retardant and a preparation method thereof are characterized in that: the structure of the flame retardant is shown as the following general formula (I):
in the general formula (I), M is Zn 2+ ，Cu 2+ ，Mn 2+ ，Co 3+ N =1 to 5; has the advantages of good thermal stability, high decomposition temperature, easy processing and recycling, and no need of compounding with montmorillonite or molecular sieve.
Description
Technical Field
The invention belongs to the field of environment-friendly flame retardant additives, and particularly relates to a metal coordination intumescent flame retardant and a preparation method thereof.
Background
In recent years, research and development of flame retardant materials are increasingly active in countries around the world, and various flame retardant products are continuously made. Although the halogen flame retardant has a good flame retardant effect, toxic and corrosive gases are released during combustion, and great hidden danger exists for human beings and the environment. Therefore, in the two commands of ' scrap electronic and electric equipment command ' (WEEE) and ' harmful substance forbidding in electronic and electric appliances ' command ' (RoHS) issued in 2003 in the european union, the addition of harmful halogen flame retardants such as polybrominated diphenyl ethers to electronic and electric appliances is strictly prohibited. Compared with halogen flame retardants, inorganic flame retardants and Intumescent Flame Retardants (IFR) are currently recognized as environment-friendly 'green' flame retardants in the scientific and industrial circles, but the flame retardants have poor thermal stability and low decomposition temperature, which causes difficulties in processing and recycling of flame-retardant high polymers.
Patent application documents with publication numbers of CN101168607A, CN101186828A, CN101230275A, CN1018641112A and the like all disclose preparation methods of flame retardants with high thermal stability, and the flame retardants are compounded by phosphorus-nitrogen intumescent flame retardants with different structures and montmorillonite or molecular sieves, so that carbonization crosslinking is promoted, and the thermal stability and the flame retardant performance of the flame retardants are improved. However, the method related to the above patent application technology requires that the intumescent flame retardant is compounded with the montmorillonite or the molecular sieve to have higher thermal stability, and the compatibility problem exists in the compounding process; moreover, the dispersion problem of the montmorillonite or molecular sieve structure is also considered, and the process requirement on experimental operation is higher.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the metal coordination intumescent flame retardant which has good thermal stability, high decomposition temperature and easy processing and recovery and does not need to be compounded with montmorillonite or molecular sieve.
In order to solve the technical problems, the invention adopts the technical scheme that: a metal coordination intumescent flame retardant has a structure shown in a general formula (I):
in the general formula (I), M is Zn 2+ ，Cu 2+ ，Mn 2+ ，Co 3+ N =1 to 5.
The metal coordination intumescent flame retardant of the invention is a single substance satisfying the above general formula or a mixture of substances, such as a mixture of any more of the corresponding substances obtained as possible n =1,2,3,4,5.
The invention also provides a preparation method of the metal coordination intumescent flame retardant, and the specific synthesis route diagram is as follows:
specifically, the invention also provides a detailed preparation step of the preparation method of the metal coordination intumescent flame retardant, which comprises the following steps:
(1) Carrying out amination reaction on salicylaldehyde and an o-phenylenediamine compound in an ethanol solvent for 5-10 hours under a reflux state and normal pressure, wherein the salicylaldehyde and the o-phenylenediamine compound have a molar ratio of 1:
(2) Putting the product (II) obtained in the step (1) in an alkaline solution, wherein the mass ratio of alkaline substances in the alkaline solution to the product (II) is 0.26, and the condensation reaction is carried out under the oxidation action of an oxidant, the reaction temperature is 50-80 ℃, the reaction time is 5-24 hours, and then the product (III) is neutralized by concentrated hydrochloric acid to be neutral, so that the product (III) is obtained, and the structure is as follows:
(3) Pentaerythritol and concentrated phosphoric acid react for 3-6 hours at 100-150 ℃ according to the molar ratio of phosphoric acid/pentaerythritol of 2 to obtain a phosphorus-containing product (IV) with the structure:
(4) The dimethyl formamide solution of the product (III) obtained in the step (2) and metal acetate (M (OOCCH) 3 ) 2 ) The dimethyl formamide solution and the product (IV) react for 5 to 10 hours at the temperature of between 80 and 110 ℃ to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I).
The alkaline solution in step (2) of the present invention is a 10wt% potassium hydroxide aqueous solution, and the oxidizing agent is one or a mixture of more of perchloric acid, hypobromous acid, hypochlorous acid, sodium hypochlorite, chlorous acid, permanganic acid, perbromic acid, hydrogen peroxide, oxygen, and the like.
The concentrated phosphoric acid in the step (3) of the invention has a mass percentage concentration of 85% and a mass concentration of 4 mol/L.
The metal acetate in the step (4) of the invention is any one or mixture of a plurality of zinc acetate, manganese acetate, nickel acetate and cobalt acetate; the molar concentration of the dimethylformamide solution of the metal acetate (M (OOCCH 3) 2) is 0.25-0.75mol/L (namely 1L of dimethylformamide contains 0.25-0.75mol of metal acetate).
The concentration of the product (III) in the dimethylformamide solution in the step (4) of the present invention is 75 to 80g/L, preferably 78.5g/L; in the step (4), the molar ratio of the product (III) to the product (IV) to the metal acetate is = 0.05.
The invention has the advantages and beneficial effects that:
1. the invention combines metal ions and the intumescent flame retardant by a coordination mode, so that the whole flame retardant structure tends to be stabilized. On the other hand, the catalytic flame-retardant effect of the metal element can improve the flame-retardant effect of the intumescent flame retardant, and the environment-friendly intumescent flame retardant with high thermal stability can be obtained. The flame retardant with a specific structure provided by the invention has very important influence on the final performance by the position of metal ions and the functional group coordinated and lapped with the metal ions; the flame retardants of the prior art, if not coordinated with metals, result in poor thermal stability; the phosphorus structure of the prior art, if not provided with a cyclic structure, also causes poor thermal stability; meanwhile, if the phosphorus structures in the prior art are still connected in a covalent bond mode, nitrogen protection is needed in the operation process, the control requirement on the operation process conditions is high, and the operation is complex. The flame retardant structure of the invention does not have the condition of the prior art, and the metal coordination and phosphorus-containing structure in the invention are cyclic structures, so that the thermal stability can be improved; the flame retardant with a specific structure of the application has the difference in comparison with the prior art that 1) the coordination position of metal ions has different essence: the metal ions are coordinated between unsaturated amine = N-of a benzene ring side group, hydroxyl oxygen-OH of the benzene ring and a phosphoric acid structure of the annular phosphorus flame retardant; in the prior art, metal ions are coordinated between saturated amino and hydroxyl of a benzene ring; 2) The coordination structure of the metal ions in the application is superior in that double bonds of unsaturated amino groups and double bonds on benzene rings exist in the same coordination hexahydric ring, so that a more stable conjugated structure is formed, and the thermal stability of the structure is improved; 3) The phosphorus element in the phosphorus flame retardant used in the application is positioned in two connected five-membered ring structures, and the five-membered ring structures are more stable, so that the structural system of the application has higher thermal stability; 4) In the prior art, phosphorus-containing groups are combined into a metal type flame retardant in a covalent bond mode, sodium ethoxide is used as a catalyst in a synthesis process, as is well known, sodium ethoxide is generally prepared at any time, and needs to be reacted by metal sodium and ethanol, and the metal sodium is extremely easy to catch fire when meeting water and is an extremely dangerous chemical; meanwhile, the sodium ethoxide is stronger in alkalinity than the sodium hydroxide, so that the danger of the operation process is increased; the phosphorus-containing group is combined into the flame retardant in a coordination bond mode, and sodium ethoxide is not needed in the process, so that the phosphorus-containing group has better operation safety; 5) The flame retardant related in the prior art is a micromolecule, and is added into a macromolecular matrix, so that the migration effect is easy to generate, and the flame retardant effect has timeliness; the flame retardant is of a polymer structure with a certain long chain, is added into a high molecular substrate needing flame retardance, and is not easy to migrate, so that the flame retardant effect is superior to that of a small molecular structure flame retardant in aging.
2. The method has the advantages of simple and convenient operation, mild reaction conditions, high yield, cheap and easily-obtained raw materials, and the obtained metal coordination intumescent flame retardant has high thermal stability and flame retardant property. The preparation method combines methods such as amination, condensation and metal organic coordination, elements such as phosphorus and nitrogen with expansion flame-retardant function can be combined with metal ions with catalytic flame-retardant function, and the obtained product has a certain molecular chain length, can have good compatibility with an organic polymer system, and has a certain flame-retardant effect. The method has simple operation and high yield. The obtained flame retardant has a longer molecular chain and is better in compatibility with a polymer matrix; the obtained flame retardant structure is a complex of metal ions and an intumescent flame retardant, the stable metal coordination structure can effectively improve the thermal stability of the flame retardant, the flame retardant has excellent char formation, and the residual char content of the flame retardant after degradation at 700 ℃ in a nitrogen atmosphere can reach over 64 percent.
Drawings
FIG. 1 is an infrared test comparison spectrogram of a product structure (III) obtained by recondensing an intumescent flame retardant product structure (I) coordinated with metal cobalt, manganese, nickel and zinc and a product obtained by reacting salicylaldehyde with o-phenylenediamine.
FIG. 2 shows a nuclear magnetic hydrogen spectrum comparison of the product structure (II) after the reaction of salicylaldehyde with o-phenylenediamine with the product structure (III) after the recondensation of the product structure (II).
FIG. 3 shows the comparison chart of the thermogravimetric test of the product structure (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant.
Detailed Description
The present invention is described in further detail below by way of examples, but the present invention is not limited to only the following examples.
The technical effects to be realized by the invention are as follows: good thermal stability and high decomposition temperature, does not need to compound an intumescent flame retardant with montmorillonite or molecular sieve, and can effectively ensure the flame retardant property of the organic polymer matrix.
Example 1
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to reflux, then 10.8g of o-phenylenediamine is dissolved in 200ml of absolute ethanol and slowly dripped into the flask, the dripping is completed within 2 hours, the reaction is continued for 6 hours, the obtained solid and liquid mixture is cooled to room temperature, filtered and washed by absolute ethanol for 3 times, and dried in a vacuum drying oven under reduced pressure at 50 ℃ for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81 percent.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into 1000ml of a flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of DMF (dimethyl formamide) solution of oligomeric salicylaldehyde o-phenylenediamine (III) with the concentration of 78.5g/L and 200ml of DMF solution of 0.5mol/L zinc acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure general formula (I).
30g of the flame retardant obtained in the embodiment is added into 70g of low-density polyethylene, the oxygen index of the obtained flame retardant material can reach 28.5%, and the vertical combustion reaches UL 94V 0 level.
Example 2
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to reflux, then 10.8g of o-phenylenediamine is dissolved in 200ml of absolute ethanol and slowly dripped into the flask, the dripping is completed within 2 hours, the reaction is continued for 6 hours, the obtained solid and liquid mixture is cooled to room temperature, filtered and washed by absolute ethanol for 3 times, and dried in a vacuum drying oven under reduced pressure at 50 ℃ for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81 percent.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylidene o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of nickel acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 4h to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of low-density polyethylene, the oxygen index of the obtained flame retardant material can reach 27.9%, and the vertical combustion can pass UL 94V 0 level.
Example 3
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10wt% potassium hydroxide aqueous solution in a 250ml three-neck flask at room temperature by magnetic stirring, introducing oxygen to react for 24 hours, neutralizing the solution to be neutral by hydrochloric acid after the reaction is finished to obtain brown solid, washing the brown solid by deionized water for 3 times, and drying the brown solid in a vacuum drying oven at 50 ℃ under reduced pressure for 24 hours to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 65%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylidene o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of zinc acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 4h to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of polypropylene, the oxygen index of the obtained flame retardant material can reach 29.1%, and the vertical combustion can pass UL 94V 0 level.
Example 4
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dropwise adding 25ml of 27.5% hydrogen peroxide aqueous solution within 20min, neutralizing the solution to be neutral by using hydrochloric acid after the reaction is finished, obtaining brown solid, washing the brown solid for 3 times by using deionized water, and drying the brown solid in a vacuum drying oven at 50 ℃ under reduced pressure for 24 hours to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 78%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into a 1000ml flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylidene o-phenylenediamine (III) and 200ml of 0.5mol/L DMF solution of manganese acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 4h to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of PC/ABS alloy (wherein the mass ratio of PC to ABS in the alloy is 70/30), the oxygen index of the obtained flame retardant material can reach 31.2%, and the vertical combustion can pass UL 94V 0 level.
Example 5
100ml of absolute ethanol solution containing 24.4g of salicylaldehyde is added into a 500ml flask with condensation reflux and magnetic stirring, the temperature is increased to 78 ℃ to cause reflux, then 10.8g of o-phenylenediamine is dissolved into 200ml of absolute ethanol and slowly dripped into the flask, dripping is finished within 2 hours, the reaction is continued for 6 hours, the temperature is cooled to room temperature, the obtained solid and liquid mixture is filtered, the washing is carried out for 3 times by using the absolute ethanol, and the mixture is dried in a vacuum drying oven at 50 ℃ under reduced pressure for 4 hours to obtain an orange granular salicylaldehyde o-phenylenediamine (II) product, wherein the yield is about 81%.
Dissolving 20g of salicylaldehyde o-phenylenediamine (II) in 52ml of 10wt% potassium hydroxide aqueous solution by magnetic stirring in a 250ml three-neck flask at room temperature, dripping 87ml of sodium hypochlorite solution with effective chlorine being more than or equal to 7.5% within 20min, heating to 60 ℃ for reaction for 5h after dripping, cooling to room temperature, neutralizing the solution to be neutral by hydrochloric acid to obtain brown solid, washing 3 times by deionized water, and drying under reduced pressure in a vacuum drying oven at 50 ℃ for 24h to obtain the oligomeric salicylaldehyde o-phenylenediamine (III), wherein the yield is about 87%.
Adding 11.6ml of concentrated phosphoric acid and 13.6g of pentaerythritol into 1000ml of a flask with condensation reflux and magnetic stirring, heating to 120 ℃, reducing the temperature to 98 ℃ after reacting for 4h, respectively adding 200ml of 78.5g/L DMF solution of oligomeric salicylaldehyde o-phenylenediamine (III) and 200ml of 0.3mol/L DMF solution of cobalt acetate, reacting for 7h at 98 ℃, cooling to room temperature, filtering the obtained solid and liquid mixture, washing for 3 times by using absolute ethyl alcohol, and drying for 4h at 50 ℃ under reduced pressure in a vacuum drying oven to obtain the powdery metal coordination intumescent flame retardant with the structure general formula (I). 30g of the flame retardant obtained in the embodiment example is added into 70g of polypropylene, the oxygen index of the obtained flame retardant material can reach 28.3%, and the vertical combustion can pass UL 94V 0 level.
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, simplifications and equivalents which do not depart from the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Test results
The comparative spectrum analysis of the infrared test of the product structure (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant shown in the figure 1, the example 2, the example 4 and the example 5 respectively shows that: it is evident from FIG. 1 that 1590-1700cm before and after coordination -1 All have absorption peaks for group C = N; after the coordination of metal and phosphate, the concentration is 1000-1200cm -1 A very distinct characteristic peak of phosphate ester appears; at 521-627cm -1 The peaks appeared are the peaks of chemical bonds Co-O, mn-O, ni-O and Zn-O generated after coordination of metal cobalt, manganese, nickel and zinc, and the above shows that the metal coordination intumescent flame retardant is successfully synthesized.
The nuclear magnetic hydrogen spectrum comparison of the product structure (II) after the reaction of salicylaldehyde and o-phenylenediamine and the product structure (III) after the recondensation of the product structure (II) shown in FIG. 2 shows that: the nuclear magnetic peak position of the product structure (II) is basically similar to that of the product structure (III) obtained after condensation, because the condensation position occurs on the benzene ring of salicylaldehyde, and no new group structure is generated except that the same chain link unit is added, so the positions of hydrogen are similar and no new displacement is generated. The nuclear magnetic hydrogen spectrum of the product structure (III) has larger noise between delta 6 ppm and 9ppm because the polymerized product has poor solubility in a deuterated reagent used for testing, so the nuclear magnetic spectrum has larger noise. Wherein a is a peak shift of a hydrogen atom on a hydroxyl group on a benzene ring, b is a peak shift of a hydrogen atom on a carbon atom above a carbon atom in a C = N bond, C is a peak shift of a hydrogen atom on a carbon atom in a meta position of a hydroxyl group on a benzene ring, d is a peak shift of a hydrogen atom on a carbon atom on a benzene ring to which bis N is bonded, and e is a peak shift of a hydrogen atom on a carbon atom in ortho-position and para-position to a hydroxyl group on a benzene ring.
FIG. 3 shows the thermogravimetric analysis of the product structure (I) of the metallic cobalt, manganese, nickel and zinc coordinated intumescent flame retardant: the metal-coordinated intumescent flame retardants are degraded steadily throughout the temperature scanning process, and their carbon residue amounts are 77.6%, 72.1%, 64.5%, and 89.4%, respectively. This shows that the structural combination of metal, phosphorus and nitrogen elements can obtain higher thermal stability organic-inorganic hybrid products.
Claims (9)
1. A metal coordination intumescent flame retardant is characterized in that: the structure of the flame retardant is shown as the following general formula (I):
( I )
in the general formula (I), M is Zn 2+ ，Cu 2+ ，Mn 2+ ，Co 3+ N =1 to 5.
2. The metal-coordinating intumescent flame retardant of claim 1, wherein: the flame retardant is any one of corresponding substances corresponding to the condition that n =1,2,3,4,5 in the general formula (I) or a mixture comprising a plurality of substances.
3. A preparation method of a metal coordination intumescent flame retardant is characterized by comprising the following steps: the specific synthetic scheme is:
4. The process for preparing a metal-coordinated intumescent flame retardant of claim 3, wherein: the preparation method comprises the following steps:
carrying out amination reaction on salicylaldehyde and an o-phenylenediamine compound in an ethanol solvent for 5 to 10 hours under a reflux state and normal pressure, wherein the molar ratio of the salicylaldehyde to the o-phenylenediamine compound is 1:
（Ⅱ）；
putting the product (II) obtained in the step (1) in an alkaline solution, wherein the mass ratio of alkaline substances to the product (II) is 0.26, and the condensation reaction is carried out under the oxidation action of an oxidant, the reaction temperature is 50-80 ℃, the reaction time is 5-24 hours, and then neutralizing the product to be neutral by concentrated hydrochloric acid to obtain a product (III), and the structure of the product is as follows:
（Ⅲ）；
pentaerythritol and concentrated phosphoric acid react for 3-6 hours at 100-150 ℃ according to the molar ratio of phosphoric acid/pentaerythritol of 2 to obtain a phosphorus-containing product (IV) with the structure:
（Ⅳ）；
(4) Dimethyl formamide solution of the product (III) obtained in the step (2) and metal acetate (M (OOCCH) 3 ) 2 ) The dimethyl formamide solution and the product (IV) react for 5 to 10 hours at a temperature of between 80 and 110 ℃ to obtain the powdery metal coordination intumescent flame retardant with the structure of the general formula (I).
5. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the concentrated phosphoric acid in the step (3) is concentrated phosphoric acid with the mass percentage concentration of 85% and the mass concentration of 4 mol/L.
6. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the metal acetate in the step (4) is any one or more of zinc acetate, manganese acetate, nickel acetate and cobalt acetate.
7. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 4, characterized in that: the molar concentration of the dimethylformamide solution of the metal acetate is 0.25-0.75mol/L.
8. The process for preparing a metal-coordinated intumescent flame retardant of claim 4, wherein: the concentration of the product (III) in the dimethylformamide solution in the step (4) is 75-80g/L.
9. The process for the preparation of a metal-coordinated intumescent flame retardant according to claim 8, characterized in that: the concentration of the product (III) in the dimethylformamide solution in the step (4) is 78.5g/L; in the step (4), the molar ratio of the product (III) to the product (IV) to the metal acetate is = 0.05.
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