CN105037287A - Melamine polyphosphoric acid rare earth metal salt, synthetic method and application - Google Patents
Melamine polyphosphoric acid rare earth metal salt, synthetic method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/56—Preparation of melamine
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- 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
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
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Abstract
Melamine polyphosphoric acid rare earth metal salt, a synthetic method and application belong to the field of chemical synthesis. According to the invention, by combining stable melamine polyphosphoric acid with light rare earth elements with unique electron distribution and corresponding electron cloud density, a dual effect of being good in thermal stability, high in phosphorus content and high in char forming catalytic efficiency and improving compatibility and flame-retardant synergistic effect by rare earth coordinate bonding is fully exerted, and the melamine polyphosphoric acid rare earth metal salt can be applied to an intumescent flame-retardant system. The chemical synthetic method comprises a solution method and a calcining method. The formula is shown in the description, wherein M is a rare earth element in lanthanide series, n1 is an integer which is greater than or equal to 2 and n2 is an integer of 1, 2 or 3.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of phosphorus-nitrogen cooperative flame retardant Halogen rare earth compound and preparation technology thereof, be specifically related to a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt and preparation method thereof, this compound can do polyester, polyamide-based, containing the retardant applications of the macromolecular materials such as epoxy resins.
Background technology
The development of phosphorus flame retardant.
Along with the enforcement in succession of domestic and international environmental regulation, the substitution problem of halogenated flame retardant is more and more urgent.Phosphorus flame retardant, because it is in the balance, range of product diversity, product suitability etc. of flame retardant properties and physical and mechanical properties, is the kind promising to be main flow fire retardant of future generation most.
In current global range, under the fire-retardant non-halogen megatrend of synthetic materials, development of new, environmental protection, halogen-free flame retardants that is efficient, malicious without (low), nothing (low) cigarette have become the key content of the fire-retardant research of macromolecular material.Wherein, P-N type fire retardant, based on the collaborative and synergism between phosphorus-nitrogen, demonstrates good flame retardant properties, becomes one of study hotspot in recent years.The features such as P-N type fire retardant--it is high that melamine polyphosphate has heat decomposition temperature as important, and water-soluble low, the amount of being fuming is little, and Poisonous Gas is few.Phosphorus is a kind of valence variation element, and almost the compound of its all valence state is all successfully applied to flame retardant area, as alkyl phosphine oxide, the red phosphorus of 0 valence state, the phosphinates of+1 valence state, the phosphorous acid ester of+3 valence states, the phosphoric acid ester of+5 valence states of-1 valency.The subject range of phosphorus flame retardant is very wide, from the thermoplastic resin of the general-purpose plastics such as polyolefine, polyester, polymeric amide, polyethers and engineering plastics class, to the thermosetting resin such as epoxy resin, urethane, all has good application.
The Molecular Structure Design principle of New Phosphorus of the present invention, nitrogenated flame retardant is substantially based on expansion type flame retardant (IFR) the onset principle of acid source, source of the gas, charcoal source " trinity ".
Current fire retardant mainly comprises inorganic combustion inhibitor and organic fire-retardant.Inorganic combustion inhibitor mainly contains aluminium hydroxide (ATH), magnesium hydroxide (MDH), red phosphorus, antimonous oxide, zinc borate etc.ATH and MDH addition is comparatively large, and the physical and mechanical properties of deteriorated material, has process for treating surface and nanotechnology to be improved at present.Red phosphorus limits use range because of its color.Other do not account for main flow as auxiliary flame retardant and smoke suppressant composition.The mainstream product of organic fire-retardant is halogenated flame retardant, especially bromide fire retardant, has good fire-retardant cost performance, and is the fire retardant kind that consumption is maximum in the market, but the dispute of its environmental protection and wholesomeness limits it uses further.Phosphorus type flame retardant phosphorus content is high, has high flame retardant, few additive, the feature little to finished product material properties affect.It has fire-retardant with plasticising dual-use function, can make fire retardant realize completely non-halogen, improve flow processability energy in plastic shaping and reduce ablation, improve heat aging performance, improve heat-drawn wire, and the resistates after burning can be suppressed, be a kind of fire retardant of environment-friendly type.Phosphorus flame retardant is current most study; a kind of fire retardant that technology is comparatively advanced; possess unique fire-retardant mechanism and Halogen, low cigarette, low toxicity characteristic; meet the requirement that current people preserve the ecological environment, especially become the fire retardant mechanism and product line of comparatively praising highly at present with its Intumscent Flame Retardant System being core group/mono-.Expandable flame retardant system forms fine and close porous foam layer of charcoal when burning in material surface because of the synergy of its acid source, charcoal source, source of the gas " three sources ", both the further degraded of internal layer superpolymer and combustiblematerials can have been stoped to the release on surface, thermal source can be stoped again to the transmission of superpolymer and isolated oxygen source, thus stop spreading and propagating of flame.Compared with traditional halogenated flame retardant, this flame retardant systems greatly reduces generation that is poisonous and corrosive gases in combustion, is thus subject to the consistent high praise on fire-retardant boundary, is the main flow of fire retardant material development from now on.
The application of rare earth element in fire retardant.
The outer shell structure of rare earth element uniqueness, demonstrates not only abundant but also unique physics-chemical property, also determines its compound and have much peculiar function, and this is the basis of rare-earth additive application.
At present, the additive agent field of rare earth element successful Application have be applied to combine with calcium zinc and rare earth in PVC thermo-stabilizer, be applied to the beta crystal-type nucleater forming binuclear complex in PP with rare earth multicomponent complex compound or rare earth and the IIth A race metal.And in flame retardant area, rare earth organic phosphine (phosphorus) the hydrochlorate structure founded in CN101475706, can be applicable in electronic material, strongthener.
Summary of the invention
An object of the present invention is to propose a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt, and its synthesis technique is simple, and physical and chemical performance is stablized, and flame-retarded efficiency is high.
A kind of trimeric cyanamide polyphosphoric acid rare earth metal salt that the present invention relates to, it is characterized in that, the structural formula of such rare earth metal salt is shown below:
Wherein, M system group of the lanthanides light rare earths can be the lanthanide series rare-earth elements such as lanthanum (La), cerium (Ce), scandium (Sc), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb);
N
1be be more than or equal to 2 integer;
N
2for integer 1,2 or 3.
In trimeric cyanamide polyphosphoric acid rare earth metal salt as above, it is characterized in that, described M rare earth element comprises the lanthanide series rare-earth elements such as lanthanum (La), cerium (Ce), scandium (Sc), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), preferred lanthanum, cerium, praseodymium, neodymium.
Another object of the present invention is to the preparation method proposing trimeric cyanamide polyphosphoric acid rare earth metal salt, its technique is simple, and be convenient to control, and cheaper starting materials is easy to get, equipment is simple, with low cost, is easy to large-scale production.
The preparation method of trimeric cyanamide polyphosphoric acid rare earth metal salt as above, is characterized in that, this preparation method comprises solution method and calcination method two kinds of methods.
In the solution method preparation method of trimeric cyanamide polyphosphoric acid rare earth metal salt as above, be specially:
At 80 DEG C-100 DEG C, be 1:2.1:(0.35-0.65 according to mol ratio) trisodium phosphate, trimeric cyanamide and rare earth compound are reacted 2.0h-3.5h, vacuum filtration, distilled water wash in water, dry trimeric cyanamide polyphosphoric acid rare earth metal salt.
Further, the method is specially:
Be that 2.1:0.35-0.65 is soluble in water by trimeric cyanamide and rare earth compound according to mol ratio, with hydrochloric acid, the pH value of its aqueous solution is adjusted to 5-6, after being slowly warming up to 80 DEG C-100 DEG C stirring 0.5h-1h, add trisodium phosphate, continue to stir 0.5-1.0h, the pH value of solution is adjusted to 2-4 by second time hydrochloric acid, 1.0h-1.5h is reacted at 80 DEG C-100 DEG C, vacuum filtration, distilled water wash, dry trimeric cyanamide polyphosphoric acid rare earth metal salt.
In the calcination method preparation method of trimeric cyanamide polyphosphoric acid rare earth metal salt as above, be specially:
With trimeric cyanamide and phosphoric acid for raw material, be 1:(1.0-1.2 according to mol ratio) soluble in water, at 80 DEG C-100 DEG C, react 1h-2h, vacuum filtration, distilled water wash, dry melamine phosphate; Again above-mentioned melamine phosphate and rare earth compound are mixed in distilled water according to certain mol proportion and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.5h-4.0h at 280 DEG C-320 DEG C, obtain trimeric cyanamide polyphosphoric acid rare earth metal salt.
The method also can be specially:
With trimeric cyanamide and phosphoric acid for raw material, be 1:(1.0-1.2 according to mol ratio) soluble in water, at 80 DEG C-100 DEG C, react 0.5h-2h, vacuum filtration, distilled water wash, dry melamine phosphate; Melamine phosphate is inserted in retort furnace and calcine 0.5h-1.0h at 280 DEG C-320 DEG C, obtain melamine polyphosphate, melamine polyphosphate and rare earth compound are mixed in distilled water according to certain mol proportion and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.0h-3.0h at 280 DEG C-320 DEG C, obtain trimeric cyanamide polyphosphoric acid rare earth metal salt.
The rare earth compound described in preparation method of trimeric cyanamide polyphosphoric acid rare earth metal salt as above is rare earth oxide, rare earth chloride or rare-earth hydroxide, preferred rare earth oxide.
Trimeric cyanamide polyphosphoric acid rare earth metal salt of the present invention is powder solid, and productive rate is 82%-91%, can be used as polyester, polyamide-based, containing the retardant applications of the macromolecular materials such as epoxy resins.This trimeric cyanamide polyphosphoric acid rare earth metal salt obtains structural formula and is:
Wherein, M system group of the lanthanides light rare earths can be the lanthanide series rare-earth elements such as lanthanum (La), cerium (Ce), scandium (Sc), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb);
N
1be be more than or equal to 2 integer;
N
2for integer 1,2 or 3.
Beneficial effect of the present invention is:
1) trimeric cyanamide polyphosphoric acid rare earth metal salt of the present invention is a kind of rare-earth phosphorate salt structure, has structure innovation;
2) trimeric cyanamide polyphosphoric acid rare earth metal salt synthesis technique of the present invention is simple, and physical and chemical performance is stablized, and flame-retarded efficiency is high;
3) trimeric cyanamide polyphosphoric acid rare earth metal salt of the present invention is not halogen-containing, and environmental protection is nontoxic, "dead", and safety, has vast application prospect;
4) the present invention designs the trimeric cyanamide polyphosphoric acid rare earth metal salt obtained and contains thulium, due to valence shell structure and the physicochemical property of thulium uniqueness, can centered by thulium, effective expansion polymer segment, compare simple trimeric cyanamide Diphosphonate and melamine polyphosphate, the carbon yield after thermostability and burning can be promoted, then in conjunction with phosphorus, phosphorus-nitrogen coordinated fire-retardant, improve its flame retardant resistance further.
5) preparation method of trimeric cyanamide polyphosphoric acid rare earth metal salt that the present invention is designed into comprises solution method and calcination method two kinds of methods, another facility that thulium brings just is a simplified the synthetic method centered by salify, compare formation ammonium salt, difficulty reduces, and has impelled the easy generative nature of product; Whole synthesis technique simply easily controls, environmental protection, and equipment is simple, and the enterprise that is used in low cost carries out large-scale production.
Embodiment
Trimeric cyanamide polyphosphoric acid rare earth metal salt of the present invention, give full play to Heat stability is good, phosphorus content high, become the double effects that charcoal catalytic efficiency is high, rare earth coordination bonding improves consistency and fire-retardant synergistic, can be applicable in Intumescent Retardant System.
In following embodiment, method therefor is ordinary method if no special instructions.
Embodiment 1 trimeric cyanamide polyphosphoric acid lanthanum salt
12.5g trimeric cyanamide and 9.9g lanthanum trioxide are joined and fills 300ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 80 DEG C are slowly warmed up under stirring, drip 4.6g hydrochloric acid (37%wt) in flask, record solution ph about 6.0, after stirring 1.0h, add 22.2g trisodium phosphate, react 1h at 80 DEG C after, second time drips 16.5g hydrochloric acid (37%wt) in flask, record solution ph about 2.0, continue reaction 1.0h, be cooled to room temperature, filter, centrifugal, neutrality is washed to distilled water, dry trimeric cyanamide polyphosphoric acid lanthanum salt, productive rate is 83%.Through ultimate analysis, lanthanum element content is 13.5%.
Embodiment 2 trimeric cyanamide polyphosphoric acid cerium salt
12.5g trimeric cyanamide and 9.7g Cerium II Chloride are joined and fills 300ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 90 DEG C are slowly warmed up under stirring, drip 4.8g hydrochloric acid (37%wt) in flask, record solution ph about 5.0, after stirring 0.5h, add 22.2g trisodium phosphate, react 0.5h at 90 DEG C after, second time drips 16.5g hydrochloric acid (37%wt) in flask, record solution ph about 2.0, continue reaction 1.5h, be cooled to room temperature, filter, centrifugal, neutrality is washed to distilled water, dry trimeric cyanamide polyphosphoric acid cerium salt, productive rate is 85%.Through ultimate analysis, Ce elements content is 13.4%.
Embodiment 3 trimeric cyanamide polyphosphoric acid praseodymium salt
12.5g trimeric cyanamide and 5.9g praseodymium hydroxide are joined and fills 300ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 90 DEG C are slowly warmed up under stirring, drip 4.6g hydrochloric acid (37%wt) in flask, record solution ph about 6.0, after stirring 0.5h, add 22.2g trisodium phosphate, react 0.5h at 90 DEG C after, second time drips 16.3g hydrochloric acid (37%wt) in flask, record solution ph about 3.0, continue reaction 1.5h, be cooled to room temperature, filter, centrifugal, neutrality is washed to distilled water, dry trimeric cyanamide polyphosphoric acid praseodymium salt, productive rate is 86%.Through ultimate analysis, praseodymium constituent content is 13.0%.
Embodiment 4 trimeric cyanamide polyphosphoric acid neodymium salt
12.5g trimeric cyanamide and 10.1g Neodymium trioxide are joined and fills 300ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 100 DEG C are slowly warmed up under stirring, drip 4.8g hydrochloric acid (37%wt) in flask, record solution ph about 5.0, after stirring 1.0h, add 22.2g trisodium phosphate, react 0.5h at 100 DEG C after, second time drips 16.3g hydrochloric acid (37%wt) in flask, record solution ph about 4.0, continue reaction 1.0h, be cooled to room temperature, filter, centrifugal, neutrality is washed to distilled water, dry trimeric cyanamide polyphosphoric acid neodymium salt, productive rate is 82%.Through ultimate analysis, neodymium element content is 13.6%.
Embodiment 5 trimeric cyanamide polyphosphoric acid lanthanum salt
10g trimeric cyanamide is joined and fills 200ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 80 DEG C are slowly warmed up under stirring, slow dropping 9.6g phosphoric acid (85%wt), after being added dropwise to complete, 2.0h is reacted at 80 DEG C, filter, with distilled water wash 2-3 time, dry melamine phosphate, 10g melamine phosphate and 2.4g lanthanum trioxide are joined stirred at ambient temperature 0.5h in the 500ml beaker filling 200ml distilled water, filtration drying, goods are inserted in retort furnace and calcine 4.0h at 280 DEG C, obtain trimeric cyanamide polyphosphoric acid lanthanum salt, productive rate is 87%.Through ultimate analysis, lanthanum element content is 6.4%.
Embodiment 6 trimeric cyanamide polyphosphoric acid cerium salt
10g trimeric cyanamide is joined and fills 200ml distilled water, in the 500ml four-hole boiling flask of stirring rod and thermometer, 100 DEG C are slowly warmed up under stirring, slow dropping 9.0g phosphoric acid (85%wt), after being added dropwise to complete, 1.0h is reacted at 100 DEG C, filter, with distilled water wash 2-3 time, dry melamine phosphate, 10g melamine phosphate and 1.3g cerium oxide are joined stirred at ambient temperature 0.5h in the 500ml beaker filling 200ml distilled water, filtration drying, goods are inserted in retort furnace and calcine 2.5h at 320 DEG C, obtain trimeric cyanamide polyphosphoric acid cerium salt, productive rate is 85%.Through ultimate analysis, Ce elements content is 5.8%.
Embodiment 7 trimeric cyanamide polyphosphoric acid lanthanum salt
1) 10g trimeric cyanamide is joined fill in the 500ml four-hole boiling flask of 200ml distilled water, stirring rod and thermometer, 80 DEG C are slowly warmed up under stirring, slow dropping 9.0g phosphoric acid (85%wt), after being added dropwise to complete, 2.0h is reacted at 80 DEG C, filter, with distilled water wash 2-3 time, dry must melamine phosphate.
2) 10g melamine phosphate is placed in retort furnace and calcines 1.0h at 280 DEG C, obtain melamine polyphosphate, 10g melamine polyphosphate and 1.1g lanthanum trioxide are mixed in distilled water and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 3.0h at 280 DEG C, obtain trimeric cyanamide polyphosphoric acid lanthanum salt, productive rate is 89%.Through ultimate analysis, lanthanum element content is 4.8%.
Embodiment 8 trimeric cyanamide polyphosphoric acid cerium salt
1) 10g trimeric cyanamide is joined fill in the 500ml four-hole boiling flask of 200ml distilled water, stirring rod and thermometer, 80 DEG C are slowly warmed up under stirring, slow dropping 9.6g phosphoric acid (85%wt), after being added dropwise to complete, 0.5h is reacted at 85 DEG C, filter, with distilled water wash 2-3 time, dry must melamine phosphate.
2) 10g melamine phosphate is placed in retort furnace and calcines 0.5h at 320 DEG C, obtain melamine polyphosphate, 10g melamine polyphosphate and 0.7g cerium oxide are mixed in distilled water and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.0h at 320 DEG C, obtain trimeric cyanamide polyphosphoric acid cerium salt, productive rate is 90%.Through ultimate analysis, Ce elements content is 4.5%.
Embodiment 9 trimeric cyanamide polyphosphoric acid praseodymium salt
1) 10g trimeric cyanamide is joined fill in the 500ml four-hole boiling flask of 200ml distilled water, stirring rod and thermometer, 95 DEG C are slowly warmed up under stirring, slow dropping 10g phosphoric acid (85%wt), after being added dropwise to complete, 2h is reacted at 90 DEG C, filter, with distilled water wash 2-3 time, dry must melamine phosphate.
2) 10g melamine phosphate is placed in retort furnace and calcines 0.5h at 300 DEG C, obtain melamine polyphosphate, 10g melamine polyphosphate and 0.7g praseodymium hydroxide are mixed in distilled water and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.0h at 300 DEG C, obtain trimeric cyanamide polyphosphoric acid praseodymium salt, productive rate is 88%.Through ultimate analysis, praseodymium constituent content is 4.4%.
Embodiment 10 trimeric cyanamide polyphosphoric acid neodymium salt
1) 10g trimeric cyanamide is joined fill in the 500ml four-hole boiling flask of 200ml distilled water, stirring rod and thermometer, 100 DEG C are slowly warmed up under stirring, slow dropping 10.8g phosphoric acid (85%wt), after being added dropwise to complete, 0.5h is reacted at 100 DEG C, filter, with distilled water wash 2-3 time, dry must melamine phosphate.
2) 10g melamine phosphate is placed in retort furnace and calcines 1.0h at 280 DEG C, obtain melamine polyphosphate, 10g melamine polyphosphate and 1.2g Neodymium trioxide are mixed in distilled water and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 3.0h at 280 DEG C, obtain trimeric cyanamide polyphosphoric acid neodymium salt, productive rate is 91%.Through ultimate analysis, neodymium element content is 4.1%.
The preparation of embodiment 11 fire retardant and effect detection
By above-described embodiment 1 ~ 10 synthesize trimeric cyanamide polyphosphoric acid rare earth metal salt be crushed to 3000 orders and more than, the amount of 6 ~ 20wt% adds polyolefine (PE by mass percentage, PP etc.) or dry after engineering plastics (PA, PET, PBT etc.) in, wherein add mass percent 1 ~ 8wt% auxiliary flame retardant, as antimonous oxide, zinc borate etc., with polyolefine (PE in homogenizer, PP etc.) or dry after engineering plastics (PA, PET, PBT etc.) mixing at normal temperature to 100 DEG C, then compound is joined twin screw extruder to extrude, it is 170 ~ 220 DEG C (polyolefine) that extrusion temperature controls, or 210 ~ 270 DEG C (engineering plastics), plastics are injection molded into again through injection moulding machine, temperature is 170 ~ 220 DEG C (polyolefine), or 210 ~ 270 DEG C (engineering plastics).
With commercial solid phosphorus flame retardant be comparative example, embodiment 1 ~ 10 synthesize trimeric cyanamide polyphosphoric acid rare earth metal salt respectively with 14% addition, with 1% zinc borate, the MPP of 5%, add in PBT resin (maleic anhydride grafted polyethylene containing 3%), plastics after shaping by ANST/UL94, ASTMD2863, ASTMD2843 standard, 600 DEG C time carbon yield carry out performance test, result is see table 1.Carry out thermal weight loss test to comparative example and 1 ~ 10 embodiment, result is see table 2 simultaneously.
The flame retardant effect of table 1 phosphoric acid ester rare-earth salts flame retardant Example
Table 2 phosphoric acid ester rare-earth salts fire retardant thermal weight loss test result
Table 1 data presentation, trimeric cyanamide polyphosphoric acid rare earth metal salt fire retardant of the present invention can reach UL94 vertical combustion standard and relevant oxygen index, smoke density standard.
Illustrate that trimeric cyanamide polyphosphoric acid rare earth metal salt of the present invention is plastic working temperature stability inferior high (thermal weight loss temperature is higher), and phosphorus content is higher, catalysis carbon-forming effect better (when 600 DEG C, carbon yield is higher), there is low toxicity, low smog (smoke density index meets ASTMD2843 standard), the feature that innoxious, highly effective flame-retardant presses down cigarette.
Claims (8)
1. a trimeric cyanamide polyphosphoric acid rare earth metal salt, is characterized in that, the structural formula of such rare earth metal salt is shown below:
Wherein, M system group of the lanthanides light rare earths, n
1be be more than or equal to 2 integer;
N
2for integer 1,2 or 3.
2. according to a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1, it is characterized in that, M is lanthanum (La), cerium (Ce), scandium (Sc), yttrium (Y), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm) or ytterbium (Yb).
3. prepare the method for a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1, it is characterized in that, comprise the following steps: at 80 DEG C-100 DEG C, be 1:2.1:(0.35-0.65 according to mol ratio) sodium pyrophosphate, trimeric cyanamide and rare earth compound are reacted 2.0h-3.5h in water, vacuum filtration, distilled water wash, dry trimeric cyanamide polyphosphoric acid rare earth metal salt, rare earth compound is rare earth oxide, rare earth chloride or rare-earth hydroxide.
4. according to the method for claim 3, it is characterized in that, be specially: be that 2.1:0.35-0.65 is soluble in water by trimeric cyanamide and rare earth compound according to mol ratio, with hydrochloric acid, the pH value of its aqueous solution is adjusted to 5-6, after being slowly warming up to 80 DEG C-100 DEG C stirring 0.5h-1h, add sodium pyrophosphate, continue to stir 0.5-1.0h, the pH value of solution is adjusted to 2-4 by second time hydrochloric acid, 1.0h-1.5h is reacted at 80 DEG C-100 DEG C, vacuum filtration, distilled water wash, dry trimeric cyanamide polyphosphoric acid rare earth metal salt.
5. prepare the method for a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1, it is characterized in that, comprise the following steps: with trimeric cyanamide and phosphoric acid for raw material, be 1:(1.0-1.2 according to mol ratio) soluble in water, 1h-2h is reacted at 80 DEG C-100 DEG C, vacuum filtration, distilled water wash, dry melamine phosphate; Again melamine phosphate and rare earth compound are mixed in distilled water according to certain mol proportion and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.5h-4.0h at 280 DEG C-320 DEG C, obtain trimeric cyanamide polyphosphoric acid rare earth metal salt.
6. prepare the method for a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1, it is characterized in that: with trimeric cyanamide and phosphoric acid for raw material, be 1:(1.0-1.2 according to mol ratio) soluble in water, 0.5h-2h is reacted at 80 DEG C-100 DEG C, vacuum filtration, distilled water wash, dry melamine phosphate; Melamine phosphate is inserted in retort furnace and calcine 0.5h-1.0h at 280 DEG C-320 DEG C, obtain melamine polyphosphate, melamine polyphosphate and rare earth compound are mixed in distilled water according to certain mol proportion and stir 0.5h at normal temperatures, after suction filtration drying, powder is placed in retort furnace and calcines 2.0h-3.0h at 280 DEG C-320 DEG C, obtain trimeric cyanamide polyphosphoric acid rare earth metal salt.
7. the fire-retardant application in fire retardant of a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1.
8. the fire-retardant application in fire retardant of a kind of trimeric cyanamide polyphosphoric acid rare earth metal salt of claim 1, it is characterized in that, trimeric cyanamide polyphosphoric acid rare earth metal salt is crushed to 3000 orders and more than, the amount of 6 ~ 20wt% adds in polyolefine or the engineering plastics after drying by mass percentage, add mass percent 1 ~ 8wt% auxiliary flame retardant, mix at normal temperature to 100 DEG C with polyolefine or the engineering plastics after drying in homogenizer, then compound is joined twin screw extruder to extrude, it is 170 ~ 220 DEG C that extrusion temperature controls polyolefine, or engineering plastics are 210 ~ 270 DEG C, plastics are injection molded into again through injection moulding machine, polyolefin temperature is 170 ~ 220 DEG C, engineering plastics or 210 ~ 270 DEG C.
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| CN114181431B (en) * | 2021-12-21 | 2023-08-15 | 包头稀土研究院 | Flame retardant, preparation method and application thereof and polyolefin composition |
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