CN104311981A - Halogen-free flame-retardant EVA (ethylene vinyl-acetate) composite material - Google Patents
Halogen-free flame-retardant EVA (ethylene vinyl-acetate) composite material Download PDFInfo
- Publication number
- CN104311981A CN104311981A CN201410541370.6A CN201410541370A CN104311981A CN 104311981 A CN104311981 A CN 104311981A CN 201410541370 A CN201410541370 A CN 201410541370A CN 104311981 A CN104311981 A CN 104311981A
- Authority
- CN
- China
- Prior art keywords
- aliphatic amide
- halogen
- hexachlorocyclotriphosphazene
- matrix material
- trioxa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a halogen-free flame-retardant EVA (ethylene vinyl-acetate) composite material which comprises ethylene vinyl-acetate and a composite flame retardant in a mass ratio of 3:2. The composite flame retardant is prepared from ammonium polyphosphate, tri(1-oxo-1-phospha-2,6,7-trioxa bicycle[2,2,2]octane-4-methylene) phosphate and a fatty amine substituted phosphonitrile derivative, wherein the mass ratio of ammonium polyphosphate and tri(1-oxo-1-phospha-2,6,7-trioxa bicycle[2,2,2]octane-4-methylene) phosphate is 2:1, and the mass ratio of the fatty amine substituted phosphonitrile derivative and the mixture of ammonium polyphosphate and tri(1-oxo-1-phospha-2,6,7-trioxa bicycle[2,2,2] octane-4-methylene) phosphate is (1-15):(25-39). The composite material disclosed by the invention has good comprehensive flame retardance and mechanical properties. In the processing and preparing process, the compatibility and processibility of the composite flame retardant and EVA are good and the composite material can be widely applied as cable raw materials and the like.
Description
Technical field
The present invention relates to a kind of bittern-free flame-proof material, specifically a kind of halogen-free flameproof EVA matrix material of satisfactory mechanical property.
Background technology
Ethylene-vinyl acetate copolymer (EVA) itself belongs to and compares combustible polymers material, its limiting oxygen index(LOI) only 17.0-19.0%, with the increase of vinyl acetate content, limiting oxygen index(LOI) increases to some extent, but charring rate is low, molten drop is produced, so all require to carry out flame-retardant modified to it in a lot of application scenario during burning.At present, mainly additive flame retardant is adopted to ethylene-vinyl acetate fire-retardant finish both at home and abroad.According to " advanced polymer processing techniques " (Polymers for Advanced Technologies, 2011, introduce 22: 379-394), use and can be used in the Halogen additive flame retardant of flame-proof ethylene-vinyl acetate, hydroxide flame retardant the most often uses, it is inexpensive, nontoxic, presses down cigarette.Hydroxide flame retardant, mainly by completely cutting off flame by Thermal release water vapour, dilution oxygen, decomposing metal oxide promoted polymkeric substance condensed ring charing when burning of generation simultaneously, playing solid phase fire retardation.But while interpolation hydroxide flame retardant reaches fire-retardant object, hydroxide flame retardant can worsen the mechanical property of ethylene-vinyl acetate composite material.
Phosphonitrile and derivative thereof are a class Halogen, environmentally friendly nitrogen-phosphorus flame retardant, and because it has, thermostability is higher, only containing a series of advantages such as P, N two kinds of ignition-proof elements, the high and low poison of flame retarding efficiency, studied person expands Study and appliance widely.At present, the ring phosphazene flame retardant kind being added on plastic polymer mainly contains: 1. hydroxyl ring three phosphonitrile fire retardant, 2. amino-contained ring three phosphonitrile fire retardant, 3. containing double bond ring three phosphonitrile fire retardant.Wherein amino-contained ring three phosphonitrile is a kind of phosphazene compound simultaneously possessing synthesis and application performance.At present, in industry, scholar is aniline basic ring three phosphonitrile for studying more in amino-contained ring three phosphonitrile fire retardant, as CN101597308 discloses the preparation method of a kind of hexaaniline cyclotriphosphazene and halogen-free flame retardant epoxy resin composition; Its technique adds in reaction unit by organic solvent, hexachlorocyclotriphosphazene, aniline, acid binding agent; stir; pass into nitrogen protection, be heated to 50-120 DEG C, in reaction unit, add Tetrabutyl amonium bromide catalyzer; reaction 5-16 h; suction filtration after cooling, carries out underpressure distillation to filtrate, evaporative removal organic solvent; gained target compound product is dry, obtain six phenylamino basic ring three phosphonitriles.This compound is for the preparation of EMC Halogen matrix material, and its excellent fireproof performance, charring rate are high, toxicity is little, corrodibility is little and preparation method is simple; But, this based flame retardant and conventional inorganic and organic fire-retardant system similar, join the mechanical mechanics property that EVA plastic polymer easily worsens its matrix material, and its poor compatibility, melting range is wide, purity is low, fusing point is high, in plastic polymer (as EVA, PP), use its processing characteristics poor.At present, for overcoming this problem in industry, improve it to the processing of plastic polymer material and mechanical mechanics property often through the addition reducing phosphazene flame retardant, simultaneously, its flame retardant effect will reduce.
Summary of the invention
Object of the present invention is just to provide a kind of halogen-free flameproof EVA matrix material, adds in EVA plastic matrix to solve existing fire retardant, there is poor processability, easily worsens the problem of the mechanical mechanics property of matrix material while can reaching flame retardant effect.
The object of the invention is to be achieved through the following technical solutions: a kind of halogen-free flameproof EVA matrix material, comprise ethylene-vinyl acetate (EVA) and composite flame-retardant agent, the mass ratio of described ethylene-vinyl acetate and composite flame-retardant agent is 3 ﹕ 2, described composite flame-retardant agent is by ammonium polyphosphate (APP), three (1-oxo-1-phosphas-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) phosphoric acid ester replaces phosphazene derivative composition with (Trimer) and aliphatic amide, polyphosphoric acid amine and three (1-oxo-1-phospha-2 in described composite flame-retardant agent, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) mass ratio of phosphoric acid ester is 2 ﹕ 1, described aliphatic amide replace phosphazene derivative with by described polyphosphoric acid amine and three (1-oxo-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1-15 ﹕ 25-39, the chemical general formula that described aliphatic amide replaces phosphazene derivative is:
The R that described aliphatic amide replaces in phosphazene derivative chemical general formula is 7 or 11.
The mass ratio preferably 1 ﹕ 3-19 of the mixture that described aliphatic amide replacement phosphazene derivative and described polyphosphoric acid amine and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester form.
In described halogen-free flameproof EVA matrix material, the preparation method of aliphatic amide replacement phosphazene derivative is as follows:
A hexachlorocyclotriphosphazene and acid binding agent are dissolved in organic solvent by (), pass into N
2protection, stirs, obtains mixed solution at temperature is 50-80 DEG C; In described mixed solution, drip aliphatic amide while stirring, after dropwising in 0.5-2h at 50-80 DEG C back flow reaction 9-12h, obtain reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative.
Described halogen-free flameproof EVA matrix material, is obtained by following preparation method:
A hexachlorocyclotriphosphazene and acid binding agent are dissolved in organic solvent by (), pass into N
2protection, stirs 5-10 min, obtains Homogeneous phase mixing liquid at temperature is 50-80 DEG C; In described mixed solution, drip aliphatic amide while stirring, after dropwising in 0.5-2h at 50-80 DEG C back flow reaction 9-12h, obtain reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative;
C described aliphatic amide is replaced phosphazene derivative and ammonium polyphosphate, three (1-oxo-1-phosphas-2 by (), 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, be that 2 ﹕ 3 mix in mass ratio by described composite flame-retardant agent and ethylene-vinyl acetate, mixing 10-20 min at temperature is 120-130 DEG C, pressing plate or granulation, obtain halogen-free flameproof EVA matrix material; Polyphosphoric acid amine and three (1-oxo-1-phospha-2 in described composite flame-retardant agent, 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of phosphoric acid ester is 2 ﹕ 1, described aliphatic amide replaces phosphazene derivative and described polyphosphoric acid amine and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1-15 ﹕ 25-39.
The technique of step (a) described in above-mentioned preparation technology also can be: the technique of described step (a) is replaced by: be dissolved in by hexachlorocyclotriphosphazene in organic solvent, passes into N
2protection, stir at temperature is 50-80 DEG C, drip acid binding agent and aliphatic amide while stirring, dropwise in 0.5-2h in hexachlorocyclotriphosphazene solution, at 50-80 DEG C, back flow reaction 9-12 h, obtains reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane.
In above-mentioned preparation technology, described in step (a), acid binding agent is triethylamine.
In above-mentioned preparation technology, organic solvent described in step (a) is any one in dioxane or tetrahydrofuran (THF).
When in above-mentioned preparation technology, described in step (a), aliphatic amide is amino dodecane, the mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is preferably 1 ﹕ 10 ﹕ 6.0.
When in above-mentioned preparation technology, described in step (a), aliphatic amide is n-octyl amine, the mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is preferably 1 ﹕ 6 ﹕ 6.6.
In above-mentioned preparation technology, the mass volume ratio of hexachlorocyclotriphosphazene and organic solvent described in step (a) is 1: 8-50, when dripping aliphatic amide in described mixed solution, first described aliphatic amide is dissolved in appropriate dioxane or tetrahydrofuran (THF), then drips.
In above-mentioned preparation technology when the aliphatic amide in step (a) is amino dodecane, described separate targets product the technique be dried are: by the reaction solution suction filtration after leaving standstill, obtain white precipitate, the described organic solvent of white precipitate is rinsed, use deionized water rinsing again, vacuum-drying 12-20 h at precipitation after flushing is placed in 50-90 DEG C, obtains six-amino dodecane base-ring triphosphine nitrile (H-12).
In above-mentioned preparation technology when the aliphatic amide in step (a) is n-octyl amine, separate targets product in described step (b) the technique be dried are: by the reaction solution suction filtration after leaving standstill, filtrate rotary evaporation is obtained dope, vacuum-drying 12-20 h at described dope is placed in 50-90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8).
The described granulation of above-mentioned steps (c) mixing rear material is joined twin screw extruder granulate, its twin screw extruder is set to 120 DEG C, 130 DEG C, 130 DEG C, 120 DEG C from spout, the second heating zone, the 3rd heating zone, the 4th heating zone respectively to the temperature of head, and screw speed is set to 40 r/min.
The described making sheet of above-mentioned steps (c) refers to that under 12-13MPa, hot pressing 10-20min, colds pressing afterwards again, obtains fire-retardant EVA sheet material by the material after mixing on 130-140 DEG C of vulcanizing press.
The present invention have selected amino dodecane in aliphatic amide and n-octyl amine, have employed specific feed composition ratio and processing condition, under the condition of catalyst-free, replace hexachlorocyclotriphosphazene, prepared melting range narrow range, purity is high, consistency good and six-amino dodecane of excellent fireproof performance base-ring triphosphine nitrile and six-n-octyl amine base-ring triphosphine nitrile; The present invention is by these two kinds of phosphonitrile fire retardants of preparation and APP, Trimer are composite in specific proportions obtains composite flame-retardant agent, is then added in EVA by suitable proportion by composite flame-retardant agent, then prepares matrix material by scientific and reasonable method.Prove by experiment, this EVA matrix material not only has the vertical combustion performance of higher limiting oxygen index(LOI) and resistance to molten drop, but also matrix material viscosity of melt in the course of processing can be made low, good processability, the good dispersity of component, thus realize comprehensive flame retardant properties good while, reach the mechanical mechanics property object that fracture of composite materials elongation is high, tensile strength is large.
The present invention obtains good effect, the first is the interpolation of freshly prepd two kinds of phosphonitrile fire retardants, the long fat chain structure of described aliphatic amide replacement phosphazene derivative fire retardant can reduce the fusing point of fire retardant, make fire retardant under the processing temperature of macromolecular material EVA in molten state, and then reduce the viscosity of melt, promote the dispersion of fire retardant in macromolecule matrix, thus reach and improve Flame Retardancy energy, physical and mechanical properties and processing characteristics, it two is the proportionings being that in composite flame-retardant agent, each component is scientific and reasonable, and the conditional parameter of suitable complete processing makes the EVA matrix material finally preparing excellent performance.
Simultaneously, the successful preparation of the present invention's two kinds of aliphatic amides replacement phosphazene derivatives overcomes the problem that the product caused owing to there is embedding problem in the preparation process of fatty amido replacement hexachlorocyclotriphosphazene all the time in industry is impure, productive rate is low, cannot apply.
In a word, EVA matrix material prepared by the present invention not only has good comprehensive flame retardant resistance and mechanical mechanics property, and in processing preparation process, the consistency of composite flame-retardant agent and EVA and good processability, can be used as cable raw material etc. and carry out suitability for industrialized production and widespread use.
Accompanying drawing explanation
Fig. 1 is the Infrared Characterization figure of six-amino dodecane base-ring triphosphine nitrile prepared by embodiment 1; Its 3239cm
-1for the stretching vibration of N-H; 2956-2850cm
-1place is C-H stretching vibration; 1468cm
-1locate as C-H asymmetric bending vibration; 1378cm
-1the symmetric curvature vibration that place is C-H in methyl; 1240cm
-1place is the hexa-atomic skeletal vibration of phosphine nitrile; 1180,1103cm
-1place is P=N stretching vibration; 904cm
-1place is P-N stretching vibration; 721cm
-1place is-(CH
2)
n-middle C-H out-of-plane deformation vibration;
Fig. 2 is the hydrogen spectrum phenogram of six-amino dodecane base-ring triphosphine nitrile prepared by embodiment 1; The theoretical number ratio of four kinds of hydrogen in hydrogen spectrum should be a:b:c:d=1:1:9:1.5; Actual specific a:b:c:d=1:0.95:9.21:1.60 and theory than basically identical, so can target product be thought;
Fig. 3 is the phosphorus spectrum nuclear-magnetism figure of six-amino dodecane base-ring triphosphine nitrile prepared by embodiment 1; Phosphorus spectrum nuclear-magnetism only has a kind of phosphorus at 14.09 places, consistent with theory;
Fig. 4 is the Infrared Characterization figure of six-n-octyl amine base-ring triphosphine nitrile prepared by embodiment 6; 3242cm
-1for the stretching vibration of N-H; 2960-2852cm
-1place is C-H stretching vibration; 1466cm
-1locate as C-H asymmetric bending vibration; 1376cm
-1the symmetric curvature vibration that place is C-H in methyl; 1241cm
-1place is the hexa-atomic skeletal vibration of phosphine nitrile; 1191,1100cm
-1place is P=N stretching vibration; 930cm
-1place is P-N stretching vibration; 721cm
-1place is-(CH
2)
n-middle C-H out-of-plane deformation vibration;
Fig. 5 is the hydrogen spectrum phenogram of six-n-octyl amine base-ring triphosphine nitrile prepared by embodiment 6; The theoretical number ratio of four kinds of hydrogen in hydrogen spectrum should be a:b:c:d=1:1:5:1.5; Actual specific a:b:c:d=1:0.95:4.78:1.41 and theory than basically identical, so can target product be thought;
Fig. 6 is the phosphorus spectrum nuclear-magnetism figure of six-n-octyl amine base-ring triphosphine nitrile prepared by embodiment 6; Phosphorus spectrum nuclear-magnetism only has a kind of phosphorus at 13.77 places, consistent with theory;
Fig. 7 is the SEM figure that embodiment 3 prepares material brittle failure end face in liquid nitrogen, fire retardant being uniformly dispersed in the sample to which, and the interface between fire retardant and EVA matrix is fuzzy, and the consistency of illustrative material is improved;
Fig. 8 is the SEM figure that embodiment 9 prepares material brittle failure end face in liquid nitrogen, fire retardant being uniformly dispersed in the sample to which, and the interface between fire retardant and EVA matrix is fuzzy, and the consistency of illustrative material is improved;
Fig. 9 is the SEM figure that comparative example 1 prepares material brittle failure end face in liquid nitrogen;
Figure 10 is the SEM figure that comparative example 2 prepares material brittle failure end face in liquid nitrogen, and fire retardant APP and the dispersion of Trimer mixture in EVA matrix present certain agglomeration, and consistency is poor;
Figure 11 is that embodiment 3,4 and comparative example 1,2 prepare the complex viscosity phenogram of sample at 155 DEG C, show the characteristic that laboratory sample shows shear shinning in figure, the viscosity of matrix material disclosed by the invention reduces along with the increase of six-amino dodecane base-ring triphosphine nitrile (H-12) addition in whole frequency field;
Figure 12 is that embodiment 3,4 and comparative example 1,2 prepare the storage modulus phenogram of sample at 155 DEG C, from figure, laboratory sample shows composite flame-retardant agent and can reduce the viscosity of EVA material and improve the mobility of melt, thus improves the flame retardant resistance of matrix material;
Figure 13 is that embodiment 8,9 and comparative example 1,2 prepare the complex viscosity phenogram of sample at 155 DEG C, show the characteristic that laboratory sample shows shear shinning in figure, the viscosity of matrix material disclosed by the invention reduces along with the increase of six-n-octyl amine base-ring triphosphine nitrile (H-8) addition in whole frequency field;
Figure 14 is that embodiment 8,9 and comparative example 1,2 prepare the storage modulus phenogram of sample at 155 DEG C, from figure, laboratory sample shows composite flame-retardant agent and can reduce the viscosity of EVA material and improve the mobility of melt, thus improves the flame retardant resistance of matrix material.
Embodiment
Embodiment is for further describing the present invention below, but does not limit the present invention in any form.
Embodiment 1
(1) by 3.00g(0.0086 mol) hexachlorocyclotriphosphazene and 8.73g(0.086mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 100ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 80 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 50ml containing 9.546g(0.0516mol) dioxane solution of amino dodecane, drip while stirring, 2h drips off, after dropwising at 80 DEG C back flow reaction 12h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, decompress filter obtains white precipitate, first rinse with dioxane, then use a large amount of deionized water rinsing, finally precipitation is put into dry 12 h of vacuum drying oven of 80 DEG C, obtain product six-amino dodecane base-ring triphosphine nitrile, productive rate is 79.74%, and melting range is 101-104 DEG C, molecular formula: P
3n
9c
72h
156(H-12); Chemical formula is:
(3) by 1g six-amino dodecane base-ring triphosphine nitrile (H-12) and 26 g ammonium polyphosphates (APP), 13g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester (Trimer) mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate (EVA), be mixing 20min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
The Infrared Characterization figure of the six-amino dodecane base prepared in above-described embodiment (2) step-ring triphosphine nitrile, hydrogen compose phenogram and phosphorus spectrum nuclear-magnetism figure is shown in shown in Fig. 1, Fig. 2 and Fig. 3; Nitrogen in its each elemental analysis, carbon, hydrogen richness test data are in table 1.
The table 1 six-amino dodecane base-nitrogen of ring triphosphine nitrile, carbon, hydrogen richness test data
As shown in table 1: N:C:H theoretical content ratio be 10.16: 69.68: 12.67, the content of actual N:C:H is than being 9.75:66.63:12.38, basic consistent with theoretical value, and illustrating further the middle compound prepared of step (2) is target product.
Embodiment 2
(1) by 3.00g(0.0086 mol) hexachlorocyclotriphosphazene and 8.73g(0.086mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 100ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 50 DEG C by round-bottomed flask, magnetic agitation 8 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 50ml containing 9.546g(0.0516mol) dioxane solution of amino dodecane, drip while stirring, 2h drips off, after dropwising at 80 DEG C back flow reaction 10h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, decompress filter obtains white precipitate, first rinse with dioxane, use a large amount of deionized water rinsing again, finally precipitation is put into dry 12 h of vacuum drying oven of 80 DEG C, obtain product six-amino dodecane base-ring triphosphine nitrile, productive rate is 79.54%, and melting range is 101-104 DEG C;
(3) by 2g six-amino dodecane base-ring triphosphine nitrile and 25.33 g ammonium polyphosphates, 12.67g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 15min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 130 DEG C, hot pressing 15min under 12MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 3
(1) by 3.00g(0.0086 mol) hexachlorocyclotriphosphazene is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 100ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 80 DEG C by round-bottomed flask, magnetic agitation 8 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 50ml containing 9.546g(0.0516mol) amino dodecane and 8.73g(0.086mol) dioxane solution of triethylamine, drip while stirring, 1h drips off, after dropwising at 75 DEG C back flow reaction 12h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, decompress filter obtains white precipitate, first rinse with dioxane, use a large amount of deionized water rinsing again, finally precipitation is put into dry 12 h of vacuum drying oven of 80 DEG C, obtain product six-amino dodecane base-ring triphosphine nitrile, productive rate is 81.24%, and melting range is 101-104 DEG C;
(3) by 5g six-amino dodecane base-ring triphosphine nitrile and 23.33 g ammonium polyphosphates, 11.67g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 10min on the duplex roller of 120 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 20min under 12MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 4
(1) by 3.00g(0.0086 mol) hexachlorocyclotriphosphazene and 8.73g(0.086mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 100ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 80 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 50ml containing 9.546g(0.0516mol) dioxane solution of amino dodecane, drip while stirring, 1 h drips off, after dropwising at 80 DEG C back flow reaction 9h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, decompress filter obtains white precipitate, first rinses with dioxane, then uses a large amount of deionized water rinsing, finally precipitation is put into dry 12 h of vacuum drying oven of 80 DEG C, obtains product six-amino dodecane base-ring triphosphine nitrile; Productive rate is 82.55%, and melting range is 100-104 DEG C;
(3) by 10g six-amino dodecane base-ring triphosphine nitrile and 20 g ammonium polyphosphates, 10g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 15min on the duplex roller of 125 DEG C in temperature, on the vulcanizing press of 140 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 5
(1) by 3.00g(0.0086 mol) hexachlorocyclotriphosphazene is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 100ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 65 DEG C by round-bottomed flask, magnetic agitation 5 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 50ml containing 9.546g(0.0516mol) amino dodecane and 8.73g(0.086mol) dioxane solution of triethylamine, drip while stirring, 1h drips off, after dropwising at 50 DEG C back flow reaction 12h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, decompress filter obtains white precipitate, first rinses with dioxane, then uses a large amount of deionized water rinsing, finally precipitation is put into dry 18 h of vacuum drying oven of 60 DEG C, obtains product six-amino dodecane base-ring triphosphine nitrile; Productive rate is 79.88%, and melting range is 100-103 DEG C;
(3) by 15g six-amino dodecane base-ring triphosphine nitrile and 16.67 g ammonium polyphosphates, 8.33g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 20min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 6
(1) by 5.8g(0.0167 mol) hexachlorocyclotriphosphazene and 10.1g(0.10mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 50ml tetrahydrofuran (THF) (with condensing works), passes into N
2protection, puts into the oil bath pan of 50 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 14.19g(0.11mol) n-octyl amine, drip while stirring, drip off with 1h, after dropwising at 80 DEG C back flow reaction 12h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leave standstill to layering, by leave standstill after reaction solution suction filtration, (U.S. TA company AR-2000EX type rotary evaporation rheometer is utilized to test filtrate rotary evaporation, temperature 50 C, 20 minutes to 40 minutes time, to going out without obvious liquid evaporation) obtain dope, vacuum-drying 20 h at described dope is placed in 90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8); Productive rate is 89.52%, and melting range is 85-92 DEG C, and its chemical formula is:
(3) by 1g six-n-octyl amine base-ring triphosphine nitrile and 26 g ammonium polyphosphates, 13g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 20min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
The Infrared Characterization figure of the six-n-octyl amine base prepared in the present embodiment (2) step-ring triphosphine nitrile, hydrogen compose phenogram and phosphorus spectrum nuclear-magnetism figure is shown in shown in Fig. 1, Fig. 2 and Fig. 3; Nitrogen in its each elemental analysis, carbon, hydrogen richness test data are in table 1.
The table 2 six-n-octyl amine base-nitrogen of ring triphosphine nitrile, carbon, hydrogen richness test data
As shown in table 2: N:C:H theoretical content ratio be 13.94: 63.74: 12.04, the content of actual N:C:H is than being 12.28:61.91:11.06, basic consistent with theoretical value, and illustrating further the middle compound prepared of step (2) is target product.
Embodiment 7
(1) by 5.8g(0.0167 mol) hexachlorocyclotriphosphazene and 10.1g(0.01mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 50ml dioxane (with condensing works), passes into N
2protection, puts into the oil bath pan of 80 DEG C by round-bottomed flask, magnetic agitation 8 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 14.19g(0.11mol) n-octyl amine, drip while stirring, 1h drips off, after dropwising at 80 DEG C back flow reaction 10h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leaves standstill to layering, by leave standstill after reaction solution suction filtration, filtrate rotary evaporation is obtained dope, vacuum-drying 20 h at described dope is placed in 90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8); Productive rate is 89.40%, and melting range is 86-91 DEG C;
(3) by 2g six-n-octyl amine base-ring triphosphine nitrile and 25.33 g ammonium polyphosphates, 12.67g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 15min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 8
(1) by 5.8g(0.0167 mol) hexachlorocyclotriphosphazene and 10.1g(0.10mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 50ml tetrahydrofuran (THF) (with condensing works), passes into N
2protection, puts into the oil bath pan of 50 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 14.19g(0.11mol) n-octyl amine, drip while stirring, drip off with 1h, after dropwising at 50 DEG C back flow reaction 18h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leaves standstill to layering, by leave standstill after reaction solution suction filtration, filtrate rotary evaporation is obtained dope, vacuum-drying 20 h at described dope is placed in 90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8); Productive rate is 89.50%, and melting range is 85-91 DEG C;
(3) by 5g six-n-octyl amine base-ring triphosphine nitrile and 23.33 g ammonium polyphosphates, 11.67g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 10min on the duplex roller of 120 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 9
(1) by 5.8g(0.0167 mol) hexachlorocyclotriphosphazene and 10.1g(0.10mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 50ml tetrahydrofuran (THF) (with condensing works), passes into N
2protection, puts into the oil bath pan of 90 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 14.19g(0.11mol) n-octyl amine, drip while stirring, drip off with 1h, after dropwising at 50 DEG C back flow reaction 18h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leaves standstill to layering, by leave standstill after reaction solution suction filtration, filtrate rotary evaporation is obtained dope, vacuum-drying 20 h at described dope is placed in 90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8); Productive rate is 93.24%, and melting range is 85-90 DEG C;
(3) by 10g six-n-octyl amine base-ring triphosphine nitrile and 20 g ammonium polyphosphates, 10g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 15min on the duplex roller of 125 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Embodiment 10
(1) by 5.8g(0.0167 mol) hexachlorocyclotriphosphazene and 10.1g(0.10mol) triethylamine is dissolved in the oblique three mouthfuls of round-bottomed flasks filling 50ml tetrahydrofuran (THF) (with condensing works), passes into N
2protection, puts into the oil bath pan of 90 DEG C by round-bottomed flask, magnetic agitation 10 min makes it dissolve to mix, obtain Homogeneous phase mixing liquid; Now, in mixed solution, dropwise add 14.19g(0.11mol) n-octyl amine, drip while stirring, drip off with 1h, after dropwising at 50 DEG C back flow reaction 18h, obtain reaction solution;
(2) reaction solution is cooled to room temperature, leaves standstill to layering, by leave standstill after reaction solution suction filtration, filtrate rotary evaporation is obtained dope, vacuum-drying 20 h at described dope is placed in 90 DEG C, obtains six-n-octyl amine base-ring triphosphine nitrile (H-8);
(3) by 15g six-n-octyl amine base-ring triphosphine nitrile and 16.67 g ammonium polyphosphates, 8.33g tri-(1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, this composite flame-retardant agent is mixed with 60g ethylene-vinyl acetate, be mixing 20min on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing 10min under 13MPa, cold pressing afterwards, obtain halogen-free flameproof EVA matrix material.
Comparative example 1
Get 100g ethylene-vinyl acetate, be mixing on the duplex roller of 130 DEG C in temperature, then on the vulcanizing press of 135 DEG C, hot pressing under 13MPa, cold pressing afterwards again and obtain the different model of thickness, finally on universal sampling machine, sample preparation obtains EVA test bars.
Comparative example 2
Get 60 g ethylene-vinyl acetates and 26.67 g ammonium polyphosphates and 13.33 g tri-(1-oxo-1-phosphas-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixes, and is then mixing on the duplex roller of 130 DEG C in temperature, on the vulcanizing press of 135 DEG C, hot pressing under 13MPa, colds pressing afterwards again and obtains model, and finally on universal sampling machine, sample preparation obtains fire-retardant EVA test bars.
Embodiment 11
Detect the properties of the present invention and the material prepared by comparative example.
Experimental technique:
(1), according to GB/T1040.3-2006, characterize its elongation at break and tensile strength thereof with electronic tension tester, detected result is in table 1.
(2), limiting oxygen index(LOI) (LOI): in nitrogen oxygen mixed gas, maintain minimum oxygen percentage ratio needed for sample combustion, be used for the flame retardant effect of characterizing sample.By ASTM D2863-2000 standard, use HC-2 oxygen index instrument (Jiangning, Nanjing analytical instrument factory) to measure, specimen size 140mm × 6mm × 3mm, detected result is in table 1.
(3), vertical combustion grade: vertical combustion test adopts CZF-3 type horizontal vertical burning determinator (analytical instrument factory of Jiangning county), test sample with reference to GB GB/T2408-1996, sample size is 130 mm × 3, mm × 10 mm.Batten is vertically fixed on sample holder; Adjustment flame height is 20mm, applies flame time 10s, anneal and record primary flaming combustion time t1 sample first time; After flaming combustion is extinguished, carry out second time and apply flame time 10s, anneal and record second time flaming combustion time t2 and glowing time t3, and recording the absorbent cotton whether having dropping to ignite below, detected result is in table 1.
(4), EVA matrix material carries out observation and analysis by Japanese JSM-7500F scanning electronic microscope.
(5), infrared analysis completes on the tensor 27 type infrared tester of German Brooker company, take KBr as background, and the mass ratio of sample and KBr is that the ratio of 1:100 carries out grinding, test after compressing tablet; Hydrogen spectrum and phosphorus spectrum nuclear magnetic data are tested on the ADVANCE III 600 type nuclear-magnetism tester of German Brooker company, take deuterochloroform as the test that solvent carries out; Rheological data utilizes U.S. TA-AR2000EX type rotational rheometer, carries out mensuration and obtain at 155 DEG C.
Detected result:
Table 3 product of the present invention is to the fire-retardant of fire-retardant EVA and Effect on Mechanical Properties
As shown in Table 3, material limits oxygen index prepared by comparative example 1 only has 19.2%, and belong to inflammable product, and very easily drip when burning, ignite absorbent cotton, do not test by UL-94.After the expanding fire retardant APP adding 40% and Trimer mixture, it is 26.5% that oxygen index significantly improves, and can reach the V-0 level of UL-94, but adding of expanding fire retardant APP and Trimer makes the tensile strength of EVA and elongation at break greatly reduce.When preparing matrix material according to formula rate provided by the invention and preparation method, flame retardant effect and the mechanics of machinery over-all properties of embodiment 3 and embodiment 9 resulting materials are best.
Claims (10)
1. a halogen-free flameproof EVA matrix material, it is characterized in that, comprise ethylene-vinyl acetate and composite flame-retardant agent, the mass ratio of described ethylene-vinyl acetate and composite flame-retardant agent is 3 ﹕ 2, described composite flame-retardant agent is by ammonium polyphosphate, three (1-oxo-1-phosphas-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) phosphoric acid ester and aliphatic amide replace phosphazene derivative composition, polyphosphoric acid amine and three (1-oxo-1-phospha-2 in described composite flame-retardant agent, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) mass ratio of phosphoric acid ester is 2 ﹕ 1, described aliphatic amide replace phosphazene derivative with by described polyphosphoric acid amine and three (1-oxo-1-phospha-2, 6, 7-trioxa-l-phosphabicyclo [2, 2, 2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1-15 ﹕ 25-39, the chemical general formula that described aliphatic amide replaces phosphazene derivative is:
R in described chemical general formula is 7 or 11.
2. halogen-free flameproof EVA matrix material according to claim 1, it is characterized in that, described aliphatic amide replace phosphazene derivative with by described polyphosphoric acid amine and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1 ﹕ 3-19.
3. halogen-free flameproof EVA matrix material according to claim 1, is characterized in that, the preparation method that described aliphatic amide replaces phosphazene derivative is:
A hexachlorocyclotriphosphazene and acid binding agent are dissolved in organic solvent by (), pass into N
2protection, stirs, obtains mixed solution at temperature is 50-80 DEG C; In described mixed solution, drip aliphatic amide while stirring, after dropwising in 0.5-2h at 50-80 DEG C back flow reaction 9-12h, obtain reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative.
4. halogen-free flameproof EVA matrix material according to claim 1, is characterized in that, the preparation method that described aliphatic amide replaces phosphazene derivative is:
A hexachlorocyclotriphosphazene is dissolved in organic solvent by (), pass into N
2protection, stir at temperature is 50-80 DEG C, in hexachlorocyclotriphosphazene solution, drip acid binding agent and aliphatic amide while stirring, after dropwising in 0.5-2h at 50-80 DEG C back flow reaction 9-12h, obtain reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative.
5. halogen-free flameproof EVA matrix material according to claim 1, it is characterized in that, its preparation method comprises the following steps:
A hexachlorocyclotriphosphazene and acid binding agent are dissolved in organic solvent by (), pass into N
2protection, stirs 5-10 min, obtains Homogeneous phase mixing liquid at temperature is 50-80 DEG C; In described mixed solution, drip aliphatic amide while stirring, after dropwising in 0.5-2h at 50-80 DEG C back flow reaction 9-12h, obtain reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative;
C described aliphatic amide is replaced phosphazene derivative and ammonium polyphosphate, three (1-oxo-1-phosphas-2 by (), 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, be that 2 ﹕ 3 mix in mass ratio by described composite flame-retardant agent and ethylene-vinyl acetate, mixing 10-20 min at temperature is 120-130 DEG C, pressing plate or granulation, obtain halogen-free flameproof EVA matrix material; Polyphosphoric acid amine and three (1-oxo-1-phospha-2 in described composite flame-retardant agent, 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of phosphoric acid ester is 2 ﹕ 1, described aliphatic amide replace phosphazene derivative with by described polyphosphoric acid amine and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1-15 ﹕ 25-39.
6. halogen-free flameproof EVA matrix material according to claim 1, it is characterized in that, its preparation method comprises the following steps:
A hexachlorocyclotriphosphazene is dissolved in organic solvent by (), pass into N
2protection, stir at temperature is 50-80 DEG C, drip acid binding agent and aliphatic amide while stirring, dropwise in 0.5-2h in hexachlorocyclotriphosphazene solution, at 50-80 DEG C, back flow reaction 9-12 h, obtains reaction solution; The mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6-10 ﹕ 6.0-6.6, and described aliphatic amide is the one in n-octyl amine or amino dodecane;
B described reaction solution cools by (), stratification, and separate targets product is also dried, and obtains aliphatic amide and replaces phosphazene derivative;
C described aliphatic amide is replaced phosphazene derivative and ammonium polyphosphate, three (1-oxo-1-phosphas-2 by (), 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) phosphoric acid ester mixing composition composite flame-retardant agent, be that 2 ﹕ 3 mix in mass ratio by described composite flame-retardant agent and ethylene-vinyl acetate, mixing 10-20 min at temperature is 120-130 DEG C, pressing plate or granulation, obtain halogen-free flameproof EVA matrix material; Polyphosphoric acid amine and three (1-oxo-1-phospha-2 in described composite flame-retardant agent, 6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of phosphoric acid ester is 2 ﹕ 1, described aliphatic amide replace phosphazene derivative with by described polyphosphoric acid amine and three (1-oxo-1-phospha-2,6,7-trioxa-l-phosphabicyclo [2,2,2] octane-4-methylene radical) mass ratio of mixture of phosphoric acid ester composition is 1-15 ﹕ 25-39.
7. the halogen-free flameproof EVA matrix material according to claim 3,4,5 or 6, it is characterized in that, acid binding agent described in step (a) is triethylamine.
8. the halogen-free flameproof EVA matrix material according to claim 3,4,5 or 6, is characterized in that, organic solvent described in step (a) is any one in dioxane or tetrahydrofuran (THF).
9. the halogen-free flameproof EVA matrix material according to claim 3,4,5 or 6, is characterized in that, when described in step (a), aliphatic amide is amino dodecane, the mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 10 ﹕ 6.0.
10. the halogen-free flameproof EVA matrix material according to claim 3,4,5 or 6, is characterized in that, when described in step (a), aliphatic amide is n-octyl amine, the mol ratio of described hexachlorocyclotriphosphazene, acid binding agent and aliphatic amide is 1 ﹕ 6 ﹕ 6.6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410541370.6A CN104311981B (en) | 2014-10-14 | 2014-10-14 | A kind of halogen-free flameproof EVA composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410541370.6A CN104311981B (en) | 2014-10-14 | 2014-10-14 | A kind of halogen-free flameproof EVA composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104311981A true CN104311981A (en) | 2015-01-28 |
| CN104311981B CN104311981B (en) | 2016-08-24 |
Family
ID=52367307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410541370.6A Active CN104311981B (en) | 2014-10-14 | 2014-10-14 | A kind of halogen-free flameproof EVA composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104311981B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285989A (en) * | 2020-02-07 | 2020-06-16 | 山东理工大学 | Preparation of high-performance reaction type polyurethane flame retardant compounded by cyclic triphosphazenyl hexaphosphoric acid and derivative thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177370A2 (en) * | 1984-10-05 | 1986-04-09 | Ethyl Corporation | Process for phosphazene trimer purification |
| CN1242784A (en) * | 1997-10-15 | 2000-01-26 | 大塚化学株式会社 | Crosslinked phenoxyphosphazene compounds, flame-retardant, flame-retardant resin compositions, and moldings of flame-retardant resins |
| JP2003128909A (en) * | 2001-10-23 | 2003-05-08 | Asahi Kasei Corp | Flame-retardant thermosetting resin composition |
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
-
2014
- 2014-10-14 CN CN201410541370.6A patent/CN104311981B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0177370A2 (en) * | 1984-10-05 | 1986-04-09 | Ethyl Corporation | Process for phosphazene trimer purification |
| CN1242784A (en) * | 1997-10-15 | 2000-01-26 | 大塚化学株式会社 | Crosslinked phenoxyphosphazene compounds, flame-retardant, flame-retardant resin compositions, and moldings of flame-retardant resins |
| JP2003128909A (en) * | 2001-10-23 | 2003-05-08 | Asahi Kasei Corp | Flame-retardant thermosetting resin composition |
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
Non-Patent Citations (2)
| Title |
|---|
| HARRY R. ALLCOCK AND J. STEVEN RUTT: "Synthesis of Polyphosphazenes with Isothiocyanato, Thiourethane, and Thiourea Side Groups", 《MACROMOLECULES》 * |
| 鲍治宇 等编著: "《膨胀阻燃技术及应用》", 28 February 2005, 哈尔滨工业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285989A (en) * | 2020-02-07 | 2020-06-16 | 山东理工大学 | Preparation of high-performance reaction type polyurethane flame retardant compounded by cyclic triphosphazenyl hexaphosphoric acid and derivative thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104311981B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104292504A (en) | Phosphonitrile fire retardant and preparation method and application thereof | |
| CN104403128B (en) | Preparation method containing the biradical structure phosphonium flame retardants of phosphonitrile/DOPO | |
| Liu et al. | Economical and facile synthesis of a highly efficient flame retardant for simultaneous improvement of fire retardancy, smoke suppression and moisture resistance of epoxy resins | |
| Xu et al. | Synthesis and characterization of a novel epoxy resin based on cyclotriphosphazene and its thermal degradation and flammability performance | |
| CN105542160B (en) | Bicyclo cage shaped macromolecular expansion type flame retardant of one-component phosphorus nitrogen and its preparation method and application | |
| Zhan et al. | Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant | |
| Wang et al. | A new intumescent flame‐retardant: preparation, surface modification, and its application in polypropylene | |
| Wen et al. | One-pot synthesis of a novel s-triazine-based hyperbranched charring foaming agent and its enhancement on flame retardancy and water resistance of polypropylene | |
| Feng et al. | Synergistic effect of a novel triazine charring agent and ammonium polyphosphate on the flame retardant properties of halogen-free flame retardant polypropylene composites | |
| Wang et al. | Synthesis of N-methyl triazine-ethylenediamine copolymer charring foaming agent and its enhancement on flame retardancy and water resistance for polypropylene composites | |
| Feng et al. | Preparation and characterization of a novel oligomeric charring agent and its application in halogen-free flame retardant polypropylene | |
| CN103289084B (en) | Melamine polymer type intumescent flame retardant and preparation method and application thereof | |
| Liu et al. | Preparation, characterization and properties of a halogen‐free phosphorous flame‐retarded poly (butylene terephthalate) composite based on a DOPO derivative | |
| Huang et al. | Synthesis and characterization of a novel charring agent and its application in intumescent flame retardant polypropylene system | |
| CN104311876A (en) | Polymerization type phosphorus-containing flame retardant as well as preparation method and application thereof as epoxy resin flame retardant | |
| Yin et al. | Red phosphorus acts as second acid source to form a novel intumescent-contractive flame-retardant system on ABS | |
| Xiang et al. | A novel halogen‐free intumescent flame retardant containing phosphorus and nitrogen and its application in polypropylene systems | |
| Ba et al. | Synthesis and characterization of a novel charring agent and its application in intumescent flame retardant polyethylene system | |
| CN101429438A (en) | Phosphor-nitrogen expansion type combustion inhibitor and method of producing the same | |
| Liu et al. | An efficient and convenient strategy toward fire safety and water resistance of polypropylene composites through design and synthesis of a novel mono‐component intumescent flame retardant | |
| CN104131463A (en) | Metal ion-modified ammonium polyphosphate and its preparation method and use | |
| CN109679138B (en) | Halogen-free flame retardant melamine polyphosphate borate salt and preparation method and application thereof | |
| CN109627758B (en) | Halogen-free flame-retardant glass fiber reinforced nylon | |
| CN100484993C (en) | Halogen-free flame-proof antistatic modified polypropylene composition useable in electric appliance casing | |
| CN103881333A (en) | Preparation method of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based halogen-free flame retardant polybutylece terephthalate (PBT) resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170717 Address after: LAN Cheng Cun 065000 Langfang city of Hebei province Yongqing Rilan County town (unprocessed Station West) Patentee after: Yongqing Sanli rubber material Co. Ltd. Address before: 071002 East Road, Hebei, Baoding No. 54 Patentee before: Hebei University |