CN108264720B - Precipitation-free halogen-free flame retardant composition - Google Patents

Precipitation-free halogen-free flame retardant composition Download PDF

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CN108264720B
CN108264720B CN201711474672.6A CN201711474672A CN108264720B CN 108264720 B CN108264720 B CN 108264720B CN 201711474672 A CN201711474672 A CN 201711474672A CN 108264720 B CN108264720 B CN 108264720B
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flame retardant
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dcd
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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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Abstract

The invention relates to a precipitation-free halogen-free flame retardant composition, which comprises the following components in percentage by mass: 30-80% of piperazine inorganic acid salt; PAN (personal area network)-DCD and/or FB is 15-55%; 5-10% of metal oxide and/or metal salt; 0-5% of an organosilicon material; the structural formula of PAN-DCD is as follows:
Figure DDA0001532586750000011
the structural formula of FB is as follows:
Figure DDA0001532586750000012
wherein w is an integer of 10 or more, k, m, n, p and q are integers of 1 or more, A‑The flame retardant polypropylene article comprising the composition, in an amount of 28wt% for ions formed after giving protons to metal oxo acids, showed no white precipitates on the surface after soaking in purified water at 70 c for 168 hours. The composition has the characteristics of good thermal stability, high flame-retardant efficiency, good compatibility with polymers, excellent char formation property and comprehensive performance and the like, can realize green and environment-friendly production, and has extremely good popularization value.

Description

Precipitation-free halogen-free flame retardant composition
Technical Field
The invention belongs to the field of preparation of flame retardants, and relates to a precipitation-free halogen-free flame retardant composition.
Background
In recent years, polymer materials have been widely used in various fields of national economy and daily life of people due to their excellent comprehensive properties and convenient processing and molding. However, most of polymer materials are easy to burn, and the burning process is accompanied with the generation of toxic and harmful gases, so that serious fire hazard exists, and the flame retardant modification of the polymer materials is particularly important in the environment. At present, the flame retardant function of the flame retardant polymer material is realized mainly by adding a flame retardant, and since the 80 s in the 20 th century, the development of halogen-free flame retardants is increased in various countries, wherein the halogen-free intumescent flame retardants are one of the solutions. The halogen-free intumescent flame retardant comprises three elements of an acid source (catalytic char formation effect), a gas source (foaming) and a carbon source (char formation), and at high temperature, the intumescent flame retardant can form a compact foamed intumescent carbon layer on the surface of a high polymer material, so that oxygen and heat can be isolated, the smoke generation amount is small, toxic and harmful gases are not generated, and the flame retardant effect is good, so that the flame retardant is concerned more and more widely.
Melamine can be regarded as a polymer containing diaminotriazine with one amino group in the triazine ring, and melamine and its salt can be used as flame retardant materials. The melamine salt flame retardant mainly comprises melamine cyanurate, melamine phosphate, melamine pyrophosphoric acid, melamine polyphosphate, melamine borate, melamine phthalate, melamine oxalate, melamine hydrobromide, melamine hypophosphite and the like, and the derivatives of the melamine are respectively suitable for flame retardant modification of different polymers, and the flame retardant effect can also be different. Compared with the traditional halogen flame retardant, the melamine and the salt flame retardant thereof have the characteristics of low smoke density, low toxicity, small corrosivity, good coloring capability, excellent electrical property and the like, meet the environmental protection requirement, have proper price and the like, and are increasingly applied to the flame retardant field. However, the flame retardant is an agglomerated particle structure with compact and high hardness and is difficult to effectively disperse in resin, so that the flame retardant performance or mechanical property of the flame retardant material is reduced, and most salts have certain solubility and hygroscopicity, and particularly, the solubility is gradually increased along with the rise of temperature. For example, Melamine Cyanurate (MCA) is the melamine salt flame retardant with the largest dosage at present, but has the problems of poor dispersibility, unstable flame retardant efficiency in flame retardant nylon or polyolefin and the like; the Melamine Phosphate (MP) not only has high solubility (0.54 g/100 g water), but also has low flame retardant efficiency for polymers such as nylon. Therefore, a new and efficient melamine flame retardant is needed to be further developed to solve the problems of low flame retardant efficiency, high solubility, easy precipitation, poor compatibility with polymers, and the like of melamine flame retardants.
In addition to melamine, few reports have been made on compounds containing diaminotriazine groups as flame retardants. The patent with application number 201110194940.5 reports that benzoguanamine carboxyethyl phenyl phosphinic acid condensate is used as a raw material to be compounded with other synergistic flame retardants to be used as a flame retardant, and the benzoguanamine can be regarded as a polymer containing diaminotriazine with one phenyl group on a triazine ring. However, after condensation reaction of benzoguanamine and carboxyethyl phenyl phosphinic acid, the foaming effect of imide groups and phosphoryl imine groups on molecular chains of the benzoguanamine and carboxyethyl phenyl phosphinic acid is obviously reduced, so the flame retardant mainly plays a role in carbon formation in a halogen-free flame retardant system.
The product synthesized by the reaction of polyacrylonitrile and dicyandiamide is often used as a polymeric flocculant because the molecules contain both acidic and basic groups, and is widely applied to the field of wastewater treatment. The Reaction product of polyacrylonitrile with dicyandiamide is reported in document 1(Reaction Products of Polyacrylonitrle with dicyandiamide. die Angewandte makromolekulare Chemie,1986,141:57-67) as a mixture containing diaminotriazine, amide group, carboxylic acid group and amidine structure; the reaction product of polyacrylonitrile and dicyandiamide is reported as a flocculant in document 2 (a novel flocculant for dye wastewater treatment-a reaction product of polyacrylonitrile and dicyandiamide, 1992,3: 119-; the use of a product synthesized by reacting industrial polyacrylonitrile with dicyandiamide using the method of document 1 as a dye wastewater decolorization treatment agent is reported in document 3(PAN-DCD for decolorization study of dye wastewater. environmental chemistry. 1995,14(6):531-536), but the specific structure of the synthesized compound is not reported; the document 4 (intermolecular interaction between a decolorizing agent and a reactive dye, Ministry of southern Kokai university (Nature science edition 1999,32(3):140-145) reports that a product synthesized by reacting industrial polyacrylonitrile as a raw material with dicyandiamide according to the synthesis method of the document 1 is used as a dye decolorizing agent, and in the document, authors report that the synthesized product is a mixture containing a plurality of groups such as cyano group, diaminotriazine, amide group, carboxylic acid group and amidine structure, similar to the structure reported in the document 1.
Therefore, the research on the precipitation-free halogen-free flame retardant composition with good compatibility with the polymer and high flame retardant effect is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a precipitation-free halogen-free flame retardant composition with good compatibility and excellent flame retardant effect. The composition contains PAN-DCD and/or FB flame retardant which are products prepared by taking polyacrylonitrile and dicyandiamide as raw materials. Among them, PAN-DCD has good thermal stability and compatibility. The FB flame retardant is prepared by taking PAN-DCD and metal oxyacid as raw materials and reacting under certain conditions, wherein when the metal oxyacid reacts with amino in PAN-DCD molecules, a metal oxyacid radical ion structure part can form a coordination structure with diaminotriazine and amidine structure groups in the same PAN-DCD molecule, and the formation of the coordination structure can induce a ring structure shown as a formula (B) in the PAN-DCD molecule to rapidly form carbon on one hand, and on the other hand, the metal oxyacid radical ion can rapidly promote the carbonization of a flame-retardant organic matrix or the crosslinking carbonization of a PAN-DCD molecular chain, and the amino in the PAN-DCD molecule is gasified and expanded, so that the flame retardant efficiency is greatly improved by the synergistic effect of the flame retardant, the matrix and the metal ligand, and the prepared flame retardant composition has excellent expansion flame retardant performance and char formation performance, the flame retardant has high flame retardant efficiency, and meanwhile, the existence of macromolecules and metal coordination structures also greatly improves the thermal stability of the flame retardant. Wherein the amidine structure, the diaminotriazinyl group and the structural formula (B) in the PAN-DCD molecule are specifically as follows:
amidine structure:
Figure BDA0001532586740000031
diamino triazinyl group:
Figure BDA0001532586740000032
formula (B):
Figure BDA0001532586740000033
the flame retardant composition obtained by the invention is a novel environment-friendly precipitate-free halogen-free flame retardant composition, and has a molecular structure simultaneously with a char forming group, a metal oxoacid radical for inducing and catalyzing a char forming structure and a foaming gas source (amino group), so that the flame retardant composition has the characteristics of good thermal stability, high flame retardant efficiency, good compatibility with polymers, excellent char forming property and comprehensive performance and the like, and can be widely used for flame retardant modification of resins, plastics, rubber, paper, coatings, fibers and formed bodies thereof and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
Figure BDA0001532586740000041
the structural formula of PAN-DCD is as follows:
Figure BDA0001532586740000042
wherein w is an integer of 10 or more, k, m, n, p and q are integers of 1 or more, A-Ions formed after giving protons to the metal oxo acids;
the flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
As a preferred technical scheme:
the precipitation-free halogen-free flame retardant composition has good thermal stability, the initial decomposition temperature is higher than 275 ℃, the char formation performance is good, the char formation rate at 600 ℃ is higher than 70% (by adopting thermogravimetric analysis, loading of a platinum crucible, air atmosphere and heating rate of 10 ℃/min), the compatibility with polyolefin is good, and the surface of a flame-retardant polypropylene or polyethylene product containing the composition is not precipitated after being heated in a blast oven at 100 ℃ for 500 hours, wherein the flame-retardant polypropylene or polyethylene product contains 25-35 wt% of the composition.
The precipitation-free halogen-free flame retardant composition comprises the following components in percentage by weight: uniformly mixing PAN-DCD, metal oxyacid and a solvent, reacting for 2-16 h at 30-150 ℃, cooling, washing, separating and drying to obtain FB.
The precipitation-free halogen-free flame retardant composition comprises PAN-DCD, metal oxoacid and a solvent, wherein the mass ratio of the PAN-DCD, the metal oxoacid and the solvent is 1: 0.05-10.0: 5-100.
A bleed-free, halogen-free flame retardant composition as described above, the metal oxo acid being an inorganic acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium or a heteropoly acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium.
A non-precipitating halogen-free flame retardant composition as described above, wherein the inorganic acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium is tungstic acid, molybdic acid, titanic acid, stannic acid, antimonic acid or vanadic acid; the heteropoly acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium is phosphomolybdic acid, silicomolybdic acid, titanium molybdic acid, zirconium molybdic acid, stannomolybdic acid, antimony molybdic acid, nickel molybdic acid, phosphomolybdovanadium heteropoly acid, phosphotungstic acid, silicotungstic acid, borotungstic acid, titanium tungstic acid, nickel tungstic acid, antimony tungstic acid, platinum tungstic acid or phosphotungstovanadic heteropoly acid.
The precipitation-free halogen-free flame retardant composition comprises a solvent and a non-polar solvent, wherein the solvent is one or more of water, methanol, ethanol, propanol, N-butanol, isobutanol, N-pentanol, cyclohexanol, acetone, cyclohexanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
The precipitation-free halogen-free flame retardant composition comprises piperazine inorganic acid salt, wherein the piperazine inorganic acid salt is one or more of piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, piperazine borate, piperazine silicotungstate, piperazine zinc stannate composite salt and piperazine phosphotungstate.
The non-precipitation halogen-free flame retardant composition is characterized in that the metal oxide is more than one of magnesium oxide, zinc oxide, titanium dioxide, silicon dioxide, tin dioxide and antimony trioxide; the metal salt is more than one of magnesium silicate, aluminum silicate, zinc borate, zinc stannate, sodium antimonate, lithium titanate, calcium titanate, magnesium titanate and barium titanate; the organosilicon material is one or more of silane coupling agent, silicone oil and liquid silicone rubber (Dow Corning liquid silicone rubber FL60-9201 and FL65-9001, silica gel TSE399, TN30851 and TIA207GN of Momentive company).
The composition is characterized in that the silane coupling agent has a general formula of RSiX3Wherein R is amino, sulfydryl, vinyl, epoxy group, cyano or methacryloxy, X is methoxy or ethoxy, and the product model is KH151, KH171, KH172, KH550, KH560, KH570, KH590 or SG-Si6490 of Nanjing eosin chemical group company; the viscosity of the silicone oil is 500-5000 mm at 25 DEG C2Dimethyl polysiloxane per second (Dow Corning PMX-1000CS and Xinyue KH96), methyl hydrogen polysiloxane (Xinyue KF99), amino modified dimethyl polysiloxane (Xinyue KF393), or epoxy modified dimethyl polysiloxane (Xinyue KF 102).
Has the advantages that:
(1) according to the precipitation-free halogen-free flame retardant composition, due to the formation of the coordination structure of the metal oxoacid radical ions and the amino groups in the molecules, FB in the components can induce the cyclic structure in the PAN-DCD molecules to rapidly form carbon on the one hand, and on the other hand, the metal oxoacid radical ions can rapidly promote the carbonization of the flame-retardant organic matrix on the other hand, the amino groups in the PAN-DCD molecules are gasified and expanded at the moment, and the flame retardant efficiency is greatly improved due to the synergistic effect of the flame retardant, the matrix and the metal ligand, so that the prepared flame retardant has excellent expansion flame retardant property and carbon formation property and high flame retardant efficiency, and meanwhile, the heat stability of the whole flame retardant composition is also greatly improved due to the existence of the macromolecules and the;
(2) the molecular structure of FB in the composition simultaneously has the char forming group, the induced and catalyzed char forming structure and the foaming gas source (amino group), so that the composition formed by the composition has the characteristics of good thermal stability, high flame retardant efficiency, good compatibility with polymers, excellent migration resistance, excellent char forming property and comprehensive performance and the like;
(3) the precipitation-free halogen-free flame retardant composition provided by the invention has the advantages that the raw materials are easy to obtain, and the environment-friendly requirement is met.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Figure BDA0001532586740000061
Figure BDA0001532586740000071
In the formulae (I) and (II), w is an integer of 10 or more, and k, m, n, p and q are each 10 or more
An integer equal to 1.
Example 1
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
44% of piperazine phosphate; the mixture of PAN-DCD and FB (mass ratio of 1:1) is 42%; 10% of magnesium oxide; the silane coupling agent (KH 151 from Nanjing eosin chemical group Co.) was 4%;
the preparation method of the FB comprises the following steps: PAN-DCD, tungstic acid and water in a mass ratio of 1:0.05:5 are uniformly mixed, react for 16 hours at 30 ℃, and FB is prepared by cooling, washing, separating and drying, wherein the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective goods of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving a proton to tungstic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 281 ℃, a char formation rate of 73% at 600 ℃, a flame retardant polyethylene article comprising 30% by weight of the composition having a flame retardant rating of UL94V1 (1.6mm), and no precipitates appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 2
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
62% of piperazine pyrophosphate; FB is 32%; 5% of zinc oxide; 1% of a silane coupling agent (KH 171 by Nanjing eosin chemical group Co.);
the preparation method of the FB comprises the following steps: PAN-DCD, molybdic acid and methanol in a mass ratio of 1:0.1:10 are uniformly mixed, then react for 15 hours at 36 ℃, and FB is prepared by cooling, washing, separating and drying, wherein the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective goods of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-The ion formed after giving a proton to molybdic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition was 288 ℃, the char formation rate at 600 ℃ was 78%, the flame retardant polypropylene article comprising 30 wt% of the composition was rated UL94V0 (3.2mm), and no precipitation appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 3
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
50% of polyphosphoric acid piperazine; FB is 40%; 5 percent of titanium dioxide; the silane coupling agent (KH 172 from Nanjing eosin chemical group Co.) was 5%;
the preparation method of the FB comprises the following steps: PAN-DCD, titanic acid and ethanol in a mass ratio of 1:1:15 are uniformly mixed, react for 14 hours at 40 ℃, and FB is prepared through cooling, washing, separating and drying, wherein the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective products of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming Shi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to titanic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition is 280 ℃, the char forming rate at 600 ℃ is 73%, the flame retardant rating of a flame retardant EVA product containing 35wt% of the composition is UL94V1 grade (1.6mm), and no precipitation appears on the surface after heating in a blast oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 4
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
45% of piperazine borate; 45% of a mixture of PAN-DCD and FB (in a mass ratio of 1: 2); 10% of silicon dioxide;
the preparation method of the FB comprises the following steps: uniformly mixing PAN-DCD, stannic acid and propanol with the mass ratio of 1:1.5:20, reacting at 45 ℃ for 13 hours, cooling, washing, separating and drying to obtain FB, wherein the structural formula of PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing PAN-DCD is Shanghai Shi chemical companyPreparing waste silk and poor inferior products of the three-people brand 3.33dtex and 6.67dtex bright acrylic fiber (terpolymer acrylonitrile) high-shrinkage short fiber; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to stannic acid.
The resulting precipitate-free halogen-free flame retardant composition had an initial decomposition temperature of 279 ℃ and a char formation rate of 72% at 600 ℃ and a flame retardant ABS article comprising 32% by weight of the composition had a flame retardant rating of UL94V0 (1.6mm) and showed no precipitate on the surface when heated in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 5
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
37% of piperazine silicotungstate; the mass ratio of the mixture of PAN-DCD and FB (2: 1) is 55 percent; 5% of stannic oxide; the silane coupling agent (KH 560 from Nanjing eosin chemical group Co.) was 3%;
the preparation method of the FB comprises the following steps: PAN-DCD, antimonic acid and n-butyl alcohol in a mass ratio of 1:2:25 are uniformly mixed, and react for 12 hours at 52 ℃, FB is prepared through cooling, washing, separating and drying, and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to antimonic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 285 ℃ and a char formation rate of 79% at 600 ℃, and a flame-retardant polyethylene article comprising 35% by weight of the composition had a flame retardancy rating of UL94V0 (1.6mm), and no precipitates appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 6
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
36% of zinc piperazine stannate composite salt; FB is 50%; antimony trioxide is 10%; the silane coupling agent (KH 570 from Nanjing eosin chemical group Co.) was 4%;
the preparation method of the FB comprises the following steps: PAN-DCD, vanadic acid and isobutanol with the mass ratio of 1:2.8:30 are uniformly mixed and react for 2 hours at the temperature of 60 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective products of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming Shi company; the structural formula of FB is shown as formula (II), A-Ion formed after giving proton to vanadic acid.
The resulting precipitate-free, halogen-free, flame retardant composition had an initial decomposition temperature of 279 ℃ and char formation at 600 ℃ of 76%, and a flame retardant HIPS article comprising 30% by weight of the composition had a flame retardant rating of UL94V0 (1.6mm) and showed no precipitate on the surface when heated in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 7
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
48% of piperazine phosphotungstate; FB is 42%; the mass ratio of the mixture of magnesium oxide and zinc oxide is 1:1, 8%; the silane coupling agent (KH 590 of Nanjing eosin chemical group Co.) was 2%;
the preparation method of the FB comprises the following steps: PAN-DCD, phosphomolybdic acid and n-amyl alcohol in a mass ratio of 1:3.2:35 are uniformly mixed, and then react for 3 hours at 65 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and poor inferior products of high-shrinkage short fibers of three-person brand 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-The ions formed after giving protons to phosphomolybdic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 290 ℃ and a char formation rate of 75% at 600 ℃, and a flame-retardant polyethylene article comprising 30% by weight of the composition had a flame retardancy rating of UL94V0 (1.6mm), and the surface of the article was free from precipitates when heated in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 8
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the mass ratio of the mixture of piperazine phosphate and piperazine pyrophosphate is 65 percent (2: 3); the mixture of PAN-DCD and FB (mass ratio of 1:2) is 22%; the mass ratio of the mixture of titanium dioxide and silicon dioxide is 1:1, and is 10 percent; 3% of a silane coupling agent (SG-Si 6490 from Nanjing eosin optical chemical group Co., Ltd.);
the preparation method of the FB comprises the following steps: PAN-DCD, silicomolybdic acid and cyclohexanol in the mass ratio of 1:3.5:40 are uniformly mixed and react for 4 hours at 72 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to silicomolybdic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 281 ℃, a char formation rate of 80% at 600 ℃, a flame retardant polypropylene article comprising 28% by weight of the composition having a flame retardant rating of UL94V0 (1.6mm), and no precipitation appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 9
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the mass ratio of the mixture of polyphosphoric acid piperazine and piperazine borate is 1:3, and is 62%; the mixture of PAN-DCD and FB (1: 1 by mass) is 28 percent; 5 percent of mixture of tin dioxide and antimony trioxide (the mass ratio is 3: 1); dow Corning PMX-1000CS is 5%;
the preparation method of the FB comprises the following steps: PAN-DCD, titanium molybdic acid and acetone in a mass ratio of 1:4:45 are uniformly mixed, and react for 5 hours at 80 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective products of three-brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming Shi company; the structural formula of FB is shown as formula (II), A-The ions formed after giving protons to the titanium molybdic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition was 283 ℃, the char formation rate at 600 ℃ was 84%, the flame retardant polyethylene article comprising 32 wt% of the composition was rated UL94V1 (1.6mm), and no precipitation appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 10
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the mixture of piperazine silicotungstate and piperazine zinc stannate composite salt (mass ratio is 2:1) is 70%; 15% of mixture of PAN-DCD and FB (mass ratio of 1: 4); 10 percent of mixture (mass ratio is 1:2:1) of magnesium oxide, tin dioxide and antimony trioxide; KH96 is 5%;
the preparation method of the FB comprises the following steps: PAN-DCD, zirconium molybdic acid and cyclohexanone in a mass ratio of 1:4.2:55 are uniformly mixed and react for 6 hours at 83 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and poor defective products of 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to the zirconium molybdic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition is 288 ℃, the char formation rate at 600 ℃ is 85%, the flame retardant rating of a flame retardant nitrile rubber product containing 30 wt% of the composition is UL94V1 grade (1.6mm), and no precipitation appears on the surface after heating in a blast oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 11
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the mass ratio of the mixture of piperazine phosphate and piperazine silicotungstate is 77%; 15% of a mixture of PAN-DCD and FB (mass ratio of 4: 1); 7 percent of magnesium silicate; methyl hydrogen polysiloxane (shin-Etsu KF99) was 1%;
the preparation method of the FB comprises the following steps: PAN-DCD, tin molybdic acid and methyl isobutyl ketone with the mass ratio of 1:4.8:60 are uniformly mixed, then react for 7 hours at 90 ℃, FB is prepared by cooling, washing, separating and drying, and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to tin molybdic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition is 284 ℃, the char forming rate at 600 ℃ is 79%, the flame retardant grade of a flame retardant styrene-butadiene rubber product containing 35wt% of the composition is UL94V0 grade (1.6mm), and no precipitation appears on the surface after heating in a blast oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 12
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
66% of a mixture (mass ratio of 2:1:2) of piperazine phosphate, piperazine pyrophosphate and piperazine phosphotungstate; FB is 25%; the content of aluminum silicate is 7 percent; amino-modified dimethylpolysiloxane (shin KF393) 2%;
the preparation method of the FB comprises the following steps: PAN-DCD, nickel molybdic acid and N, N-dimethylformamide with the mass ratio of 1:5:70 are uniformly mixed, then the mixture reacts for 8 hours at 96 ℃, FB is prepared by cooling, washing, separating and drying, and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming company; the structural formula of FB is shown as formula (II), A-The ions formed after giving protons to the nickel molybdic acid.
The resulting precipitate-free halogen-free flame retardant composition had an initial decomposition temperature of 286 deg.C, char formation of 72% at 600 deg.C, flame retardant rating of UL94V0 (1.6mm) for flame retardant SBS-containing articles comprising 33 wt% of the composition, and no precipitate appeared on the surface when heated in a forced air oven at 100 deg.C for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 13
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
48% of piperazine phosphate; FB is 42%; zinc borate 7% dimethylpolysiloxane (shin KF102) 3%;
the preparation method of the FB comprises the following steps: PAN-DCD, phosphomolybdovanadophosphoric acid and N, N-dimethylacetamide with the mass ratio of 1:5.8:76 are uniformly mixed, react at 102 ℃ for 9 hours, and FB is prepared by cooling, washing, separating and drying, wherein the structural formula of the PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and poor defective products of three-brand 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to phosphomolybdovanadophosphoric acid.
The initial decomposition temperature of the finally obtained non-precipitation halogen-free flame retardant composition is 289 ℃, the char forming rate at 600 ℃ is 77%, the flame retardant rating of a flame retardant SEBS product containing 36 wt% of the composition is UL94V1 grade (1.6mm), and no precipitation appears on the surface after heating in a blowing oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 14
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
71% of piperazine pyrophosphate; FB is 20%; the zinc stannate accounts for 8 percent; the liquid silicone rubber (Dow Corning liquid silicone rubber FL60-9201) is 1%;
the preparation method of the FB comprises the following steps: PAN-DCD, phosphotungstic acid and dimethyl sulfoxide are uniformly mixed according to the mass ratio of 1:6.2:80, the mixture reacts for 10 hours at 110 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as the formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective goods of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming Shi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to phosphotungstic acid.
The resulting precipitation-free, halogen-free, flame-retardant composition had an initial decomposition temperature of 281 ℃ and a char formation rate of 79% at 600 ℃, and flame-retardant, expanded polystyrene articles comprising 20% by weight of the composition had an LOI value of 28.2% and a flame-retardant rating of UL94V1 rating (1.6mm), and showed no precipitation on the surface when heated in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 15
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
70% of polyphosphoric acid piperazine; the mixture of PAN-DCD and FB (mass ratio of 1:1) is 20%; 5% of sodium antimonate; the liquid silicone rubber (Dow Corning liquid silicone rubber FL65-9001) is 5%;
the preparation method of the FB comprises the following steps: uniformly mixing PAN-DCD, antimony tungstic acid and a solvent (a mixture of water and methanol (the volume ratio is 1:1)) in a mass ratio of 1:6.8:82, and then heating at 120 DEG CReacting for 11h, cooling, washing, separating and drying to obtain FB, wherein the structural formula of PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to antimony tungstic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 287 ℃ and a char formation rate of 75% at 600 ℃, and a flame-retardant polyethylene article comprising 28% by weight of the composition had a flame retardancy rating of UL94V2 (1.6mm), and no precipitates appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 16
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the piperazine borate is 80%; 15% of a mixture of PAN-DCD and FB (mass ratio of 3: 1); 5% of lithium titanate;
the preparation method of the FB comprises the following steps: PAN-DCD with the mass ratio of 1:7.5:85, borotungstic acid and a solvent (a mixture of n-butyl alcohol, isobutyl alcohol and n-amyl alcohol (the volume ratio is 1:2:1)) are uniformly mixed, the mixture reacts for 12 hours at 125 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective short fiber of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) prepared by Shanghai Shi Kaishi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to borotungstic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 289 ℃ and a char formation rate of 71% at 600 ℃, and a flame-retardant polypropylene article comprising 25 wt% of the composition had a flame retardancy rating of UL94V2 (1.6mm) and showed no precipitation on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 17
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
45% of piperazine borate; FB accounts for 47%; 5% of calcium titanate; liquid silicone rubber (silica gel TN30851 by Momentive, Michji photo) was 3%;
the preparation method of the FB comprises the following steps: uniformly mixing PAN-DCD with the mass ratio of 1:8:90, titanium tungstic acid and a solvent (a mixture of N, N-dimethylacetamide and dimethyl sulfoxide (the volume ratio is 1:1)), reacting at 130 ℃ for 13 hours, and cooling, washing, separating and drying to obtain FB, wherein the structural formula of the PAN-DCD is shown in formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective goods of three-brand 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to the titanium tungstic acid.
The resulting precipitation-free, halogen-free, flame-retardant composition had an initial decomposition temperature of 286 deg.C, a char formation of 76% at 600 deg.C, and a flame-retardant polyethylene article comprising 28% by weight of the composition was heated in a forced air oven at 100 deg.C for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 18
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
piperazine silicotungstate 32%; FB is 55%; the magnesium titanate is 8 percent; liquid silicone rubber (TIA 207GN silicone rubber from Momentive, meiji) 5%;
the preparation method of the FB comprises the following steps: PAN-DCD, nickel tungstic acid and cyclohexanone in a mass ratio of 1:8.5:92 are uniformly mixed and react for 14 hours at 140 ℃, the structural formula of FB is obtained by cooling, washing, separating and drying, and the polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective short fibers of 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) prepared by Shanghai Shi chemical company(ii) a The structural formula of FB is shown as formula (II), A-Ions formed after giving protons to nickel tungstic acid.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition was 284 ℃, the char formation rate at 600 ℃ was 82%, the flame retardant grade of a flame retardant polypropylene article comprising 30 wt% of the composition was UL94V1 grade (1.6mm), and no precipitation appeared on the surface after heating in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 19
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the content of zinc piperazine stannate composite salt is 80%; 15% of mixture (mass ratio of 1:1) of PAN-DCD and FB; 5% of barium titanate;
the preparation method of the FB comprises the following steps: PAN-DCD, platinic acid and N, N-dimethylacetamide are evenly mixed according to the mass ratio of 1:9:95, the mixture reacts for 15 hours at 145 ℃, FB is prepared by cooling, washing, separating and drying, the structural formula of PAN-DCD is shown as formula (I), and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Ming Shi company; the structural formula of FB is shown as formula (II), A-The ions formed after giving protons to plattinous acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 283 ℃ and a char formation rate of 76% at 600 ℃, and a flame-retardant polyethylene article comprising 30% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation appearing on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 20
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
75% of piperazine phosphotungstate; the mixture of PAN-DCD and FB (mass ratio of 2:1) is 17%; the mass ratio of the mixture of magnesium silicate and aluminum silicate is 1:1, and is 6 percent; the mixture (mass ratio of 3:1) of the silane coupling agent (KH 171 of Nanjing eosin optical chemical group company) and methyl hydrogen polysiloxane (Xinyue KF99) was 2%;
the preparation method of the FB comprises the following steps: PAN-DCD, phosphotungstic vanadic acid and dimethyl sulfoxide in a mass ratio of 1:10:100 are uniformly mixed and react for 16 hours at 150 ℃, FB is prepared by cooling, washing, separating and drying, and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to the phosphotungstic vanadic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 285 ℃ and a char formation rate of 74% at 600 ℃, and a flame-retardant polypropylene article comprising 30% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 21
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
the mass ratio of the mixture of piperazine pyrophosphate and piperazine silicotungstate is 34%; the mass ratio of the mixture of PAN-DCD and FB (1: 1) is 55 percent; the mass ratio of the mixture of zinc borate and lithium titanate is 1:1, and is 6 percent; the mixture (mass ratio of 2:1) of amino modified dimethyl polysiloxane (Xinyue KF393) and liquid silicone rubber (Dow Corning liquid silicone rubber FL60-9201) is 5%;
the preparation method of the FB comprises the following steps: PAN-DCD with the mass ratio of 1:10:100, antimonic acid and a solvent (dimethyl sulfoxide: water is 1:1 by mass) are uniformly mixed, the mixture reacts for 20 hours at 120 ℃, FB is prepared by cooling, washing, separating and drying, the polyacrylonitrile used for preparing PAN-DCD is waste silk and ternary copolymerized acrylonitrile of three-brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fiber prepared by Shanghai Shi Ming Shi companyDefective and defective products; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to antimony molybdic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 291 ℃ and a char formation rate of 77% at 600 ℃, and a flame-retardant polyethylene article comprising 29% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 22
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
68% of a mixture (mass ratio of 2:2:3) of piperazine phosphate, piperazine pyrophosphate and piperazine polyphosphate; FB is 22%; the mass ratio of the mixture of zinc borate, calcium titanate and magnesium titanate is 7 percent (the mass ratio is 1:2: 1); the mixture (mass ratio of 1:1) of epoxy modified dimethylpolysiloxane (Xinyue KF102) and liquid silicone rubber (silica gel TSE399 from Momentive, Mitigo) was 3%;
the preparation method of the FB comprises the following steps: PAN-DCD with the mass ratio of 1:10:100, silicotungstic acid and a solvent (dimethyl sulfoxide: water is 1:1 in mass) are uniformly mixed, the mixture reacts for 20 hours at 120 ℃, FB is prepared by cooling, washing, separating and drying, and polyacrylonitrile used for preparing PAN-DCD is waste silk and poor defective products of three-brand 3.33dtex and 6.67dtex bright acrylic fibers (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi Kaishi company; the structural formula of FB is shown as formula (II), A-Ions formed after giving protons to silicotungstic acid.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 295 ℃ and a char formation rate of 78% at 600 ℃, and a flame-retardant polypropylene article comprising 32% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 23
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
75% of piperazine phosphate; PAN-DCD is 18%; the mass ratio of the mixture of magnesium oxide and magnesium silicate is 1:1, and is 5 percent; a mixture (mass ratio of 1:2:3) of a silane coupling agent (KH 172 from Nanjing eosin optical chemical group Co.), dimethyl polysiloxane (Xinyue KH96) and liquid silicone rubber (Dow Corning liquid silicone rubber FL65-9001) was 2%;
the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective inferior-quality products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 285 ℃ and a char formation rate of 81% at 600 ℃, and a flame-retardant polyethylene article comprising 30% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 24
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
70% of polyphosphoric acid piperazine; PAN-DCD is 15%; the mass ratio of the mixture of zinc oxide and zinc borate is 2:1, and is 10 percent; 5% of a mixture (mass ratio of 2:3:1) of a silane coupling agent (KH 560 available from Nanjing eosin optical chemical group Co.), methyl hydrogen polysiloxane (Xin Yuan KF99) and liquid silicone rubber (silica gel TIA207GN available from Momentive Co., Ltd., Miyamo);
the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective inferior-quality products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company.
The finally obtained precipitation-free halogen-free flame retardant composition had an initial decomposition temperature of 285 ℃ and a char formation rate of 82% at 600 ℃, and a flame-retardant polyethylene article comprising 30% by weight of the composition was heated in a forced air oven at 100 ℃ for 500 hours with no precipitation on the surface. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 25
A precipitation-free halogen-free flame retardant composition comprises the following components in percentage by mass:
piperazine silicotungstate 40%; PAN-DCD was 50%; the mass ratio of the mixture of titanium dioxide and calcium titanate is 9 percent (the mass ratio is 1: 3); 1% of a mixture (mass ratio of 1:3:1) of a silane coupling agent (KH 570 from Nanjing eosin optical chemical group Co.), dimethyl polysiloxane (Dow Corning PMX-1000CS) and liquid silicone rubber (Dow Corning liquid silicone rubber FL 60-9201);
the structural formula of the PAN-DCD is shown as a formula (I), and polyacrylonitrile used for preparing the PAN-DCD is waste silk and defective inferior-quality products of three-person brand 3.33dtex and 6.67dtex bright acrylic fiber (ternary copolymerized acrylonitrile) high-shrinkage short fibers prepared by Shanghai Shi chemical company.
The initial decomposition temperature of the finally obtained precipitation-free halogen-free flame retardant composition was 276 ℃, the char formation rate at 600 ℃ was 82%, and the surface of the flame-retardant polypropylene article comprising the composition was free from precipitates when heated in a forced air oven at 100 ℃ for 500 hours. The flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
Example 26
A preparation method of flame-retardant polyethylene comprises the steps of uniformly mixing the flame retardant composition prepared in the embodiment 21 with polyethylene (the trademark is China petrochemical 5000S), and then carrying out melt extrusion by using a double-screw extruder to prepare a flame-retardant polyethylene product, wherein the content of the flame retardant composition in the flame-retardant polyethylene is 28wt%, the LOI of the flame-retardant polyethylene product is finally measured to be 28%, the UL94 flame-retardant test grade is V1 grade (1.6mm sample strip) and is free of molten drops, and the char formation rate at 600 ℃ (by adopting thermogravimetric analysis, platinum crucible sample loading, air atmosphere and the heating rate of 10 ℃/min) is 25%. The flame-retardant polyethylene product is soaked in purified water at 70 ℃ for 168 hours without precipitation.
Comparative example 1
A preparation method of flame-retardant polyethylene comprises the steps of uniformly mixing a flame retardant composition (except FB, other compositions and contents are consistent with those of example 26) containing melamine cyanurate (namely a nitrogen flame retardant MCA) with polyethylene (with the trademark of China petrochemical 5000S) and then carrying out melt extrusion by using a double-screw extruder to prepare a flame-retardant polyethylene product, wherein the content of the flame retardant in the flame-retardant polyethylene is 28wt%, the LOI of the flame-retardant polyethylene is finally measured to be 23%, all grades cannot be reached in a UL94 flame-retardant test, molten drops exist during combustion, and the char formation rate at 600 ℃ (by adopting thermal weight loss analysis, loading a platinum crucible, and air atmosphere, the heating rate is 10 ℃/min) is 4.2%. White substances are separated out when the flame-retardant product is soaked in purified water for 168 hours at 70 ℃. Comparing example 26 with comparative example 1, it can be seen that the flame retardant composition of the present invention has higher flame retardant efficiency, is beneficial to the char formation of the polymer during combustion, and has better compatibility with the polymer and excellent migration resistance.
Example 27
A preparation method of flame-retardant polypropylene resin comprises the steps of uniformly mixing polypropylene (trade mark K8303), the flame retardant composition prepared in example 22, a silane coupling agent KH560, stearic acid amide and an antioxidant 1010, and then carrying out melt extrusion by using a double-screw extruder to prepare the flame-retardant polypropylene, wherein the content of the flame retardant composition in the flame-retardant polypropylene is 30 wt%, the content of the silane coupling agent KH560, stearic acid amide and the content of the antioxidant 1010 are all 0.2 wt%, finally, the LOI of the flame-retardant polypropylene is 32.5%, the UL94 flame-retardant test grade is V0 grade (3.2mm sample strip), no molten drop exists during combustion, and the char formation rate at 600 ℃ (adopting thermal weight loss analysis, platinum crucible sample loading, air atmosphere and the heating rate of 10 ℃/min) is 27.5%. The flame-retardant product is soaked in purified water for 168 hours at 70 ℃ without precipitation.
Comparative example 2
A preparation method of flame-retardant polypropylene resin comprises the steps of uniformly mixing polypropylene (trade mark K8303), a flame retardant composition (FB is a compound flame-retardant system of polyphosphoric acid piperazine and melamine polyphosphate according to a mass ratio of 2:1, and other compositions and contents are consistent with those of example 27), a silane coupling agent KH560, stearic acid amide and an antioxidant 1010, and then carrying out melt extrusion by using a double-screw extruder to prepare the flame-retardant polypropylene, wherein the flame retardant content in the flame-retardant polypropylene is 30 wt%, the silane coupling agent KH560, stearic acid amide and the antioxidant 1010 are all 0.2 wt%, the LOI of the flame-retardant polypropylene is finally measured to be 30.0%, the UL94 flame-retardant test grade is V1 (3.2mm sample strip), molten drops exist during combustion, and the char formation rate at 600 ℃ (adopting thermal weight loss analysis, platinum crucible loading, air atmosphere and the heating rate of 10 ℃/min) is 13.5%. White substances are separated out when the flame-retardant product is soaked in purified water for 168 hours at 70 ℃. Comparing example 27 with comparative example 2, it can be seen that the flame retardant composition of the present invention has higher flame retardant efficiency, is beneficial to the char formation of the polymer during combustion, and has better compatibility with the polymer and excellent migration resistance.

Claims (10)

1. A precipitation-free halogen-free flame retardant composition is characterized by comprising the following components in percentage by mass:
30-80% of piperazine inorganic acid salt;
15-55% of PAN-DCD and/or FB;
5-10% of metal oxide and/or metal salt;
0-5% of an organic silicon material;
the structural formula of PAN-DCD is as follows:
Figure DEST_PATH_IMAGE002
；
the structural formula of FB is as follows:
Figure DEST_PATH_IMAGE004
；
wherein w is an integer of 10 or more, k, m, n, p and q are integers of 1 or more, A-Ions formed after giving protons to the metal oxo acids;
the flame-retardant polypropylene article comprising the composition in an amount of 28wt% showed no white precipitate on the surface after soaking in purified water at 70 ℃ for 168 hours.
2. The composition of claim 1, wherein the composition has an initial decomposition temperature of more than 275 ℃, a char formation rate of more than 70% at 600 ℃, and 25-35 wt% of flame retardant polypropylene or polyethylene products comprising the composition, and the composition is heated in a forced air oven at 100 ℃ for 500 hours without precipitate on the surface.
3. The bleed-free, halogen-free flame retardant composition of claim 1 or 2 wherein the FB is prepared by a process comprising: uniformly mixing PAN-DCD, metal oxyacid and a solvent, reacting for 2-16 h at 30-150 ℃, cooling, washing, separating and drying to obtain FB.
4. The composition of claim 3, wherein the mass ratio of the PAN-DCD to the metal oxoacid to the solvent is 1: 0.05-10.0: 5-100.
5. The composition of claim 4, wherein the metal oxyacid is an inorganic acid containing tungsten, molybdenum, titanium, tin, antimony, or vanadium or a heteropoly acid containing tungsten, molybdenum, titanium, tin, antimony, or vanadium.
6. The composition of claim 5, wherein the inorganic acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium is tungstic acid, molybdic acid, titanic acid, stannic acid, antimonic acid or vanadic acid; the heteropoly acid containing tungsten, molybdenum, titanium, tin, antimony or vanadium is phosphomolybdic acid, silicomolybdic acid, titanium molybdic acid, zirconium molybdic acid, stannomolybdic acid, antimony molybdic acid, nickel molybdic acid, phosphomolybdovanadium heteropoly acid, phosphotungstic acid, silicotungstic acid, borotungstic acid, titanium tungstic acid, nickel tungstic acid, antimony tungstic acid, platinum tungstic acid or phosphotungstovanadic heteropoly acid.
7. The composition of claim 4, wherein the solvent is at least one selected from the group consisting of water, methanol, ethanol, propanol, N-butanol, isobutanol, N-pentanol, cyclohexanol, acetone, cyclohexanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
8. The non-bleeding halogen-free flame retardant composition according to claim 1 or 2, wherein the piperazine inorganic acid salt is one or more of piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, piperazine borate, piperazine silicotungstate, piperazine zinc stannate complex salt, and piperazine phosphotungstate.
9. The bleed-free, halogen-free, flame retardant composition of claim 8 wherein the metal oxide is one or more of magnesium oxide, zinc oxide, titanium dioxide, tin dioxide, and antimony trioxide; the metal salt is more than one of magnesium silicate, aluminum silicate, zinc borate, zinc stannate, sodium antimonate, lithium titanate, calcium titanate, magnesium titanate and barium titanate; the organic silicon material is more than one of silane coupling agent, silicone oil and liquid silicone rubber.
10. The composition as claimed in claim 9, wherein the silane coupling agent has the formula RSiX3Wherein R is amino, mercapto, vinyl, epoxy, cyano or methacryloxy, and X is methoxy or ethoxy; the viscosity of the silicone oil is 500-5000 mm at 25 DEG C2Dimethyl polysiloxane, methyl hydrogenpolysiloxane, amino modified dimethyl polysiloxane or epoxy modified dimethyl polysiloxane.
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