CN103756015A - Hyperbranched triazine charring agent microcapsule flame retardant and preparation method thereof - Google Patents
Hyperbranched triazine charring agent microcapsule flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched triazine charring agent microcapsule flame retardant. The hyperbranched triazine charring agent microcapsule flame retardant is characterized in that a solvent of cyanuric chloride, diamine and disperse cyanuric chloride, a solvent into which diamine is dissolved, a flame retardant, a surfactant and an acid-binding agent are taken as raw materials; the microcapsule flame retardant taking a hyperbranched triazine charring agent as a coating layer and taking the flame retardant as a core is obtained from the cyanuric chloride and the diamine under the action of the acid-binding agent and the surfactant. The hyperbranched triazine charring agent microcapsule flame retardant disclosed by the invention is continuous in reaction process, short in reaction time, and high in production efficiency, the reaction cost is reduced, the flame retardant has better heat stability, high charring property, good dispersion property and good flame retardant property in a polymer; the flame retardant product is good in overall performance; the hyperbranched triazine charring agent microcapsule flame retardant can be widely applied to polymer materials such as plastics, rubber, coatings and adhesives, and has a broad application prospect.
Description
Technical field
The present invention relates to flame retardant area, particularly relating to a kind of hyperbranched triazine char-forming agent is capsule material, halogen-free flame retardants that employing in-situ polymerization take fire retardant as core is coated and preparation method thereof.
Background technology
Fire retardant is to make polymkeric substance and associated materials be difficult for maybe can slow down a kind of auxiliary agent of combustionvelocity of ignition.From whether Halogen can be divided into fire retardant halogen containing flame-retardant and halogen-free flame retardants, wherein halogen containing flame-retardant can produce more smog and poisonous corrosive gas in combustion process, environment is produced and polluted, and European Union has announced " waste electronic andelectrical equipment instruction " (be called for short " WEEE ") for 2003 and two instructions of " about ban use of some harmful substance instruction in electronic electric equipment " (abbreviation " RolS ") ask electronic product to realize heavy metal free, halogen-free flameproof, solvent free for this reason.In view of the serious drawback of halogen containing flame-retardant, halogen-free flame retardants becomes one of important development direction of following fire retardant.
Halogen-free flame retardants is mainly divided into metal hydroxide combustion inhibitor and nitrogen phosphorus compound flame redundant.Wherein nitrogen phosphorus compound flame redundant is not halogen-containing, and this based flame retardant foaming and intumescing when being heated forms the foamed char of porous in combustion processes, can play the effect of heat insulation oxygen barrier; The shortcomings such as but nitrogen phosphorus compound flame redundant exists, and consistency is poor, poor water resistance, poor durability, easy migration.Metal hydroxide combustion inhibitor source is abundant, low price, absorbs heat by decomposition in combustion processes, decomposes the water vapor generating simultaneously inflammable gas is played to diluting effect, when its advantage is to burn, do not produce toxic gas, there is fire-retardant and but the double effects of cigarette.Just because of numerous advantage like this, metal hydroxide combustion inhibitor is widely used among the materials such as plastics, rubber, elastomerics.But metal hydroxides is because polarity is large, incompatible with macromolecular material, in use addition is large, and this will reduce the physicals that worsens material.The dispersion problem that how to solve this type of halogen-free flame retardants is a difficult problem of current fire-retardant research.
Microcapsulary (micro encapsulation) refers to that with natural or synthesized polymer material, solid or liquid composition being rolled into diameter is micron-sized capsule, after developing successfully by the U.S. NCR Corp. fifties, develop into gradually flame retardant area, by fire retardant being carried out to micro encapsulation processing, make it in performance fire retardation, improve water tolerance and the consistency of fire retardant, suppress the untoward reaction that fire retardant occurs in the course of processing.For example German patent DE 2,949,537, DE3,005,253 and DE3,316,880 disclose take P-F or melamine-formaldehyde resin as capsule material ammonium polyphosphate have been carried out to coated method, and the microcapsule flame retardant of preparing has good resistant to hydrolysis, anti-moisture absorption.Chinese Patent Application No. 200910145092.1 has been reported use micro encapsulation fire retardant frie retardant coating, makes frie retardant coating have good ageing resistance and water tolerance.
Find that new to have the capsule material that greater functionality turns use into be a prior development direction of micro encapsulation fire retardant.Research discovery, pyrrolotriazine derivatives is the compound that a large class is rich in tertiary N structure, it not only has good one-tenth charcoal effect and water tolerance, and carbon-collecting source and source of the gas one.In recent years, some pyrrolotriazine derivatives article and patent synthetic and application are constantly published, application number is 200910099717.5 Chinese patent < < containing the triazine char-forming agent of aromatic series chain structure and preparation method thereof > > (mandate publication number is CN101586033A), this patent has been described a kind of triazine char-forming agent containing aromatic series chain structure and preparation method thereof, the long-chain triazine that the Chinese patent < < of application number 201010165863.6 has phosphate ester structure is macromole fire retardant and method > > (application publication number is CN 102234516A) thereof, it is macromole fire retardant and method thereof containing the long-chain triazine with phosphate ester structure that this patent has been described a kind of, the expansibility flame-proof agent of gained is thermally-stabilised good, under high temperature, charring rate is high, expansion character is remarkable.As such macro molecular triazine series carbon forming agent being used for to coated halogen-free flame retardants, will reduce the surface polarity of fire retardant, improve its dispersing property.Although it is so many that triazine char-forming agent has advantages of, but use the coated fire retardant of triazine char-forming agent but so far there are no, for reducing the surface polarity of fire retardant, increase the surface compatability of fire retardant and fire retardant material, improve fire retardant the comprehensive physical property of flame retarding efficiency, dispersiveness and raising fire-retardant product.
Summary of the invention
The present invention is for solving the existing weak point of above-mentioned prior art, propose a kind ofly to use triazine hyperbranched macromolecular carbon forming agent that Heat stability is good, charring rate are high as capsule material, fire retardant is carried out to hyperbranched triazine char-forming agent micro encapsulation fire retardant that micro encapsulation is coated and preparation method thereof, large to solve existing fire retardant polarity, the difficult problems such as dispersing property is poor in fire retardant material, the comprehensive physical property of deterioration fire retardant material.
The object of the invention is to be achieved through the following technical solutions:
The hyperbranched triazine char-forming agent of the present invention micro encapsulation fire retardant, its feature is: described micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, using the cyanuric chloride after disperseing with dissolve after the hyperbranched triazine char-forming agent that obtained under the effect of acid binding agent and tensio-active agent of diamines as coating layer, the micro encapsulation fire retardant using fire retardant as core.
The hyperbranched triazine char-forming agent of the present invention micro encapsulation fire retardant, its feature is also:
The each raw material of described micro encapsulation fire retardant by the proportioning of mass parts is: cyanuric chloride 2～10 mass parts; Disperse the solvent 10-100 mass parts of cyanuric chloride, the solvent 150-580 mass parts of dissolving diamines; Fire retardant 100 mass parts; Tensio-active agent 0.1～10 mass parts; The mol ratio of described diamines and described cyanuric chloride is 2:1-3:1; The mol ratio of described acid binding agent and cyanuric chloride is 3:1-4:1.
By in said ratio gained micro encapsulation fire retardant, the weight ratio of hyperbranched triazine char-forming agent and fire retardant is 4～50:100.
The solvent of described dissolving diamines is selected from one or more in water, acetone, butanone and ethanol to be mixed in any proportion;
The solvent of described dispersion cyanuric chloride is ethanol.
Described diamines is selected from piperazine, quadrol, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 2,6-tolylene diamine, diethyl toluene diamine, hydroxyethylethylene diamine, 3, one or more in 3-diaminodiphenylsulfone(DDS) and 2 methyl pentamethylenediamine are mixed in any proportion.
Described fire retardant is selected from one or more in aluminium hydroxide, magnesium hydroxide, magnesium aluminum double hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, ferronickel double-hydroxide, zinc borate, Zinc aluminate, zinc, zinc hydroxyl stannate, molybdic oxide, molybdenumdisulphide, ammonium molybdate, red phosphorus, ammonium polyphosphate, inorganic hypo-aluminum orthophosphate, organic phospho acid aluminium and triphenylphosphate to be mixed in any proportion.
Described tensio-active agent is selected from OP-10, Brij, cetomacrogol, peregal, Ai Moerfu, carboxylic acid polyoxyethylene ester, Pluronic F68, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, three nonyl ammonio methacrylates, didecyl Dimethy ammonium chloride, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, one or more in distearyl dimethyl ammonium chloride or Sodium palmityl sulfate mix in any proportion.
Described acid binding agent is selected from one or more in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate to be mixed in any proportion; Described alkali metal hydroxide is selected from NaOH or KOH; Described alkaline carbonate is selected from Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is selected from as aHCO
3or KHCO
3.
The preparation method of the hyperbranched triazine char-forming agent of the present invention micro encapsulation fire retardant, its feature is to carry out as follows:
A, diamines is dissolved in and is dissolved in the solvent of diamines, obtain two amine aqueous solutions; Cyanuric chloride is dispersed in the solvent that disperses cyanuric chloride, obtains cyanuric chloride dispersion liquid;
B, at 0-10 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add two amine aqueous solutions, add again fire retardant and tensio-active agent, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation and keep thermotonus 1-4 hour;
C, be warming up to 30-70 ℃, in there-necked flask, add acid binding agent, reaction 3-6 hour;
D, be warming up to 90-150 ℃, reaction 6-10 hour, obtains mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, dry, pulverize and obtain hyperbranched triazine char-forming agent micro encapsulation fire retardant.
Dry described in step e is under 50 ℃ of-100 ℃ of conditions dry 2 hours to 10 hours.
The reaction principle of cyanuric chloride of the present invention and diamines is as shown in Equation 1:
Gained is as the general structure of the hyperbranched triazine char-forming agent of coating layer as shown in Equation 2:
Wherein, Z is NH or N; Between straight chained alkyl, aryl or multiple phenyl ring that R is piperazine ring, contain 1-30 carbon atom with the aryl of alkyl.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, the prepared hyperbranched triazine char-forming agent micro encapsulation fire retardant reaction process of the present invention is continuous, reaction times is short, production efficiency is high, has reduced reaction cost, makes fire retardant have better thermostability, become charcoal high, the advantages such as dispersing property is good in polymkeric substance, and flame retardant properties is good, fire-retardant product good combination property, can be widely used in, in the macromolecular materials such as plastics, rubber, coating, tackiness agent, having broad application prospects;
2, the present invention's capsule material material used mostly is the starting material cheaply such as the industrial cyanuric chloride being easy to get, piperazine, quadrol, has broad application prospects;
3, hyperbranched triazine char-forming agent microencapsulation inorganic flaming-resistant agent Shell Materials provided by the invention is that expandable flame retardant char-forming agent has hyperbranched macromolecular structure, as source of the gas and the charcoal source of expanding fire retardant system, the fire-retardant fire retardant systems of expansible that itself and core core acid source form, there is fabulous charcoal and the excellent flame retardant effect of being foamed into, and not halogen-containing, low toxicity, environmental protection, have extraordinary application foundation;
4, in the present invention, tensio-active agent contributes to the dispersion of fire retardant, avoids fire retardant to reunite and is block, forms stable dispersion system; Tensio-active agent is conducive to the deposition of the hyperbranched triazine char-forming agent of shell on fire retardant surface simultaneously, thereby forms than more completely coated shell, avoids forming the particle of hyperbranched triazine char-forming agent.
Specific embodiment
Embodiment 1
The hyperbranched triazine char-forming agent of the present embodiment micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, cyanuric chloride and diamines are obtained to hyperbranched triazine char-forming agent as coating layer, the micro encapsulation fire retardant using fire retardant as core under the effect of acid binding agent and tensio-active agent.Wherein diamines is selected piperazine, is disperseed the solvent of cyanuric chloride to select the solvent of ethanol, dissolving diamines to select acetone, fire retardant to select aluminium hydroxide, tensio-active agent to select OP-10, acid binding agent to select NaOH, is prepared as follows:
A, by 44.79g (0.52mol) piperazine dissolved in the acetone of 14.5L, obtain piperazine solution; By 46.10g(0.25mol) cyanuric chloride is dispersed in and disperses, in the ethanol of 250ml, to obtain cyanuric chloride dispersion liquid;
B, at 0 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add piperazine solution, add again 2500g aluminium hydroxide and 2.5gOP-10, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation reaction 4 hours;
C, be warming up to 50 ℃, in there-necked flask, add the 0.78molNaOH being dissolved in 80mL water, react 6 hours;
D, be warming up to 95 ℃, react 9 hours, obtain mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, 80 ℃ of vacuum-dryings 8 hours, pulverize (making it from the bulk of reuniting separately), obtaining hyperbranched triazine char-forming agent micro encapsulation aluminium hydroxide quality is 2560.13g.
When carrying out step a, b, c and d, agitator constantly stirs, and stops stirring when carrying out step e.
Embodiment 2
The hyperbranched triazine char-forming agent of the present embodiment micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, cyanuric chloride and diamines are obtained to hyperbranched triazine char-forming agent as coating layer, the micro encapsulation fire retardant using fire retardant as core under the effect of acid binding agent and tensio-active agent.Wherein diamines is selected quadrol, is disperseed the solvent of cyanuric chloride to select the solvent of ethanol, dissolving diamines to select water, fire retardant to select ferronickel double-hydroxide, tensio-active agent to select tetradecyl trimethyl ammonium chloride, acid binding agent to select Na2CO3, is prepared as follows:
A, by 30.05g(0.5mol) quadrol is dissolved in the water of 240ml, obtains ethylenediamine solution; By 46.10g(0.25mol) cyanuric chloride is dispersed in and disperses, in the ethanol of 48ml, to obtain cyanuric chloride dispersion liquid;
B, at 10 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add piperazine solution, add again 160g ferronickel double-hydroxide and 16g tetradecyl trimethyl ammonium chloride, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation reaction 1 hour;
C, be warming up to 70 ℃, in there-necked flask, add the Na that is dissolved in the 0.4mol in 40mL water
2cO
3, react 3 hours;
D, be warming up to 150 ℃, react 6 hours, obtain mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, 100 ℃ of vacuum-dryings 2 hours, pulverize (making it from the bulk of reuniting separately), obtaining hyperbranched triazine char-forming agent micro encapsulation ferronickel double-hydroxide quality is 206.5g.
When carrying out step a, b, c and d, agitator constantly stirs, and stops stirring when carrying out step e.
Embodiment 3
The hyperbranched triazine char-forming agent of the present embodiment micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, cyanuric chloride and diamines are obtained to hyperbranched triazine char-forming agent as coating layer, the micro encapsulation fire retardant using fire retardant as core under the effect of acid binding agent and tensio-active agent.Wherein diamines is selected N-aminoethyl piperazine, is disperseed the solvent of cyanuric chloride to select the solvent of ethanol, dissolving diamines to select water and alcohol mixed solvent, fire retardant to select inorganic hypo-aluminum orthophosphate, tensio-active agent to select peregal, acid binding agent to select KOH, is prepared as follows:
A, by 19.38g(0.15mol) N-aminoethyl piperazine be dissolved in the water of 300mL and the mixing solutions of ethanol (volume ratio is 4:1), obtain N-aminoethyl piperazine solution; By 9.22g(0.05mol) cyanuric chloride is dispersed in and disperses, in the ethanol of 100ml, to obtain cyanuric chloride dispersion liquid;
B, at 5 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add piperazine solution, add again the inorganic hypo-aluminum orthophosphate of 100g and 4g peregal, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation reaction 3 hours;
C, be warming up to 30 ℃, in there-necked flask, add the KOH that is dissolved in the 0.18mol in 180mL water, react 8 hours;
D, be warming up to 90 ℃, react 10 hours, obtain mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, 50 ℃ of vacuum-dryings 10 hours, pulverize (making it from the bulk of reuniting separately), obtaining hyperbranched triazine char-forming agent micro encapsulation aluminium hydroxide quality is 115.56g.
When carrying out step a, b, c and d, agitator constantly stirs, and stops stirring when carrying out step e.
Embodiment 4
The hyperbranched triazine char-forming agent of the present embodiment micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, cyanuric chloride and diamines are obtained to hyperbranched triazine char-forming agent as coating layer, the micro encapsulation fire retardant using fire retardant as core under the effect of acid binding agent and tensio-active agent.Wherein diamines is selected hydroxyethylethylene diamine, is disperseed the solvent of cyanuric chloride to select the solvent of ethanol, dissolving diamines to select water, fire retardant to select red phosphorus, tensio-active agent to select three nonyl ammonio methacrylates, acid binding agent to select KHCO
3, be prepared as follows:
A, by 26.04g(0.25mol) hydroxyethylethylene diamine be dissolved in the water of 450mL, obtain N-aminoethyl piperazine solution; By 18.44g(0.1mol) cyanuric chloride is dispersed in and disperses, in the ethanol of 30ml, to obtain cyanuric chloride dispersion liquid;
B, at 8 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add piperazine solution, add again 100g red phosphorus and 7g tri-nonyl ammonio methacrylates, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation reaction 2 hours;
C, be warming up to 60 ℃, in there-necked flask, add the KOH that is dissolved in the 0.32mol in 30mL water, react 5 hours;
D, be warming up to 120 ℃, react 8 hours, obtain mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, 80 ℃ of vacuum-dryings 8 hours, pulverize (making it from the bulk of reuniting separately), obtaining hyperbranched triazine char-forming agent micro encapsulation red phosphorus is 120.53g.
When carrying out step a, b, c and d, agitator constantly stirs, and stops stirring when carrying out step e.
Embodiment 5
The hyperbranched triazine char-forming agent of the present embodiment micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, cyanuric chloride and diamines are obtained to hyperbranched triazine char-forming agent as coating layer, the micro encapsulation fire retardant using fire retardant as core under the effect of acid binding agent and tensio-active agent.Wherein diamines selects 3, the solvent of 3-diaminodiphenylsulfone(DDS), dispersion cyanuric chloride selects the solvent of ethanol, dissolving diamines to select butanone, fire retardant to select zinc borate, tensio-active agent to select Varisoft 432PPG, acid binding agent to select NaHCO3, is prepared as follows:
A, by 69.52g(0.28mol) 3,3-diaminodiphenylsulfone(DDS) is dissolved in the butanone of 400mL, obtains N-aminoethyl piperazine solution; By 18.44g(0.1mol) cyanuric chloride is dispersed in and disperses, in the ethanol of 90ml, to obtain cyanuric chloride dispersion liquid;
B, at 4 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add piperazine solution, add again 100g zinc borate and 3g Varisoft 432PPG, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation reaction 3.5 hours;
C, be warming up to 65 ℃, in there-necked flask, add the NaHCO that is dissolved in the 0.37mol in 30mL water
3, react 4.5 hours;
D, be warming up to 130 ℃, react 7 hours, obtain mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, 90 ℃ of vacuum-dryings 6 hours, pulverize (making it from the bulk of reuniting separately), obtaining hyperbranched triazine char-forming agent micro encapsulation red phosphorus is 165.21g.
When carrying out step a, b, c and d, agitator constantly stirs, and stops stirring when carrying out step e.
Claims (10)
1. a hyperbranched triazine char-forming agent micro encapsulation fire retardant, it is characterized in that: described micro encapsulation fire retardant is take the solvent of cyanuric chloride, diamines, dispersion cyanuric chloride, dissolves solvent, fire retardant, tensio-active agent and the acid binding agent of diamines as raw material, using the cyanuric chloride after disperseing with dissolve after the hyperbranched triazine char-forming agent that obtained under the effect of acid binding agent and tensio-active agent of diamines as coating layer, the micro encapsulation fire retardant using fire retardant as core.
2. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, is characterized in that:
The each raw material of described micro encapsulation fire retardant by the proportioning of mass parts is: cyanuric chloride 2～10 mass parts; Disperse the solvent 10-100 mass parts of cyanuric chloride, the solvent 150-580 mass parts of dissolving diamines; Fire retardant 100 mass parts; Tensio-active agent 0.1～10 mass parts; The mol ratio of described diamines and described cyanuric chloride is 2:1-3:1; The mol ratio of described acid binding agent and cyanuric chloride is 3:1-4:1.
3. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, is characterized in that:
The solvent of described dissolving diamines is selected from one or more in water, acetone, butanone and ethanol to be mixed in any proportion;
The solvent of described dispersion cyanuric chloride is ethanol.
4. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, is characterized in that:
Described diamines is selected from piperazine, quadrol, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 2,6-tolylene diamine, diethyl toluene diamine, hydroxyethylethylene diamine, 3, one or more in 3-diaminodiphenylsulfone(DDS) and 2 methyl pentamethylenediamine are mixed in any proportion.
5. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, is characterized in that: described fire retardant is selected from one or more in aluminium hydroxide, magnesium hydroxide, magnesium aluminum double hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, ferronickel double-hydroxide, zinc borate, Zinc aluminate, zinc, zinc hydroxyl stannate, molybdic oxide, molybdenumdisulphide, ammonium molybdate, red phosphorus, ammonium polyphosphate, inorganic hypo-aluminum orthophosphate, organic phospho acid aluminium and triphenylphosphate to be mixed in any proportion.
6. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, it is characterized in that: described tensio-active agent is selected from OP-10, Brij, cetomacrogol, peregal, Ai Moerfu, carboxylic acid polyoxyethylene ester, Pluronic F68, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, three nonyl ammonio methacrylates, didecyl Dimethy ammonium chloride, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, one or more in distearyl dimethyl ammonium chloride or Sodium palmityl sulfate mix in any proportion.
7. hyperbranched triazine char-forming agent micro encapsulation fire retardant according to claim 1, is characterized in that: described acid binding agent is selected from one or more in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate to be mixed in any proportion; Described alkali metal hydroxide is selected from NaOH or KOH; Described alkaline carbonate is selected from Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate is selected from as aHCO
3or KHCO
3.
8. a preparation method for hyperbranched triazine char-forming agent micro encapsulation fire retardant claimed in claim 1, is characterized in that carrying out as follows:
A, diamines is dissolved in and is dissolved in the solvent of diamines, obtain two amine aqueous solutions; Cyanuric chloride is dispersed in the solvent that disperses cyanuric chloride, obtains cyanuric chloride dispersion liquid;
B, at 0-10 ℃, to being equipped with in the there-necked flask of agitator, constant pressure funnel and reflux condensing tube, add two amine aqueous solutions, add again fire retardant and tensio-active agent, then by constant pressure funnel, in there-necked flask, dropwise add cyanuric chloride dispersion liquid, be added dropwise to complete rear continuation and keep thermotonus 1-4 hour;
C, be warming up to 30-70 ℃, in there-necked flask, add acid binding agent, reaction 3-6 hour;
D, be warming up to 90-150 ℃, reaction 6-10 hour, obtains mixed solution;
E, to steps d gained mixed solution carry out suction filtration, washing, dry, pulverize and obtain hyperbranched triazine char-forming agent micro encapsulation fire retardant.
9. preparation method according to claim 8, is characterized in that: dry described in step e is under 50 ℃ of-100 ℃ of conditions dry 2 hours to 10 hours.
10. preparation method according to claim 8, is characterized in that:
The solvent of described dissolving diamines is selected from one or more in water, acetone, butanone and ethanol to be mixed in any proportion;
The solvent of described dispersion cyanuric chloride is ethanol;
Described diamines is selected from piperazine, quadrol, N, N-dimethyl-1,3-propylene diamine, N-aminoethyl piperazine, 2,6-tolylene diamine, diethyl toluene diamine, hydroxyethylethylene diamine, 3, one or more in 3-diaminodiphenylsulfone(DDS) and 2 methyl pentamethylenediamine are mixed in any proportion;
Described fire retardant is selected from one or more in aluminium hydroxide, magnesium hydroxide, magnesium aluminum double hydroxide, zinc-aluminium double-hydroxide, magnesium iron double-hydroxide, zinc-iron double-hydroxide, ferronickel double-hydroxide, zinc borate, Zinc aluminate, zinc, zinc hydroxyl stannate, molybdic oxide, molybdenumdisulphide, ammonium molybdate, red phosphorus, ammonium polyphosphate, inorganic hypo-aluminum orthophosphate, organic phospho acid aluminium and triphenylphosphate to be mixed in any proportion;
Described tensio-active agent is selected from OP-10, Brij, cetomacrogol, peregal, Ai Moerfu, carboxylic acid polyoxyethylene ester, Pluronic F68, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride, three nonyl ammonio methacrylates, didecyl Dimethy ammonium chloride, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, one or more in distearyl dimethyl ammonium chloride or Sodium palmityl sulfate mix in any proportion,
Described acid binding agent is selected from one or more in alkali metal hydroxide, alkaline carbonate or alkali metal hydrocarbonate to be mixed in any proportion; Described alkali metal hydroxide is selected from NaOH or KOH; Described alkaline carbonate is selected from Na
2cO
3or K
2cO
3; Described alkali metal hydrocarbonate NaHCO
3or KHCO
3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410016870.8A CN103756015B (en) | 2014-01-14 | 2014-01-14 | A kind of hyperbranched triazine char-forming agent micro encapsulation fire retardant and preparation method thereof |
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| CN105218714A (en) * | 2015-10-30 | 2016-01-06 | 浙江中天氟硅材料有限公司 | A kind of flame retardant microcapsule and its preparation method and application |
| CN105330803A (en) * | 2015-11-13 | 2016-02-17 | 太原理工大学 | Triazine type hyperbranched polyurea charring agent and preparing method thereof |
| CN109134939A (en) * | 2018-08-09 | 2019-01-04 | 福州大学 | A kind of piperazine modified lignin resin/magaldrate dual cladding red phosphorus combustion inhibitor and its application in PP |
| CN109942891A (en) * | 2019-03-12 | 2019-06-28 | 江南大学 | A kind of phosphorus nitrogen zinc two dimension supermolecule cladding molybdenum disulfide Hybrid fire retardant and its application |
| CN110696456A (en) * | 2019-09-23 | 2020-01-17 | 镇江荣诚管业有限公司 | Polyethylene pipe for underground coal mine and preparation process thereof |
| CN112079677A (en) * | 2020-09-16 | 2020-12-15 | 西北大学 | Insoluble energetic organic polymer coated micro-nano particle and preparation method thereof |
| CN113754860A (en) * | 2020-06-01 | 2021-12-07 | 中国科学院宁波材料技术与工程研究所 | Triazine charring agent, flame-retardant polyurethane material, and preparation method and application thereof |
| CN114380996A (en) * | 2022-01-26 | 2022-04-22 | 包头稀土研究院 | Hyperbranched polymer, preparation method and application thereof |
| CN114479183A (en) * | 2022-02-25 | 2022-05-13 | 四川金核高分子材料有限公司 | Organic modified zinc hydroxystannate-hypophosphite flame retardant and preparation method thereof |
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| CN1480253A (en) * | 2003-04-10 | 2004-03-10 | 上海化工研究院 | Method for making ammonium polyphosphate clad by microcapsules |
| CN103333336A (en) * | 2013-06-04 | 2013-10-02 | 合肥安聚达新材料科技有限公司 | Preparation method of novel hyperbranched triazine char forming agent |
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| CN105218714A (en) * | 2015-10-30 | 2016-01-06 | 浙江中天氟硅材料有限公司 | A kind of flame retardant microcapsule and its preparation method and application |
| CN105330803A (en) * | 2015-11-13 | 2016-02-17 | 太原理工大学 | Triazine type hyperbranched polyurea charring agent and preparing method thereof |
| CN105330803B (en) * | 2015-11-13 | 2017-08-15 | 太原理工大学 | A kind of hyperbranched polyureas carbon forming agent of triazines and preparation method thereof |
| CN109134939A (en) * | 2018-08-09 | 2019-01-04 | 福州大学 | A kind of piperazine modified lignin resin/magaldrate dual cladding red phosphorus combustion inhibitor and its application in PP |
| CN109134939B (en) * | 2018-08-09 | 2019-12-31 | 福州大学 | Piperazine modified lignin/magnesium aluminum hydroxide double-coated red phosphorus flame retardant and application thereof in PP |
| CN109942891A (en) * | 2019-03-12 | 2019-06-28 | 江南大学 | A kind of phosphorus nitrogen zinc two dimension supermolecule cladding molybdenum disulfide Hybrid fire retardant and its application |
| CN110696456A (en) * | 2019-09-23 | 2020-01-17 | 镇江荣诚管业有限公司 | Polyethylene pipe for underground coal mine and preparation process thereof |
| CN113754860A (en) * | 2020-06-01 | 2021-12-07 | 中国科学院宁波材料技术与工程研究所 | Triazine charring agent, flame-retardant polyurethane material, and preparation method and application thereof |
| CN112079677A (en) * | 2020-09-16 | 2020-12-15 | 西北大学 | Insoluble energetic organic polymer coated micro-nano particle and preparation method thereof |
| CN115521469A (en) * | 2021-09-14 | 2022-12-27 | 厦门理工学院 | Triazine ring structure-containing flame retardant, preparation method and application thereof in polylactic acid |
| CN114380996A (en) * | 2022-01-26 | 2022-04-22 | 包头稀土研究院 | Hyperbranched polymer, preparation method and application thereof |
| CN114380996B (en) * | 2022-01-26 | 2023-08-15 | 包头稀土研究院 | Hyperbranched polymer and preparation method and application thereof |
| CN114479183A (en) * | 2022-02-25 | 2022-05-13 | 四川金核高分子材料有限公司 | Organic modified zinc hydroxystannate-hypophosphite flame retardant and preparation method thereof |
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Application publication date: 20140430 Assignee: Baosheng Science and Technology Innovation Co., Ltd. Assignor: University of Science and Technology of China Contract record no.: 2018340000009 Denomination of invention: Hyperbranched triazine charring agent microcapsule flame retardant and preparation method thereof Granted publication date: 20160420 License type: Exclusive License Record date: 20180614 |
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