CN101376811B - Polyurethane microcapsulated inorganic phosphonium flame retardant and preparation thereof - Google Patents
Polyurethane microcapsulated inorganic phosphonium flame retardant and preparation thereof Download PDFInfo
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Abstract
The invention discloses polyurethane microencapsulated inorganic phosphonium flame retardant and a preparation method thereof. The invention is characterized in that the polyurethane generated by using polyether glycol and diisocyanate as the main monomers to be polymerized with a crosslinking monomer is used as a coating layer; inorganic phosphonium flame retardant is used as a core for preparing microcapsule flame retardant through in-situ polymerization; wherein, the weight ratio of the inorganic phosphonium flame retardant to the polyurethane is 1.5 to 9. in the invention, the weight ratio of the material of a microcapsule wall to a core material can be regulated in a larger range by using the mode of in-situ polymerization according to the cooperative retardant principle of P, N and C; simultaneously, the best water-resistance and the best retardant performance can be obtained. The fluidity of the grains of the obtained product is good; the phenomena of moisture absorption and agglomeration can not occur; simultaneously the product has the effect of cooperation retardant; therefore, the retardant efficiency is improved, the compatibility with a polymer is greatly improved as well; the harm to the physical property of a substrate is reduced; the water-solubility of the product is greatly reduced and the water-resistance is remarkably improved.
Description
Technical field
The invention belongs to the fire retardant technical field, particularly be core, be inorganic phosphorated fire retardant of capsule material, the coating of employing in-situ polymerization and preparation method thereof with urethane with inorganic phosphorated fire retardant.
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 fire burns, can be divided into halogen containing flame-retardant and halogen-free flame retardants.Halogen containing flame-retardant can produce more smog and deleterious corrosive gases in combustion processes; Environment is produced pollution; European Union announced " waste electronic andelectrical equipment instruction " (being called for short " WEEE ") and " about in electronic electric equipment, banning use of some objectionable impurities instruction " (being called for short " RolS ") two instructions in 2003 for this reason; Its core is exactly environmental protection, energy-conservation, and requires electronic product to realize heavy metal free, halogen-free flameproofization, solvent free thus.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.Wherein inorganic phosphorated fire retardant not only overcome Halogen type fire retardant combustion fumes big, can emit defectives poisonous and etchant gas and many molten drops that burn, it is high and have a strong impact on the shortcoming of the physical and mechanical properties of material to have improved the inorganic filler loading level simultaneously again.Inorganic phosphorated fire retardant comprises ammonium polyphosphate, red phosphorus and other phosphoric acid salt; Through forming full-bodied melten glass matter and fine and close carburization zone on the combustionmaterial surface; Cut off heat and oxygen, decompose generation PO-, HPO radical simultaneously, interrupt chain combustion reactions by H-, HO free-radical generating.But also there is weak point in inorganic phosphorated fire retardant; " fire retardant material with technology " magazine (2004 for example; 5:5-9) point out in " inorganic phosphorated fire retardant progress " literary composition: inorganic phosphorated fire retardant is when plastic working; Relatively poor with some macromolecular material affinity, it is oozed out in polymer product and run off, reduced its flame retardant resistance.In addition, decomposes produces micromolecular compound under the high temperature, is difficult to satisfy the requirement that thermoplasticity, thermosetting resin are processed under comparatively high temps.In order to overcome the above-mentioned shortcoming of fire retardant; In recent years; Developed the micro-capsule package technology of fire retardant in the world; Promptly use natural or synthesized polymer material solid or liquid composition are rolled into diameter is micron-sized capsule, thereby improve the water tolerance and the consistency of fire retardant, suppress the untoward reaction that fire retardant takes place in the course of processing.Generally can be divided into interfacial polymerization and in-situ polymerization, wherein the situ aggregation method principle is a kind ofly all to add reactive monomer or its solubility performed polymer and catalyzer in the disperse phase (or external phase), and the core material is a disperse phase.Since monomer or performed polymer single be soluble in mutually, and its polymkeric substance is insoluble in whole system, so polyreaction takes place on the disperse phase core.The reaction beginning, the monomer pre-polymerization, the performed polymer polymerization after performed polymer polymerization size progressively increases, is deposited on the surface of core material.
In disclosed patent about microcapsule flame retardant, German patent DE 2,949,537, DE3,005,253 and DE3,316,880 to disclose with P-F or melamine-formaldehyde resin be the method that the capsule material coats ammonium polyphosphate.Although the prepared microcapsule flame retardant that goes out of these class methods has certain anti-hydrolysis, anti-moisture absorption, this type microcapsule product can discharge obnoxious flavour formaldehyde in actual production and use, can damage with production unit healthy; In addition, the used capsule material of these class methods is thermosetting resin, in the course of processing, is prone to be extruded and partial rupture, does not finally reach the covered effect of expection.
The char-forming agent such as tetramethylolmethane (PER), N.F,USP MANNITOL (mannitol) and the sorbyl alcohol (or being referred to as first-generation char-forming agent) such as (sorbitol) that use in the tradition flame-retardant system; Its common shortcoming is to be prone in the blend process react with polymeric substrate; Or because hydrolysis and moving out, and the incompatible problem such as material mechanical performance heavy losses that causes with polymeric substrate from substrate surface." Halogenless fire retarded polymer basis and application " (Wang Jianqi; Science Press; 2005,6) a book 93-95 page or leaf is pointed out: TPUE (TPU) is as a kind of high molecular polymer with charcoal effect, the physicals of existing rubber; The processing of plastic performance is arranged again, obtaining rapid progress aspect the defective that overcomes above-mentioned traditional charcoal source.Use the cooperative flame retardant system of inorganic phosphorated fire retardant and TPU, the fire retardant material that can obtain to have better mechanical property.For example Holland's " reactivity and functional high-polymer " magazine (" Reactive andFunction Polymer " of part report is only arranged at present; 2006; 66:1118-1125) point out: not only complex process but also coating layer are how empty shape to adopt surface reaction to coat ammonium hydrogen phosphate; Covering amount also limited (≤5wt%), do not see the relevant report that utilizes urethane to adopt the method for situ aggregation method coated inorganic phosphonium flame retardant of domestic and international patent and document so far as yet.
Summary of the invention
The objective of the invention is to propose a kind of polyurethane microcapsulated inorganic phosphonium flame retardant and preparation method thereof, water tolerance and consistency to improve inorganic phosphorated fire retardant suppress the untoward reaction that inorganic phosphorated fire retardant takes place in the course of processing.
The preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant of the present invention; It is characterized in that: the mol ratio by isocyanato in hydroxyl and the vulcabond in hydroxyl in the polyether Glycols and the tetramethylolmethane is 0.333～0.931: 0.667～0.069: 1; Inorganic phosphorated fire retardant weight is polyether Glycols, tetramethylolmethane and vulcabond gross weight 9～2.3 times; Polyether Glycols and vulcabond are dissolved in the inert solvent that weight is 2～4 times of inorganic phosphorated fire retardants,, add the dimethyl sulphoxide solution of inorganic phosphorated fire retardant and 0.1～10 mol tetramethylolmethane 20～40 ℃ of insulations 15～30 minutes; Adding respectively is the tensio-active agent of inorganic phosphorated fire retardant 0.5%～10% and 0.01%～1.13% times catalyzer by weight again; Slowly be warmed up to 65～90 ℃ and be incubated 1～4 hour, reduce to room temperature then, filter; Filter cake 80～100 ℃ of dryings 4～8 hours, is promptly obtained the polyurethane microcapsulated inorganic phosphonium flame retardant product.
In the above-mentioned steps, in the preferred, polyethers divalent alcohol in hydroxyl, the tetramethylolmethane in hydroxyl and the vulcabond mol ratio of isocyanato be 0.5～0.875: 0.5～0.125: 1; The preferred preferable inorganic phosphorated fire retardant and the weight ratio of inert solvent are 1: 2～3; Preferred preferable tensio-active agent add-on is 1～5% of an inorganic phosphorated fire retardant weight; Preferred preferable catalyzer add-on is inorganic 0.05%～0.75% of the phosphorus fire retardant weight of closing.
Said inorganic phosphorated fire retardant is selected from ammonium polyphosphate, red phosphorus, Secondary ammonium phosphate, primary ammonium phosphate or ammonium pyrophosphate.
Said inert solvent is a benzene,toluene,xylene, 1,4-dioxane, hexanaphthene, acetonitrile, 1,2-ethylene dichloride, glycol dimethyl ether, trichloroethane, propionitrile, heptane, Nitromethane 99Min., nitroethane, pyridine, octane or chlorobenzene.
Said tensio-active agent is AEO, halogenated aliphatic hydrocarbon ammonium salt or lower molecular weight polypyrrole alkane ketone, and wherein AEO comprises benzyl pool, cetomacrogol, peregal, Ai Moerfu, carboxylic acid polyoxyethylene ester or T 46155 one polyoxypropylene multipolymer; The halogenated aliphatic hydrocarbon ammonium salt comprises DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium chlorine or bromine ammonium, trioctylphosphine methyl chloride or brometo de amonio, three nonyl methyl chlorides or brometo de amonio, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride or Varisoft 432PPG.
Said catalyzer is selected from dibutyl tin laurate, stannous octoate or N-methylmorpholine.
Polyurethane microcapsulated inorganic phosphonium flame retardant by method for preparing of the present invention; It is characterized in that with polyether Glycols and vulcabond being that the urethane that main monomer and the polymerization of cross-linking monomer tetramethylolmethane produce is coating layer; To be the micro encapsulation fire retardant of nuclear by surfactant modified inorganic phosphorated fire retardant, the weight ratio of said inorganic phosphorated fire retardant and urethane is 1.5～9.
The coating layer of said micro encapsulation fire retardant for by polyether Glycols and vulcabond be polymkeric substance, the molecular weight of main monomer and the polymerization of cross-linking monomer tetramethylolmethane generation be 1000～2000 gather fourth diether (HO [(CH
2)
4-O]
nH), molecular weight is 400～2050 W 166 (HO [(CH
2)
3-O]
nH) or molecular weight be polyoxyethylene glycol (the HO [(CH of 400-2000
2)
2-O]
nH); Said vulcabond is Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond or 1, the 5-naphthalene diisocyanate.
The present invention is to be raw material with polyether Glycols, vulcabond and tetramethylolmethane, under catalytic condition, carries out the inorganic phosphorated fire retardant of reaction pair and wraps up.Adopting the weight ratio of inorganic phosphorated fire retardant and solvent among the present invention is 1: 2～3; If dispersant dosage is too high, the energy consumption of its recovery is too high can to increase unnecessary cost; And if dispersant dosage is low excessively, inorganic phosphorated fire retardant dispersion effect is not good enough, possibly form reunion, the final parcel of influence effect; Adopting inorganic phosphorated fire retardant among the present invention is polyether Glycols, tetramethylolmethane and vulcabond gross weight 9～2.3 times; If selected polyether Glycols, vulcabond and tetramethylolmethane consumption are less than 5%; Can cause inorganic phosphorated fire retardant to coat not exclusively causes the inorganic phosphorated fire retardant particle of part exposed; Not only can influence flame retardant effect, simultaneously the moisture absorption deliquescence can take place easily; And if selected polyether Glycols, vulcabond and tetramethylolmethane consumption are too much, the coating layer that can make inorganic phosphorated fire retardant surface is blocked up and cost improves.
The polyurethane microcapsulated inorganic phosphonium flame retardant that the present invention prepares in the above-mentioned scope that feeds intake is compared with the inorganic phosphorated fire retardant of uncoated; Median size does not obviously increase; Moisture absorption caking phenomenon can not occur, have the cooperative flame retardant effect simultaneously, improve flame retarding efficiency; Also greatly improve with the consistency of polymkeric substance, reduced injury the matrix physicals.Products therefrom surface compact, even, it is exposed to find that single inorganic phosphorated fire retardant particle is arranged.Its water-soluble greatly reduction, water tolerance significantly improves.
The polyurethane microcapsulated inorganic phosphonium flame retardant of the present invention's preparation, with German patent DE 2,949,537 adopt urea-formaldehyde resin, DE3; 005,253 adopts melamine-formaldehyde resin and DE3,316; 880 phenol-formaldehyde resins are that cyst material is compared, and simple to operate, covered effect is good; The present invention prepares and does not have the formaldehyde gas that environment and personnel are damaged in the process, and the product surface phosphorus content only has 1.46wt%, and it is imperfect that this explanation has only few fire retardant particle to coat; And it is phosphorous about 3.5wt% with urea-formaldehyde resin and melamine-formaldehyde or phenol-formaldehyde resin product wrapping surface; Simultaneously, because urea-formaldehyde resin and melamine-formaldehyde or phenol-formaldehyde resin are thermosetting resin, cyst wall fragility is higher, and the shearing action of machinery can make the part cyst wall break in the course of processing, loses covered effect; And the micro encapsulation fire retardant cyst wall layer of the inventive method preparation is the cross-linked thermoplastic resin, has good toughness, adds and can not break man-hour.Adopt urethane can bring into play the cooperative flame retardant effect with inorganic phosphorated fire retardant in the inventive method as cyst material; Flame retarding efficiency is higher; Can also improve consistency, mechanical property with base material, fire retardant material to recycle effect better, can satisfy the strict demand of people to fire retardant.
The present invention is according to P, N, C cooperative flame retardant principle; Self chemical constitution to the urethane cyst material; As the charcoal source, in preparation micro encapsulation process, add microcapsulated inorganic phosphonium flame retardant with cyst material, adopt home polymerization mode; Can in a big way, regulate the weight ratio of cyst material and core, to obtain best water resistance and flame retardant properties simultaneously.Prepared polyurethane microcapsulated inorganic phosphonium flame retardant can be applicable to macromolecular materials such as polyolefine, urethane, rubber, also can be used for the fire-retardant of paper, timber, fabric etc.
Embodiment
Further specify the present invention with embodiment below.
Embodiment 1:
With 2.5 gram molecular weights is that 400 polyoxyethylene glycol and 17.4 gram 2,4 toluene diisocyanates join in 1000 milliliters of there-necked flasks, adds 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 200 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 5.95 gram tetramethylolmethanes then, be heated to 80 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains white polyurethane micro encapsulation fire retardant product 218 grams.
The solubleness of products therefrom in the time of 25 ℃ is 0.115g/100mlH
2O.
Selecting urethane in the present embodiment for use is cyst material; Because urethane is polar compound; According to the similar compatibility principle, resulting fire retardant product in the present embodiment is joined in Vilaterm-hexenoic acid ethyl ester, urethane, nylon-6, polymethylmethacrylate or these polar polymers of polycarbonate and can both have good consistency with matrix; Because inorganic phosphorated fire retardant surface is coating one deck urethane, intercepted the interaction of fire retardant and other auxiliary agents simultaneously, untoward reaction has taken place in the course of processing thereby can suppress inorganic phosphorated fire retardant.
Embodiment 2:
With 5 gram molecular weights is that 400 polyoxyethylene glycol and 17.4 gram 2,4 toluene diisocyanates join in 1000 milliliters of there-necked flasks, adds 500 milliliter 2; The 4-dioxane is warmed up to 35 ℃, stirs 20 minutes; Add 200 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 3.6 gram tetramethylolmethanes then, be heated to 80 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 220 grams of white microcapsuleization.
25 ℃ of solubleness of products therefrom are 0.146g/100mlH
2O, this fire retardant and matrix have good consistency.
If the 2,4 toluene diisocyanate in the present embodiment is replaced with Toluene-2,4-diisocyanate .6-vulcabond or 1, the 5-naphthalene diisocyanate under the constant situation of other conditions, has all obtained the polyurethane micro-encapsulated fire retardant product of good fluidity.
Embodiment 3
With 18.4 gram molecular weights is that 400 polyoxyethylene glycol and 16.2 gram 2,4 toluene diisocyanates join in 1000 milliliters of there-necked flasks, adds 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 200 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 1.68 gram tetramethylolmethanes then, be heated to 85 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 230 grams of white microcapsuleization.
25 ℃ of solubleness of products therefrom are 0.184g/100mlH
2O, this fire retardant and matrix have good consistency.
If with the inert solvent in the present embodiment 2; The 4-dioxane replaces with benzene,toluene,xylene, hexanaphthene, acetonitrile, 1; 2-ethylene dichloride, glycol dimethyl ether, trichloroethane, propionitrile, heptane, Nitromethane 99Min., nitroethane, pyridine, octane or chlorobenzene under the constant situation of other conditions, can both obtain polyurethane microcapsulated inorganic phosphonium flame retardant; Uniform particles, performance and pattern are all basic identical.
Embodiment 4:
Be equipped with stir and the reaction kettle of reflux in, add 10 gram molecular weights and be 1000 polyoxyethylene glycol, 13.92 gram 2,4 toluene diisocyanates and 500 milliliter 2; The 4-dioxane is warmed up to 30 ℃, stirs 20 minutes; Add 214 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 2.88 gram tetramethylolmethanes then, be heated to 90 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 230 grams of white microcapsuleization.
25 ℃ of solubleness of products therefrom are 0.086g/100mlH
2O, this fire retardant and matrix have good consistency.
If the tensio-active agent peregal in the present embodiment is replaced with the AEO that comprises benzyl pool, cetomacrogol, Ai Moerfu, carboxylic acid polyoxyethylene ester, T 46155-polyoxypropylene multipolymer; Or replace with halogenated methyl aliphatic hydrocarbon ammonium salt or the lower molecular weight polypyrrole alkane ketone that comprises DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium chlorine or bromine ammonium, trioctylphosphine methyl chloride or brometo de amonio, three nonyl methyl chlorides or brometo de amonio, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride or hexadecyldimethyl benzyl ammonium ammonium chloride; Adopt operation steps same as described above; All can obtain polyurethane micro-encapsulated fire retardant product, its particle size distribution difference is very little.
Embodiment 5:
Be equipped with stir and the reaction kettle of reflux in, add 20 gram molecular weights and be 2000 polyoxyethylene glycol, 13.92 gram 2,4 toluene diisocyanates and 600 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 294 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 2.88 gram tetramethylolmethanes then, be heated to 65 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 325 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.093g/100mlH
2O, obtained fire retardant and matrix have good consistency.
If the inorganic phosphorated ammonium polyphosphate flame retardant in the present embodiment is replaced with red phosphorus, ortho-phosphoric acid trimeric cyanamide, ortho-phosphoric acid two trimeric cyanamides, phosphoguanidine, guanyl-urea-phosphate, Ureaphil, Secondary ammonium phosphate, primary ammonium phosphate or ammonium pyrophosphate; Adopt operation steps same as described above, all can obtain the polyurethane micro-encapsulated fire retardant product about 210g.
Embodiment 6:
Be equipped with stir and the reaction kettle of reflux in, add 20 gram molecular weights and be 4000 polyoxyethylene glycol, 6.96 gram 2,4 toluene diisocyanates and 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 227 gram exsiccant ammonium polyphosphate powder and 5 gram peregals, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 1.44 gram tetramethylolmethanes then, be heated to 70 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 250 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.222g/100mlH
2O, this fire retardant and matrix have good consistency.
Embodiment 7:
Be equipped with stir and the reaction kettle of reflux in, add 3.3 gram molecular weights and be 1000 polyoxyethylene glycol, 4.64 gram 2,4 toluene diisocyanates and 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add again 178 gram exsiccant ammonium polyphosphate powder and 5 gram peregals, add the 20ML dimethyl sulphoxide solution and 0.8 gram, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 0.96 gram tetramethylolmethane then, be heated to 75 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 188 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.21g/100mlH
2O, this fire retardant and matrix have good consistency.
Embodiment 8:
Be equipped with stir and the reaction kettle of reflux in, add 20 gram molecular weights and be 1000 polyoxyethylene glycol, 27.84 gram 2,4 toluene diisocyanates and 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 214 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 4 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 5.76 gram tetramethylolmethanes then, be heated to 80 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 255 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.083g/100mlH
2O, obtained fire retardant and matrix have good consistency.
Embodiment 9:
Be equipped with stir and the reaction kettle of reflux in, add 24 gram molecular weights and be 1000 polyoxyethylene glycol, 33.41 gram 2,4 toluene diisocyanates and 500 milliliter 2; The 4-dioxane is warmed up to 20 ℃, stirs 20 minutes; Add 214 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 8 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 6.91 gram tetramethylolmethanes then, be heated to 80oC; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 270 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.081g/100mlH
2O, this fire retardant and matrix have good consistency.
Embodiment 10:
Be equipped with stir and the reaction kettle of reflux in, add 32 gram molecular weights and be 1000 polyoxyethylene glycol, 44.55 grams 2,6-tolylene diisocyanate and 500 milliliter 2; The 4-dioxane is warmed up to 40 ℃, stirs 20 minutes; Add 214 gram exsiccant ammonium polyphosphate powder and 5 gram peregals again, add the 20ML dimethyl sulphoxide solution and 2 grams, the two LAURIC ACID 99 MIN butyl tin that are dissolved with 9.21 gram tetramethylolmethanes then, be heated to 80 ℃; Be incubated 150 minutes, cool to room temperature, suction filtration, washing; Oven dry obtains inorganic phosphorated fire retardant 285 grams of white microcapsuleization.
25 ℃ of solubleness of products obtained therefrom are 0.08g/100mlH
2O, this fire retardant and matrix have good consistency.
Products therefrom among above-mentioned each embodiment of the present invention is because its skin is the polyether(poly)urethane through chemically crosslinked, and polyether(poly)urethane has good water tolerance, so micro encapsulation product water tolerance of the present invention greatly improves; According to the similar compatibility principle; Urethane has good consistency as a kind of polar polymer and Vilaterm-hexenoic acid ethyl ester, urethane, nylon-6, polymethylmethacrylate or these polar polymers of polycarbonate, so products therefrom and above-mentioned polar polymer all have good consistency in the various embodiments of the present invention; Intercepted the interaction of inorganic phosphorus fire retardant and other auxiliary agents owing to the outer field shielding effect of urethane simultaneously, thereby can suppress the untoward reaction that inorganic phosphorated fire retardant takes place in the course of processing
The solubility test method of product is among above-mentioned each embodiment: 10 gram products are suspended in the 100ml deionized water; Stirred 2 hours down at 25 ℃; Used the whizzer precipitation separation then 15 minutes, will show that clear liquid pipettes in the watch-glass that 10ml to weighed, puts into loft drier; To constant weight, calculate the solubleness in water 100 ℃ of following evaporation dryings according to the amount of evaporation residue.
Claims (8)
1. the preparation method of a polyurethane microcapsulated inorganic phosphonium flame retardant; It is characterized in that: the mol ratio by isocyanato in hydroxyl and the vulcabond in hydroxyl in the polyether Glycols and the tetramethylolmethane is 0.333～0.931: 0.667～0.069: 1; Inorganic phosphorated fire retardant weight is polyether Glycols, tetramethylolmethane and vulcabond gross weight 9～2.3 times; Polyether Glycols and vulcabond are dissolved in the inert solvent that weight is 2～4 times of inorganic phosphorated fire retardants,, add the dimethyl sulphoxide solution of inorganic phosphorated fire retardant and 0.1～10 mol tetramethylolmethane 20～40 ℃ of insulations 15～30 minutes; Adding is the tensio-active agent of inorganic phosphorated fire retardant 0.5%～10% and 0.01%～1.13% times catalyzer by weight again; Slowly be warmed up to 65～90 ℃ and be incubated 1～4 hour, reduce to room temperature then, filter; Filter cake 80～100 ℃ of dryings 4～8 hours, is promptly obtained the polyurethane microcapsulated inorganic phosphonium flame retardant product.
2. the preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant according to claim 1 is characterised in that in the said polyether Glycols in hydroxyl, the tetramethylolmethane that the mol ratio of isocyanato is 0.5～0.875: 0.5～0.125 in the hydroxyl and vulcabond: 1; The weight ratio of said inorganic phosphorated fire retardant and inert solvent is 1: 2～3; Said tensio-active agent add-on is 1～5% of an inorganic phosphorated fire retardant weight; Said catalyzer add-on is 0.05%～0.75% of an inorganic phosphorated fire retardant weight.
3. the preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant according to claim 1 is characterised in that said inorganic phosphorated fire retardant is selected from ammonium polyphosphate, red phosphorus, Secondary ammonium phosphate, primary ammonium phosphate or ammonium pyrophosphate.
4. the preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant according to claim 1; Be characterised in that said inert solvent is a benzene,toluene,xylene, 1; 4-dioxane, hexanaphthene, acetonitrile, 1,2-ethylene dichloride, glycol dimethyl ether, trichloroethane, propionitrile, heptane, Nitromethane 99Min., nitroethane, pyridine, octane or chlorobenzene.
5. the preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant according to claim 1; Be characterised in that said tensio-active agent is AEO, halogenated aliphatic hydrocarbon ammonium salt or lower molecular weight polypyrrole alkane ketone, wherein AEO is selected from benzyl pool, cetomacrogol, peregal, Ai Moerfu, carboxylic acid polyoxyethylene ester or T 46155-polyoxypropylene multipolymer; Said halogenated aliphatic hydrocarbon ammonium salt is selected from DTAC, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium chlorine or bromine ammonium, trioctylphosphine methyl chloride or brometo de amonio, three nonyl methyl chlorides or brometo de amonio, two ten alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, two tetradecyl alkyl dimethyl ammonium chloride or Varisoft 432PPG.
6. the preparation method of polyurethane microcapsulated inorganic phosphonium flame retardant according to claim 1 is characterised in that said catalyzer is selected from dibutyl tin laurate, stannous octoate or N-methylmorpholine.
7. the polyurethane microcapsulated inorganic phosphonium flame retardant of the said method of claim 1 preparation; It is characterized in that with polyether Glycols and vulcabond being that the urethane that main monomer and the polymerization of cross-linking monomer tetramethylolmethane produce is coating layer; To be the micro encapsulation fire retardant of nuclear by surfactant modified inorganic phosphorated fire retardant, the weight ratio of said inorganic phosphorated fire retardant and urethane is 1.5～9.
8. polyurethane microcapsulated inorganic phosphonium flame retardant as claimed in claim 7, the coating layer that is characterised in that said micro encapsulation fire retardant is for being that polymkeric substance, the molecular weight of main monomer and cross-linking monomer tetramethylolmethane is that 1000～2000 gather fourth diether, molecular weight are that 400～2050 W 166 or molecular weight are the polyoxyethylene glycol of 400-2000 by polyether Glycols and vulcabond.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101568844A CN101376811B (en) | 2008-09-28 | 2008-09-28 | Polyurethane microcapsulated inorganic phosphonium flame retardant and preparation thereof |
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| CN101503526B (en) * | 2009-03-05 | 2011-06-29 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated halogen-free flame retardant and preparation thereof |
| CN101608060B (en) * | 2009-07-09 | 2011-06-29 | 中国科学技术大学 | Core-shell type ammonium polyphosphate synergetic flame-retardant polyurethane elastic composite material and preparation method thereof |
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| CN109529737B (en) * | 2019-01-09 | 2022-03-15 | 天津工业大学 | One-step preparation method of polyurethane capsule |
| CN112574549B (en) * | 2020-12-09 | 2023-04-14 | 黎明化工研究设计院有限责任公司 | Flame-retardant polyurethane microcapsule and preparation method and use method thereof |
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| CN114181433B (en) * | 2021-12-14 | 2023-09-05 | 安徽长淮新材料有限公司 | Preparation method of polyurethane-based ionic liquid polymer coated red phosphorus flame retardant material |
| CN116444860A (en) * | 2022-08-29 | 2023-07-18 | 浙江新化化工股份有限公司 | Modified phosphorus-containing flame retardants, flame retardant polyamides, flame retardant polyurethanes and flame retardant polyolefins |
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