CN108264720A - It is a kind of without be precipitated halogen-free flame-retardant composition - Google Patents

It is a kind of without be precipitated halogen-free flame-retardant composition Download PDF

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CN108264720A
CN108264720A CN201711474672.6A CN201711474672A CN108264720A CN 108264720 A CN108264720 A CN 108264720A CN 201711474672 A CN201711474672 A CN 201711474672A CN 108264720 A CN108264720 A CN 108264720A
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acid
halogen
flame
dcd
pan
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CN108264720B (en
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彭治汉
高燕
顾湘明
彭治权
何小春
彭斌
李永林
义芝兴
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Shanghai Li Dao new material Polytron Technologies Inc
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SHANGHAI MEILAIPO CHEMICALS CO Ltd
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Abstract

Of the present invention a kind of without halogen-free flame-retardant composition is precipitated, each component and its mass content are as follows：Piperazine inorganic acid salt is 30~80%；PAN DCD and/or FB are 15~55%；Metal oxide and/or metal salt are 5~10%；Organosilicon material is 0~5%；The structural formula of PAN DCD is as follows：The structural formula of FB is as follows：In formula, w is integer more than or equal to 10, and k, m, n, p and q are the integer more than or equal to 1, A‑The ion formed after proton is provided for metal oxygen-containing acid, content is the polypropylene flame redardant product comprising the composition of 28wt%, and after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.The composition of the present invention have the characteristics that thermal stability is good, flame retarding efficiency is high, with polymer compatibility it is good, into charcoal and excellent combination property, environmentally protective production can be realized, with fabulous promotional value.

Description

It is a kind of without be precipitated halogen-free flame-retardant composition
Technical field
The invention belongs to fire retardant preparation fields, are related to a kind of without precipitation halogen-free flame-retardant composition.
Background technology
In recent years, high molecular material is convenient due to having the characteristics that excellent combination property and machine-shaping, and extensive Applied in the every field of national economy and people's daily life.However most high molecular materials easily burn, and It can be along with the generation of toxic and harmful gas, therefore there are serious fire hazard, in such circumstances, to height in the process of burning Molecular material carries out flame-retardant modified be particularly important.Flame retarded polymeric material is mainly fire-retardant by adding fire retardant realization at present Function, since the 1980s, various countries increase the exploitation to halogen-free flame retardants, and wherein halogen-free expansion fire retardant is exactly One of countermeasure of solution.Halogen-free intumescent flame retardant include acid source (catalysis carbon-forming effect), air source (foaming) and carbon source (into Charcoal) three elements, at high temperature, expansion type flame retardant can form fine and close foaming and intumescing layer of charcoal in polymer surface, can With starvation and heat, and raw smoke is few, does not generate toxic and harmful gas, flame retardant effect is good, therefore such Fire retardant is by more and more extensive concern.
Melamine can regard as on triazine ring there are one amino the triazine containing diamino polymer, melamine And its salt can be used as fire proofing.Melamine salt fire retardant mainly has melamine cyanurate, melamine phosphate, three Poly cyanamid pyrophosphoric acid, melamine polyphosphate, melamine borate salt, melamine phthalate, melamine grass Hydrochlorate, Tripolycyanamide hydrobromide and melamine hypophosphite etc., the derivative of these melamines are respectively suitable for difference Polymer it is flame-retardant modified, flame retardant effect can also have differences.Due to melamine and its esters fire retardant and traditional halogen system Fire retardant is compared, and is had that smoke density is low, toxicity is low, corrosivity is small, colorability is good and the characteristics such as superior electrical property and is met The a series of advantage such as environmental requirement, affordable, it is increasing in the application of flame retardant area.But the based flame retardant is causes Close, hardness is big agglomerated particle structure and be difficult in resin effectively disperse, lead to the flame retardant property or mechanical property of fire proofing The defects of declining, and most of salts have certain solubility and hygroscopicity, especially with the raising of temperature, dissolving Degree incrementally increases.Such as melamine cyanurate (MCA) is the melamine salt fire retardant of current dosage maximum, but it exists The problems such as poor dispersion and flame retarding efficiency in fire-retardant nylon or polyolefin are unstable；And melamine phosphate (MP) Not only solubility is larger (0.54 gram/100 grams water), and low to the flame retarding efficiency of the polymer such as nylon.Therefore, it also needs further New and effective melamine based flame retardant is developed, melamine class fire retardant efficiency is low, solubility is high easily to solve Be precipitated and with polymer compatibility it is poor the problems such as.
Other than melamine, the compound in relation to containing diamino triazine group is seldom as the report of fire retardant. Patent report application No. is 201110194940.5 is using Benzoguanamine propyloic phenyl phosphinic acid condensation compound as raw material Composition with other synergistic flame retardants compounding as fire retardant, benzoguanamine can regard as on triazine ring there are one benzene The polymer of the triazine containing diamino of base.But after condensation reaction occurs due to benzoguanamine and carboxyethyl phenyl phosphinic acid, The foaming effect of imide and phosphorimide base on its strand can be substantially reduced, so the fire retardant is in halogen-free flame-retardant Charcoal effect is mainly played into system.
Polyacrylonitrile reacts the product of synthesis with dicyandiamide due to frequent containing acid and basic group simultaneously in molecule It is used as high polymer coagulant, is widely used in field of waste water treatment.(the Reaction Products of Poly of document 1 acrylonitrle with Dicyandiamide.Die Angewandte makromolekulare Chemie,1986, 141:It is that one kind contains diamino triazine, amide groups, carboxylic acid that the product that polyacrylonitrile is reacted with dicyandiamide is reported in 57-67) The mixture of base and amidine structure；Document 2 (is used for novel flocculant-polyacrylonitrile of dye wastewater treatment and reacting for dicyandiamide Product chemistry worlds, 1992,3:The reaction product that polyacrylonitrile and dicyandiamide are reported in 119-123) is used as flocculant, according to It reports, is polyacrylonitrile and dicyandiamide reaction product used in the flocculant, be that one kind contains diamino triazine radical, cyanoguanidines There are acid and basic group Ampholyte polymers again simultaneously in the structures such as vinyl, amide groups and carboxylic acid group；Document 3 (PAN-DCD studies Environmental Chemistries .1995,14 (6) for the decoloration of waste water from dyestuff:It is reported in 531-536) using document 1 Method react the product of synthesis with dicyandiamide with industrial polyacrylonitrile and is used as decoloring dye waste water inorganic agent, but without reporting conjunction Into the concrete structure of compound；Document 4 (intermolecular interaction of decolorising agent and reactive dye, journal (natural section of Nankai University Learn version .1999,32 (3):The synthetic method according to document 1 is reported in 140-145) using industrial polypropylene nitrile as raw material and double cyanogen The product of amine reaction synthesis is used as dye decolored dose, and author reports what synthesized product was reported with document 1 in the publication Structure is similar, is the mixture containing a variety of groups such as cyano, diamino triazine, amide groups, carboxylic acid group and amidine structures.Due to The mixture that the product that upper polyacrylonitrile reported in the literature is reacted with dicyandiamide is all made of various structures group, each The content ratio of group is difficult to measure.Described in comprehensive literature, polyacrylonitrile is useful for flocculant at present with dicyandiamide reaction product And waste water treating agent, there are no as the report for preparing fire retardant.
Therefore, it is high without precipitation halogen-free flame-retardant composition to study a kind of and flame retardant effect good with polymer compatibility It has a very important significance.
Invention content
Good the purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of compatibility, flame retardant effect is excellent Without precipitation halogen-free flame-retardant composition.Contain the product prepared using polyacrylonitrile and dicyandiamide as raw material in the present composition PAN-DCD and/or FB fire retardants.Wherein, the thermal stability of PAN-DCD, compatibility are good.FB fire retardants are with PAN-DCD and metal Oxyacid is raw material, and reaction under certain condition is made, and metal oxygen-containing acid is reacting same with the amino in PAN-DCD molecules When, metal oxygen-containing acid ion structure division can be with the diamino triazine in same PAN-DCD molecules and amidine building stone shape Into coordination structure, on the one hand the formation of this coordination structure can induce the cyclic annular knot as shown in formula (B) in PAN-DCD molecules Rapidly into charcoal, another aspect metal oxygen-containing acid ion quicklys promote simultaneously to be carbonized or and PAN-DCD structure by fire-retardant organic matrix Strand crosslinks charing, and gasification expansion, fire retardant, matrix and metal occur at this time for the amino of PAN-DCD intramoleculars The synergistic effect of ligand three substantially increases flame retarding efficiency, therefore there is fire retardant combination obtained excellent expansion to hinder Fire performance and into charcoal, flame retarding efficiency is high, while the presence of macromolecular and metal ligand structure also substantially increases fire retardant Thermal stability.The structural formula of amidine structure, diamino triazine radical and formula (B) wherein in PAN-DCD molecules is specific as follows：
Amidine structure：
Diamino triazine radical：
Formula (B)：
The fire retardant combination of gained of the invention is a kind of novel environment friendly without halogen-free flame-retardant composition, and molecule is precipitated There is into the metal oxygen-containing acid group of charcoal group, induction and catalysis carbon-forming structure and the air source (amino) of foaming simultaneously in structure, because This have the characteristics that thermal stability is good, flame retarding efficiency is high, with polymer compatibility it is good, into charcoal and excellent combination property, can be wide It is general flame-retardant modified for resin, plastics, rubber, paper, coating, fiber and its formed body etc..
In order to achieve the above object, the technical solution adopted by the present invention is：
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
The structural formula of PAN-DCD is as follows：
In formula, w is integer more than or equal to 10, and k, m, n, p and q are the integer more than or equal to 1, A-For metal oxygen-containing Acid provides the ion formed after proton；
Content is the polypropylene flame redardant product comprising the composition of 28wt%, after 70 DEG C of pure water impregnate 168 hours, Surface occurs without white precipitate.
As preferred technical solution：
It is as described above a kind of without being precipitated halogen-free flame-retardant composition, it is described without halogen-free flame-retardant composition is precipitated Better heat stability, initial decomposition temperature is good into charcoal more than 275 DEG C, and be more than 70% in 600 DEG C of charring rates (is lost using heat Weight analysis, platinum crucible load sample, air atmosphere, 10 DEG C/min of heating rate), it is good with the compatibility of polyolefin, content for 25~ The polypropylene flame redardant or polyethylene products comprising the composition of 35wt% heats 500 hours surfaces in 100 DEG C of convection ovens No precipitate occurs.
As described above a kind of without precipitation halogen-free flame-retardant composition, the preparation method of the FB is：By PAN-DCD, Metal oxygen-containing acid and solvent after mixing, 2~16h are reacted at 30~150 DEG C, obtained through cooling down, washing, detaching and drying FB。
It is as described above a kind of without being precipitated halogen-free flame-retardant composition, the PAN-DCD, metal oxygen-containing acid and solvent Mass ratio is 1:0.05~10.0:5~100.
It is as described above a kind of without halogen-free flame-retardant composition is precipitated, the metal oxygen-containing acid is tungstenic, molybdenum, titanium, tin, The inorganic acid of antimony or vanadium or the heteropoly acid for tungstenic, molybdenum, titanium, tin, antimony or vanadium.
It is as described above a kind of without being precipitated halogen-free flame-retardant composition, the tungstenic, molybdenum, titanium, tin, antimony or vanadium it is inorganic Acid is wolframic acid, molybdic acid, metatitanic acid, stannic acid, metaantimmonic acid or vanadic acid；The tungstenic, molybdenum, titanium, tin, antimony or vanadium heteropoly acid be phosphomolybdic acid, Silicomolybdic acid, titanium molybdic acid, zirconium molybdic acid, tin molybdic acid, antimony molybdic acid, nickel molybdic acid, phosphorus molybdenum vanadium heteropolyacid, phosphotungstic acid, silico-tungstic acid, borotungstic acid, Titanium tungsten acid, nickel wolframic acid, antimony wolframic acid, platinum wolframic acid or phosphorus tungsten vanadium heteropoly acid.
As described above a kind of without halogen-free flame-retardant composition is precipitated, the solvent is water, methanol, ethyl alcohol, propyl alcohol, just Butanol, isobutanol, n-amyl alcohol, cyclohexanol, acetone, cyclohexanone, methyl iso-butyl ketone (MIBK), N,N-dimethylformamide, N, N- diformazans One or more of yl acetamide and dimethyl sulfoxide (DMSO).
As described above a kind of without halogen-free flame-retardant composition is precipitated, the piperazine inorganic acid salt is piperazine phosphate, coke In piperazine phosphate, polyphosphoric acid piperazine, piperazine borate, piperazine silicotungstate, piperazine zinc stannate complex salt and piperazine phosphotungstate More than one.
It is as described above a kind of without halogen-free flame-retardant composition is precipitated, the metal oxide is magnesia, zinc oxide, One or more of titanium dioxide, silica, stannic oxide and antimony oxide；The metal salt for magnesium silicate, alumina silicate, One or more of zinc borate, zinc stannate, sodium antimonate, lithium titanate, calcium titanate, magnesium titanate and barium titanate；The organosilicon material Material refers to that (DOW CORNING liquid silastic FL60-9201 and FL65-9001 step figure for silane coupling agent, silicone oil, liquid silastic One or more of silica gel TSE399, TN30851 and TIA207GN of Momentive companies).
It is as described above a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the silane coupling agent leads to Formula is RSiX3, R is amino, sulfydryl, vinyl, epoxy group, cyano or methacryloxy in formula, and X is methoxyl group or ethoxy Base, product type is KH151, KH171 of Nanjing dawn Chemical Group company, KH172, KH550, KH560, KH570, KH590 or SG-Si6490；The silicone oil is that viscosity is 500 to 5000mm at 25 DEG C2Dimethyl polysiloxane (the DOW CORNING of/s PMX-1000CS and SHIN-ETSU HANTOTAI KH96), methyl hydrogen polysiloxanes (SHIN-ETSU HANTOTAI KF99), amino modified dimethyl polysiloxane (SHIN-ETSU HANTOTAI ) or epoxy-modified dimethyl polysiloxane (SHIN-ETSU HANTOTAI KF102) KF393.
Advantageous effect：
(1) of the invention a kind of without halogen-free flame-retardant composition is precipitated, the FB in component is oxygen-containing due to intermetallic On the one hand the formation of acid ion and amino coordination structure can induce cyclic structure in PAN-DCD molecules rapidly into charcoal, separately One side metal oxygen-containing acid ion quicklys promote simultaneously to be carbonized by fire-retardant organic matrix, and the amino of PAN-DCD intramoleculars this Shi Fasheng gasification expansions, the synergistic effect of fire retardant, matrix and metal ligand three substantially increase flame retarding efficiency, therefore Fire retardant obtained has excellent expandable flame retardant performance and into charcoal, and flame retarding efficiency is high, while macromolecular and metal coordination The presence of structure also substantially increases the thermal stability of entire fire retardant combination；
(2) it is of the invention a kind of without halogen-free flame-retardant composition is precipitated, have simultaneously in the molecular structure of the FB in component Have into charcoal group, induction and a catalysis carbon-forming structure and the air source of foaming (amino), thus by a combination thereof into composition there is heat Stability is good, flame retarding efficiency is high, with polymer compatibility is good, resistance to migration can be excellent, special into charcoal and excellent combination property etc. Point；
(3) present invention's is a kind of without halogen-free flame-retardant composition is precipitated, and raw material is easy to get, meet the requirement of environmental protection.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.
In formula (I) and formula (II), w is integer more than or equal to 10, k, m, n, p and q to be more than or
Integer equal to 1.
Embodiment 1
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine phosphate is 44%；Mixture (the mass ratio 1 of PAN-DCD and FB:1) it is 42%；Magnesia is 10%；Silicon Alkane coupling agent (KH151 of Nanjing dawn Chemical Group company) is 4%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:0.05:5 PAN-DCD, wolframic acid and water after mixing, 30 DEG C of reaction 16h, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD institutes Polyacrylonitrile is that oil of SPC corporation has light acrylic fibers (ternary polymerization propylene for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provided for wolframic acid formed after proton from Son.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 281 DEG C, at 600 DEG C into charcoal Rate is 73%, and the flame-proof polyethylene fire block articles grade comprising 30wt% the compositions is UL94V1 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 2
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine pyrophosphate is 62%；FB is 32%；Zinc oxide is 5%；Silane coupling agent (Nanjing dawn Chemical Group company KH171) be 1%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:0.1:10 PAN-DCD, molybdic acid and methanol after mixing, 15h is reacted at 36 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD Polyacrylonitrile used has light acrylic fibers (ternary polymerization propylene for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provided for molybdic acid formed after proton from Son.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 288 DEG C, at 600 DEG C into charcoal Rate is 78%, and the polypropylene flame redardant fire block articles grade comprising 30wt% the compositions is UL94V0 grades (3.2mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 3
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Polyphosphoric acid piperazine is 50%；FB is 40%；Titanium dioxide is 5%；(Nanjing dawn Chemical Group is public for silane coupling agent The KH172 of department) it is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:1:15 PAN-DCD, metatitanic acid and ethyl alcohol after mixing, 40 DEG C of reaction 14h, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD institutes Polyacrylonitrile is that oil of SPC corporation has light acrylic fibers (ternary polymerization propylene for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provided for metatitanic acid formed after proton from Son.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 280 DEG C, at 600 DEG C into charcoal Rate is 73%, and the fire-retardant EVA fire block articles grade comprising 35wt% the compositions is UL94V1 grades (1.6mm), in 100 DEG C of air blast 500 hours surfaces are heated in baking oven without precipitate to occur.Content is the polypropylene flame redardant product comprising the composition of 28wt%, After 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 4
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine borate is 45%；Mixture (the mass ratio 1 of PAN-DCD and FB:2) it is 45%；Silica is 10%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:1.5:20 PAN-DCD, stannic acid and propyl alcohol after mixing, 13h is reacted at 45 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD Polyacrylonitrile used has light acrylic fibers (ternary polymerization propylene for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provided for stannic acid formed after proton from Son.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 279 DEG C, at 600 DEG C into charcoal Rate is 72%, and the flame-proof ABS fire block articles grade comprising 32wt% the compositions is UL94V0 grades (1.6mm), in 100 DEG C of air blast 500 hours surfaces are heated in baking oven without precipitate to occur.Content is the polypropylene flame redardant product comprising the composition of 28wt%, After 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 5
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine silicotungstate is 37%；Mixture (the mass ratio 2 of PAN-DCD and FB:1) it is 55%；Stannic oxide is 5%；Silane coupling agent (KH560 of Nanjing dawn Chemical Group company) is 3%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:2:25 PAN-DCD, metaantimmonic acid and n-butanol after mixing, 12h is reacted at 52 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD Polyacrylonitrile used has light acrylic fibers (ternary polymerization propylene for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provided for metaantimmonic acid formed after proton from Son.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 285 DEG C, at 600 DEG C into charcoal Rate is 79%, and the flame-proof polyethylene fire block articles grade comprising 35wt% the compositions is UL94V0 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 6
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine zinc stannate complex salt is 36%；FB is 50%；Antimony oxide is 10%；Silane coupling agent (Nanjing dawn The KH570 of Chemical Group company) it is 4%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:2.8:30 PAN-DCD, vanadic acid and isobutanol is uniformly mixed Afterwards, 2h is reacted at 60 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN- Polyacrylonitrile used in DCD has light acrylic fibers (ternary polymerization for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Acrylonitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-It is formed after providing proton for vanadic acid Ion.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 279 DEG C, at 600 DEG C into charcoal Rate is 76%, and the flame-retarding HIPS fire block articles grade comprising 30wt% the compositions is UL94V0 grades (1.6mm), in 100 DEG C of drums 500 hours surfaces are heated in wind baking oven without precipitate to occur.Content is the polypropylene flame redardant system for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 7
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine phosphotungstate is 48%；FB is 42%；The mixture of magnesia and zinc oxide (mass ratio 1:1) it is 8%； Silane coupling agent (KH590 of Nanjing dawn Chemical Group company) is 2%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:3.2:35 PAN-DCD, phosphomolybdic acid and n-amyl alcohol mixing is After even, 3h is reacted at 65 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares Polyacrylonitrile used in PAN-DCD has light acrylic fibers (ternary for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Copolymerized acrylonitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Proton is provided for phosphomolybdic acid The ion formed afterwards.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 290 DEG C, at 600 DEG C into charcoal Rate is 75%, and the flame-proof polyethylene fire block articles grade comprising 30wt% the compositions is UL94V0 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 8
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
The mixture of piperazine phosphate and piperazine pyrophosphate (mass ratio 2:3) it is 65%；The mixture of PAN-DCD and FB (mass ratio 1:2) it is 22%；The mixture of titanium dioxide and silica (mass ratio 1:1) it is 10%；Silane coupling agent (SG-Si6490 of Nanjing dawn Chemical Group company) is 3%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:3.5:40 PAN-DCD, silicomolybdic acid and cyclohexanol mixing is After even, 4h is reacted at 72 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares Polyacrylonitrile used in PAN-DCD has light acrylic fibers (ternary for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Copolymerized acrylonitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Proton is provided for silicomolybdic acid The ion formed afterwards.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 281 DEG C, at 600 DEG C into charcoal Rate is 80%, and the polypropylene flame redardant fire block articles grade comprising 28wt% the compositions is UL94V0 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 9
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Mixture (the mass ratio 1 of polyphosphoric acid piperazine and piperazine borate:3) it is 62%；The mixture of PAN-DCD and FB (mass ratio 1:1) it is 28%；The mixture of stannic oxide and antimony oxide (mass ratio 3:1) it is 5%；DOW CORNING PMX- 1000CS is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:4:45 PAN-DCD, titanium molybdic acid and acetone after mixing, 5h is reacted at 80 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares PAN-DCD Polyacrylonitrile used has light acrylic fibers (ternary polymerization propylene for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Nitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Provide what is formed after proton for titanium molybdic acid Ion.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 283 DEG C, at 600 DEG C into charcoal Rate is 84%, and the flame-proof polyethylene fire block articles grade comprising 32wt% the compositions is UL94V1 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 10
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine silicotungstate and the mixture (mass ratio 2 of piperazine zinc stannate complex salt:1) it is 70%；PAN-DCD and FB Mixture (mass ratio 1:4) it is 15%；Mixture (the mass ratio 1 of magnesia, stannic oxide and antimony oxide:2: 1) it is 10%；SHIN-ETSU HANTOTAI KH96 is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:4.2:55 PAN-DCD, zirconium molybdic acid and cyclohexanone mixing is After even, 6h is reacted at 83 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares Polyacrylonitrile used in PAN-DCD has light acrylic fibers (ternary for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Copolymerized acrylonitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Proton is provided for zirconium molybdic acid The ion formed afterwards.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 288 DEG C, at 600 DEG C into charcoal Rate is 85%, and the fire-retardant exterior-coated nitrile rubber article flame retardant rating comprising 30wt% the compositions is UL94V1 grades (1.6mm), 100 500 hours surfaces are heated in DEG C convection oven without precipitate to occur.Content is the flame-retardant polypropylene for including the composition of 28wt% Alkene product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 11
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Mixture (the mass ratio 1 of piperazine phosphate and piperazine silicotungstate:1) it is 77%；The mixture of PAN-DCD and FB (mass ratio 4:1) it is 15%；Magnesium silicate is 7%；Methyl hydrogen polysiloxanes (SHIN-ETSU HANTOTAI KF99) is 1%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:4.8:60 PAN-DCD, tin molybdic acid and methyl iso-butyl ketone (MIBK) After mixing, 7h is reacted at 90 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), Prepare the polyacrylonitrile used in PAN-DCD has light acrylic fibers for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex The waste silk and bad substandard products of (ternary polymerization acrylonitrile) high shrinkage short fiber；The structural formula of FB is shown in formula (II), A-It is given for tin molybdic acid Go out the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 284 DEG C, at 600 DEG C into charcoal Rate is 79%, and the fire-retardant butadiene-styrene rubber fire block articles grade comprising 35wt% the compositions is UL94V0 grades (1.6mm), 100 500 hours surfaces are heated in DEG C convection oven without precipitate to occur.Content is the flame-retardant polypropylene for including the composition of 28wt% Alkene product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 12
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Mixture (the mass ratio 2 of piperazine phosphate, piperazine pyrophosphate and piperazine phosphotungstate:1:2) it is 66%；FB is 25%；Alumina silicate is 7%；Amino modified dimethyl polysiloxane (SHIN-ETSU HANTOTAI KF393) is 2%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:5:70 PAN-DCD, nickel molybdic acid and N, N- dimethyl formyl Amine reacts 8h after mixing, at 96 DEG C, and through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepare the polyacrylonitrile used in PAN-DCD has light nitrile for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex The waste silk and bad substandard products of synthetic fibre (ternary polymerization acrylonitrile) high shrinkage short fiber；The structural formula of FB is shown in formula (II), A-For nickel molybdic acid Provide the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 286 DEG C, at 600 DEG C into charcoal Rate is 72%, and the fire-retardant SBS fire block articles grade comprising 33wt% the compositions is UL94V0 grades (1.6mm), in 100 DEG C of air blast 500 hours surfaces are heated in baking oven without precipitate to occur.Content is the polypropylene flame redardant product comprising the composition of 28wt%, After 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 13
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine phosphate is 48%；FB is 42%；Zinc borate is that 7% dimethyl polysiloxane (SHIN-ETSU HANTOTAI KF102) is 3%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:5.8:76 PAN-DCD, phosphorus molybdenum vanadium heteropolyacid and N, N- bis- Methylacetamide reacts 9h after mixing, at 102 DEG C, through cooling down, washing, detaching and drying obtained FB, the structure of PAN-DCD Formula is shown in formula (I), and the polyacrylonitrile prepared used in PAN-DCD is oil of SPC corporation for three people's board 3.33dtex and 6.67dtex There are the waste silk of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber and bad substandard products；The structural formula of FB is shown in formula (II), A-For Phosphorus molybdenum vanadium heteropolyacid provides the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 289 DEG C, at 600 DEG C into charcoal Rate is 77%, and the fire-retardant SEBS fire block articles grade comprising 36wt% the compositions is UL94V1 grades (1.6mm), in 100 DEG C of drums 500 hours surfaces are heated in wind baking oven without precipitate to occur.Content is the polypropylene flame redardant system for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 14
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine pyrophosphate is 71%；FB is 20%；Zinc stannate is 8%；Liquid silastic (DOW CORNING liquid silastic FL60-9201 it is) 1%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:6.2:80 PAN-DCD, phosphotungstic acid and dimethyl sulfoxide (DMSO) mixes After closing uniformly, 10h is reacted at 110 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), Prepare the polyacrylonitrile used in PAN-DCD has light acrylic fibers for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex The waste silk and bad substandard products of (ternary polymerization acrylonitrile) high shrinkage short fiber；The structural formula of FB is shown in formula (II), A-It is given for phosphotungstic acid Go out the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 281 DEG C, at 600 DEG C into charcoal Rate is 79%, and the retardant expanded polystyrene product LOI values comprising 20wt% the compositions are 28.2%, and flame retardant rating is UL94V1 grades (1.6mm) heat 500 hours surfaces in 100 DEG C of convection ovens and occur without precipitate.Content is the packet of 28wt% Polypropylene flame redardant product containing the composition, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 15
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Polyphosphoric acid piperazine is 70%；Mixture (the mass ratio 1 of PAN-DCD and FB:1) it is 20%；Sodium antimonate is 5%； Liquid silastic (DOW CORNING liquid silastic FL65-9001) is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:6.8:82 PAN-DCD, antimony wolframic acid and solvent (water and methanol Mixture (volume ratio 1:1) 11h) after mixing, is reacted at 120 DEG C, through cooling down, washing, detaching and drying obtained FB, The structural formula of PAN-DCD is shown in formula (I), and the polyacrylonitrile prepared used in PAN-DCD is oil of SPC corporation for three people's boards 3.33dtex and 6.67dtex has the waste silk of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber and bad substandard products；The knot of FB Structure formula is shown in formula (II), A-The ion formed after proton is provided for antimony wolframic acid.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 287 DEG C, at 600 DEG C into charcoal Rate is 75%, and the flame-proof polyethylene fire block articles grade comprising 28wt% the compositions is UL94V2 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 16
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine borate is 80%；Mixture (the mass ratio 3 of PAN-DCD and FB:1) it is 15%；Lithium titanate is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:7.5:85 PAN-DCD, borotungstic acid and solvent (n-butanol, The mixture of isobutanol and n-amyl alcohol (volume ratio 1:2:1)) after mixing, react 12h at 125 DEG C, through cooling down, washing, point FB is made from dry, the structural formula of PAN-DCD is shown in formula (I), and it is oil of SPC company to prepare the polyacrylonitrile used in PAN-DCD Preparing three people's board 3.33dtex and 6.67dtex has the waste silk of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber and bad Substandard products；The structural formula of FB is shown in formula (II), A-The ion formed after proton is provided for borotungstic acid.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 289 DEG C, at 600 DEG C into charcoal Rate is 71%, and the polypropylene flame redardant fire block articles grade comprising 25wt% the compositions is UL94V2 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 17
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine borate is 45%；FB is 47%；Calcium titanate is 5%；Liquid silastic be (Mai Tu Momentive companies Silica gel TN30851) it is 3%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:8:90 PAN-DCD, titanium tungsten acid and solvent (N, N- dimethyl The mixture of acetamide and dimethyl sulfoxide (DMSO) (volume ratio 1:1) 13h) after mixing, are reacted at 130 DEG C, through cooling down, washing, Separation and dry obtained FB, the structural formula of PAN-DCD are shown in formula (I), and the polyacrylonitrile prepared used in PAN-DCD is public for oil of SPC Department, which prepares three people's board 3.33dtex and 6.67dtex, the waste silk and not of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber Good substandard products；The structural formula of FB is shown in formula (II), A-The ion formed after proton is provided for titanium tungsten acid.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 286 DEG C, at 600 DEG C into charcoal Rate is 76%, the flame-proof polyethylene product comprising 28wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 18
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine silicotungstate is 32%；FB is 55%；Magnesium titanate is 8%；Liquid silastic (Mai Tu Momentive companies Silica gel TIA207GN) be 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:8.5:92 PAN-DCD, nickel wolframic acid and cyclohexanone mixing is After even, 14h is reacted at 140 DEG C, through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepares Polyacrylonitrile used in PAN-DCD has light acrylic fibers (ternary for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex Copolymerized acrylonitrile) high shrinkage short fiber waste silk and bad substandard products；The structural formula of FB is shown in formula (II), A-Proton is provided for nickel wolframic acid The ion formed afterwards.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 284 DEG C, at 600 DEG C into charcoal Rate is 82%, and the polypropylene flame redardant fire block articles grade comprising 30wt% the compositions is UL94V1 grades (1.6mm), at 100 DEG C 500 hours surfaces are heated in convection oven without precipitate to occur.Content is the polypropylene flame redardant for including the composition of 28wt% Product, after 70 DEG C of pure water impregnate 168 hours, surface occurs without white precipitate.
Embodiment 19
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine zinc stannate complex salt is 80%；Mixture (the mass ratio 1 of PAN-DCD and FB:1) it is 15%；Barium titanate It is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:9:95 PAN-DCD, platinum wolframic acid and N, N- dimethylacetamide Amine reacts 15h after mixing, at 145 DEG C, and through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in formula (I), prepare the polyacrylonitrile used in PAN-DCD has light nitrile for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex The waste silk and bad substandard products of synthetic fibre (ternary polymerization acrylonitrile) high shrinkage short fiber；The structural formula of FB is shown in formula (II), A-For platinum wolframic acid Provide the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 283 DEG C, at 600 DEG C into charcoal Rate is 76%, the flame-proof polyethylene product comprising 30wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 20
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine phosphotungstate is 75%；Mixture (the mass ratio 2 of PAN-DCD and FB:1) it is 17%；Magnesium silicate and silicon Mixture (the mass ratio 1 of sour aluminium:1) it is 6%；Silane coupling agent (KH171 of Nanjing dawn Chemical Group company) and methyl Mixture (the mass ratio 3 of hydrogen containing siloxane (SHIN-ETSU HANTOTAI KF99):1) it is 2%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:10:100 PAN-DCD, phosphorus tungsten vanadium heteropoly acid and dimethyl Sulfoxide reacts 16h after mixing, at 150 DEG C, and through cooling down, washing, detaching and drying obtained FB, the structural formula of PAN-DCD is shown in Formula (I), prepare the polyacrylonitrile used in PAN-DCD has light for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex The waste silk and bad substandard products of acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber；The structural formula of FB is shown in formula (II), A-For phosphorus tungsten Vanadium heteropoly acid provides the ion formed after proton.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 285 DEG C, at 600 DEG C into charcoal Rate is 74%, the polypropylene flame redardant product comprising 30wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 21
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Mixture (the mass ratio 2 of piperazine pyrophosphate and piperazine silicotungstate:3) it is 34%；The mixing of PAN-DCD and FB Object (mass ratio 1:1) it is 55%；The mixture of zinc borate and lithium titanate (mass ratio 1:1) it is 6%；Amino modified dimethyl Mixture (the mass ratio 2 of polysiloxanes (SHIN-ETSU HANTOTAI KF393) and liquid silastic (DOW CORNING liquid silastic FL60-9201): 1) it is 5%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:10:(dimethyl is sub- for 100 PAN-DCD, antimony molybdic acid and solvent Sulfone:Water=1:1 mass) after mixing, 20h is reacted at 120 DEG C, through cooling down, washing, detaching and drying obtained FB, PAN-DCD Structural formula see formula (I), prepare polyacrylonitrile used in PAN-DCD for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex has the waste silk of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber and bad substandard products；The structural formula of FB is shown in formula (II), A-The ion formed after proton is provided for antimony molybdic acid.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 291 DEG C, at 600 DEG C into charcoal Rate is 77%, the flame-proof polyethylene product comprising 29wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 22
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Mixture (the mass ratio 2 of piperazine phosphate, piperazine pyrophosphate and polyphosphoric acid piperazine:2:3) it is 68%；FB is 22%；Mixture (the mass ratio 1 of zinc borate, calcium titanate and magnesium titanate:2:1) it is 7%；The epoxy-modified poly- silica of dimethyl Mixture (the mass ratio 1 of alkane (SHIN-ETSU HANTOTAI KF102) and liquid silastic (the silica gel TSE399 of Mai Tu Momentive companies):1) It is 3%；
Wherein, the preparation method of FB is：It is 1 by mass ratio:10:(dimethyl is sub- for 100 PAN-DCD, silico-tungstic acid and solvent Sulfone:Water=1:1 mass) after mixing, 20h is reacted at 120 DEG C, through cooling down, washing, detaching and drying obtained FB, PAN-DCD Structural formula see formula (I), prepare polyacrylonitrile used in PAN-DCD for oil of SPC corporation for three people's board 3.33dtex and 6.67dtex has the waste silk of light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber and bad substandard products；The structural formula of FB is shown in formula (II), A-The ion formed after proton is provided for silico-tungstic acid.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 295 DEG C, at 600 DEG C into charcoal Rate is 78%, the polypropylene flame redardant product comprising 32wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 23
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine phosphate is 75%；PAN-DCD is 18%；The mixture of magnesia and magnesium silicate (mass ratio 1:1) it is 5%；Silane coupling agent (KH172 of Nanjing dawn Chemical Group company), dimethyl polysiloxane (SHIN-ETSU HANTOTAI KH96) and liquid Mixture (the mass ratio 1 of silicon rubber (DOW CORNING liquid silastic FL65-9001):2:3) it is 2%；
Wherein, the structural formula of PAN-DCD is shown in formula (I), and it is oil of SPC corporation to prepare the polyacrylonitrile used in PAN-DCD Standby three people's board 3.33dtex and 6.67dtex have light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber waste silk and bad time Product.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 285 DEG C, at 600 DEG C into charcoal Rate is 81%, the flame-proof polyethylene product comprising 30wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 24
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Polyphosphoric acid piperazine is 70%；PAN-DCD is 15%；The mixture of zinc oxide and zinc borate (mass ratio 2:1) it is 10%；Silane coupling agent (KH560 of Nanjing dawn Chemical Group company), methyl hydrogen polysiloxanes (SHIN-ETSU HANTOTAI KF99) and liquid Mixture (the mass ratio 2 of body silicon rubber (the silica gel TIA207GN of Mai Tu Momentive companies):3:1) it is 5%；
Wherein, the structural formula of PAN-DCD is shown in formula (I), and it is oil of SPC corporation to prepare the polyacrylonitrile used in PAN-DCD Standby three people's board 3.33dtex and 6.67dtex have light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber waste silk and bad time Product.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 285 DEG C, at 600 DEG C into charcoal Rate is 82%, the flame-proof polyethylene product comprising 30wt% the compositions heated in 100 DEG C of convection ovens 500 hours surfaces without Precipitate occurs.Content is the polypropylene flame redardant product comprising the composition of 28wt%, is impregnated 168 hours in 70 DEG C of pure water Afterwards, surface occurs without white precipitate.
Embodiment 25
It is a kind of without be precipitated halogen-free flame-retardant composition, each component and its mass content are as follows：
Piperazine silicotungstate is 40%；PAN-DCD is 50%；The mixture of titanium dioxide and calcium titanate (mass ratio 1: 3) it is 9%；Silane coupling agent (KH570 of Nanjing dawn Chemical Group company), dimethyl polysiloxane (DOW CORNING PMX- 1000CS) and the mixture (mass ratio 1 of liquid silastic (DOW CORNING liquid silastic FL60-9201):3:1) it is 1%；
Wherein, the structural formula of PAN-DCD is shown in formula (I), and it is oil of SPC corporation to prepare the polyacrylonitrile used in PAN-DCD Standby three people's board 3.33dtex and 6.67dtex have light acrylic fibers (ternary polymerization acrylonitrile) high shrinkage short fiber waste silk and bad time Product.
Finally obtain without the initial decomposition temperature of halogen-free flame-retardant composition is precipitated as 276 DEG C, at 600 DEG C into charcoal Rate is 82%, and the polypropylene flame redardant product comprising the composition heats 500 hours surfaces without precipitate in 100 DEG C of convection ovens Occur.Content is the polypropylene flame redardant product comprising the composition of 28wt%, after 70 DEG C of pure water impregnate 168 hours, table Face occurs without white precipitate.
Embodiment 26
A kind of preparation method of flame-proof polyethylene, by fire retardant combination made from embodiment 21 and polyethylene, (trade mark is Sinopec 5000S) after mixing flame-proof polyethylene product is made with double screw extruder melting extrusion, in flame-proof polyethylene The content of fire retardant combination is 28wt%, and the LOI for finally measuring the flame-proof polyethylene product is 28%, UL94 flame retardant tests etc. Grade for V1 grade (1.6mm battens) and without molten drop, 600 DEG C of charring rate (use thermogravimetic analysis (TGA), platinum crucible load sample, air atmosphere, 10 DEG C/min of heating rate) it is 25%.70 DEG C of pure water of flame-proof polyethylene product impregnate 168 hours without precipitation phenomenon.
Comparative example 1
A kind of preparation method of flame-proof polyethylene will contain melamine cyanurate (trade name nitrogenated flame retardant MCA) Fire retardant combination (except FB is different outer, other compositions and content are consistent with embodiment 26) and polyethylene (during the trade mark is State petrochemical industry 5000S) flame-proof polyethylene product is made with double screw extruder melting extrusion after mixing, it is hindered in flame-proof polyethylene The content for firing agent is 28wt%, and the LOI for finally measuring the flame-proof polyethylene is all grades of 23%, UL94 flame retardant tests up to not It arrives, there is molten drop in when burning, and 600 DEG C of charring rate is (using thermogravimetic analysis (TGA), platinum crucible load sample, air atmosphere, heating rate 10 DEG C/min) it is 4.2%.70 DEG C of pure water of fire-retardant product, which impregnate 168 hours, whiteness precipitation phenomenon.By embodiment 26 with The comparison of comparative example 1 is as can be seen that the fire retardant combination of the present invention is conducive to polymer and is burning with higher flame retarding efficiency In the process into charcoal, at the same it is preferable with polymer compatibility, and resistance to migration can be excellent.
Embodiment 27
A kind of preparation method of flame retardant polypropylene resin, by polypropylene (trade names K8303), the resistance obtained of embodiment 22 Combustion agent composition, silane coupling agent KH560, stearic amide and antioxidant 1010 are melted after mixing with double screw extruder It squeezes out and polypropylene flame redardant is made, the content of fire retardant combination is 30wt% in polypropylene flame redardant, silane coupling agent KH560, hard The content of resin acid amide and antioxidant 1010 is 0.2wt%, and the LOI for finally measuring the polypropylene flame redardant is 32.5%, UL94 Flame retardant test grade is V0 grade (3.2mm battens), (uses thermogravimetic analysis (TGA), platinum earthenware without molten drop, 600 DEG C of charring rate during burning Crucible load sample, air atmosphere, 10 DEG C/min of heating rate) it is 27.5%.70 DEG C of pure water of fire-retardant product impregnate 168 hours without analysis Occur as.
Comparative example 2
A kind of preparation method of flame retardant polypropylene resin, by polypropylene (trade names K8303), fire retardant combination (its Middle FB presses 2 for polyphosphoric acid piperazine and melamine polyphosphate:The compounding flame retardant of 1 mass ratio, other compositions and contains Amount is consistent with embodiment 27), silane coupling agent KH560, stearic amide and antioxidant 1010 use twin-screw after mixing Extruder melting extrusion is made polypropylene flame redardant, and the content of fire retardant is 30wt% in polypropylene flame redardant, silane coupling agent The content of KH560, stearic amide and antioxidant 1010 are 0.2wt%, and the LOI for finally measuring the polypropylene flame redardant is 30.0%, UL94 flame retardant test grade are V1 grade (3.2mm battens), and there is molten drop in when burning, and 600 DEG C of charring rate is (using heat mistake Weight analysis, platinum crucible load sample, air atmosphere, 10 DEG C/min of heating rate) it is 13.5%.70 DEG C of pure water of fire-retardant product impregnate There is whiteness precipitation phenomenon within 168 hours.Embodiment 27 and comparative example 2 are compared as can be seen that the flame retardant combination of the present invention Object has higher flame retarding efficiency, is conducive to polymer in combustion into charcoal, while preferable with polymer compatibility, resistance to move Move function admirable.

Claims (10)

1. it is a kind of without precipitation halogen-free flame-retardant composition, it is characterized in that, each component and its mass content are as follows：
The structural formula of PAN-DCD is as follows：
The structural formula of FB is as follows：
In formula, w is integer more than or equal to 10, and k, m, n, p and q are the integer more than or equal to 1, A-It is given for metal oxygen-containing acid Go out the ion formed after proton；
Content is the polypropylene flame redardant product comprising the composition of 28wt%, after 70 DEG C of pure water impregnate 168 hours, surface No white precipitate occurs.
It is 2. according to claim 1 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that described without precipitation nothing The initial decomposition temperature of halogen flame composition is more than 275 DEG C, is more than 70% in 600 DEG C of charring rates, content for 25~ The polypropylene flame redardant or polyethylene products comprising the composition of 35wt% heats 500 hours surfaces in 100 DEG C of convection ovens No precipitate occurs.
It is 3. according to claim 1 or 2 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the FB's Preparation method is：By PAN-DCD, metal oxygen-containing acid and solvent after mixing, 2~16h is reacted at 30~150 DEG C, through cooling down, Washing, separation and dry obtained FB.
It is 4. according to claim 3 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the PAN-DCD, The mass ratio of metal oxygen-containing acid and solvent is 1:0.05~10.0:5~100.
It is 5. according to claim 4 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the metal oxygen-containing Acid is the inorganic acid of tungstenic, molybdenum, titanium, tin, antimony or vanadium or is the heteropoly acid of tungstenic, molybdenum, titanium, tin, antimony or vanadium.
6. it is according to claim 5 it is a kind of without be precipitated halogen-free flame-retardant composition, which is characterized in that the tungstenic, molybdenum, Titanium, tin, antimony or vanadium inorganic acid be wolframic acid, molybdic acid, metatitanic acid, stannic acid, metaantimmonic acid or vanadic acid；The tungstenic, molybdenum, titanium, tin, antimony or vanadium Heteropoly acid for phosphomolybdic acid, silicomolybdic acid, titanium molybdic acid, zirconium molybdic acid, tin molybdic acid, antimony molybdic acid, nickel molybdic acid, phosphorus molybdenum vanadium heteropolyacid, phosphorus tungsten Acid, silico-tungstic acid, borotungstic acid, titanium tungsten acid, nickel wolframic acid, antimony wolframic acid, platinum wolframic acid or phosphorus tungsten vanadium heteropoly acid.
It is 7. according to claim 4 a kind of without halogen-free flame-retardant composition is precipitated, which is characterized in that the solvent is Water, methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutanol, n-amyl alcohol, cyclohexanol, acetone, cyclohexanone, methyl iso-butyl ketone (MIBK), N, N- bis- One or more of methylformamide, DMAC N,N' dimethyl acetamide and dimethyl sulfoxide (DMSO).
It is 8. according to claim 1 or 2 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the piperazine Inorganic acid salt is piperazine phosphate, piperazine pyrophosphate, polyphosphoric acid piperazine, piperazine borate, piperazine silicotungstate, piperazine zinc stannate are answered Close one or more of salt and piperazine phosphotungstate.
It is 9. according to claim 8 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the metal oxidation Object is one or more of magnesia, zinc oxide, titanium dioxide, silica, stannic oxide and antimony oxide；The metal Salt be in magnesium silicate, alumina silicate, zinc borate, zinc stannate, sodium antimonate, lithium titanate, calcium titanate, magnesium titanate and barium titanate it is a kind of with On；The organosilicon material refers to one or more of silane coupling agent, silicone oil, liquid silastic.
It is 10. according to claim 9 a kind of without precipitation halogen-free flame-retardant composition, which is characterized in that the silane is even The general formula for joining agent is RSiX3, R is amino, sulfydryl, vinyl, epoxy group, cyano or methacryloxy in formula, and X is methoxy Base or ethyoxyl；The silicone oil is that viscosity is 500 to 5000mm at 25 DEG C2The poly- silicon of dimethyl polysiloxane, methyl hydrogen of/s Oxygen alkane, amino modified dimethyl polysiloxane or epoxy-modified dimethyl polysiloxane.
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WO2021103082A1 (en) * 2019-11-30 2021-06-03 苏州和塑美科技有限公司 Hydrolysis-resistant, highly efficient flame retardant and preparation method therefor
CN113264890A (en) * 2020-11-30 2021-08-17 上海普利特复合材料股份有限公司 Synthesis and application of stain-resistant flame retardant
CN113277995A (en) * 2021-05-25 2021-08-20 江苏集萃先进高分子材料研究所有限公司 Preparation method of flame-retardant synergist of piperazine borate and imidazole borate
CN115710396A (en) * 2022-12-08 2023-02-24 合肥兴联通讯有限公司 B1-level dropless low-smoke halogen-free polyolefin cable material and preparation method thereof
CN115772285A (en) * 2022-12-12 2023-03-10 云南云天化股份有限公司 Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate

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WO2021103082A1 (en) * 2019-11-30 2021-06-03 苏州和塑美科技有限公司 Hydrolysis-resistant, highly efficient flame retardant and preparation method therefor
CN113264890A (en) * 2020-11-30 2021-08-17 上海普利特复合材料股份有限公司 Synthesis and application of stain-resistant flame retardant
CN113277995A (en) * 2021-05-25 2021-08-20 江苏集萃先进高分子材料研究所有限公司 Preparation method of flame-retardant synergist of piperazine borate and imidazole borate
CN115710396A (en) * 2022-12-08 2023-02-24 合肥兴联通讯有限公司 B1-level dropless low-smoke halogen-free polyolefin cable material and preparation method thereof
CN115772285A (en) * 2022-12-12 2023-03-10 云南云天化股份有限公司 Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate

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