CN103992512A - Microencapsulated inorganic hypophosphite flame retardant and preparation method thereof - Google Patents
Microencapsulated inorganic hypophosphite flame retardant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microencapsulated inorganic hypophosphite flame retardant and a preparation method thereof. A capsule wall material of the microencapsulated inorganic hypophosphite flame retardant is a triazine ring containing crosslinked polymer. In order to solve the problem in the prior art that inorganic hypophosphite flame retardants are liable to combust spontaneously, the microencapsulated inorganic hypophosphite flame retardant is obtained by wrapping the surface of inorganic hypophosphite with the triazine ring containing crosslinked polymer as the capsule wall material through the microencapsulation technology. The microencapsulated inorganic hypophosphite flame retardant has the advantages of higher thermal stability, difficulty in spontaneous combustion, higher flame retardance efficiency, better compatibility with polymer matrices and the like. Besides, the preparation method is simple in process, is easy to operate and is suitable for industrial production.
Description
Technical field
the invention belongs to fire retardant preparing technical field, be specifically related to microencapsulation inorganic hypophosphite fire retardant and preparation method thereof, wherein capsule material is for containing triazine ring cross-linked polymer.
Background technology
inorganic hypophosphite, as the higher fire retardant of a kind of novel phosphorus-containing amount, is widely used in engineering plastics and polyamide material with its excellent flame retarding efficiency.Inorganic hypophosphite is non-volatile under preparation and fabrication thermoplastic polymer's usual conditions, also can not cause the decomposition of polymkeric substance, has good mechanical property and anti-marquis's property in the course of processing.The main drawback of inorganic hypophosphite is exactly its poor heat stability, especially in the course of processing of engineering plastics, the higher and friction of material in addition of temperature, makes its easier spontaneous combustion, thereby can produce certain potential safety hazard, be exactly the most significantly wherein inorganic hypo-aluminum orthophosphate.In order to overcome the spontaneous combustion problem of inorganic hypophosphite, utilize organically-modified method can obtain more organic hypophosphite of high stability.It is to utilize organic reaction to change unsettled P-H key in inorganic hypophosphite into stable P-C key that inorganic hypophosphite is carried out to organically-modified principle, but this is not sufficient to fundamentally solve the spontaneous combustion problem of inorganic hypophosphite.Reason be organically-modified can only be partially modified, if all change all P-H keys into P-C key, this is not only unpractical, and can significantly reduce the phosphorus content of hypophosphite fire retardant, has a strong impact on flame retardant effect, cost is high too simultaneously.
microencapsulation technology is that micro substance is wrapped in to the technology in polymeric film, is the microdisplay package technology of a kind of store solids, liquid, gas.Refer to specifically a certain material (core or interior phase) is coated completely with various natural or synthetic macromolecular compound continuous films (wall or foreign minister); and it is at all harmless to original chemical property of this material; then little by little by some outside stimulus or slow releasing function, the function of this material is externally presented again, or rely on the shielding effect of cyst wall to play the effect of protecting core.Microencapsulation technology has developed into a kind of industrial technology of maturation with its unique advantage, be widely used in the fields such as medicine, biology, food.At present, microencapsulation technology has been introduced in flame-retarded technology field, for the modification of fire retardant provides a kind of new technological approaches.Red phosphorus, as a kind of efficient Halogen phosphorus flame retardant, originally can be brought into play its use value by its remarkable flame retarding efficiency, but because its color, the problem that is easy to spontaneous combustion have limited its business-like value.After introducing microencapsulation technology, the security of micro encapsulation red phosphorus, consistency and color problem are improved.From example above, can find out, microencapsulation technology is at the existing very ripe example of application of flame retardant area.
containing triazine ring cross-linked polymer, be the important nitrogenated flame retardant of a class, mainly comprise the derivative of trimeric cyanamide and cyanuric chloride.This based flame retardant has multiple reaction function, has the advantages such as volatility is little, flame retardant properties is excellent, nontoxic, consistency good, lasting, fast light.Conventional have melamine cyanurate, pentaerythritol phosphate melamine salt, three (tribromo phenyl) cyanurate, three (penta-bromophenyl) cyanurate etc.
melamine cyanurate is a kind of flame-resistant lubricant of the exploitation eighties, and the triazine ring molecular complex with large Planar hydrogen bonding network that it is comprised of hydrogen bonded trimeric cyanamide and tricyanic acid, belongs to nitrogenous halogen-free environment-friendly type flame-proof agent.Melamine cyanurate outward appearance is the white crystals micro mist with soapy feeling, nontoxic, tasteless, is insoluble in water and general organic solvent.It is 300 ℃ of following stablizing, and 400 ℃ start distillation and are decomposed into trimeric cyanamide and tricyanic acid.Melamine cyanurate has and uses economic, efficient, excellent electrical property and mechanical property, nondiscoloration, low cigarette, low-corrosiveness.Its low toxicity of while, to user's safety, the thermostability good, good with Environmental compatibility, the very processing of appropriate materials, can be used for power lubrication, plastic flame, Coating Matting and makeup and field of printing and dyeing.Melamine salt of pentaerythritol phosphate is a kind of efficient expansion type flame retardant, it rolls into one acid source, charcoal source and source of the gas, fundamentally solve acid source in expansion type flame retardant, charcoal source and each component of source of the gas and distributed uneven problem, there is the advantages such as Heat stability is good, consistency are good, light aging resisting, be more conducive to bring into play the synergistic effect of phosphorus-nitrogen simultaneously.Three (tribromo phenyl) cyanurate and three (penta-bromophenyl) cyanurates all belong to brominated aromatic triaizine compounds, are additive flame retardants, all have very high thermostability.Aromatic series bromine combines with cyanurate and has good melt flow property, and bromo-nitrogen synergistic effect provides better flame retardant properties simultaneously, and has the cigarette effect of pressing down.In addition, in molecular structure, contain triazines group (triazine group class photostabilizer is UV absorption agent type of new generation), also there is resistance to opticity and ultraviolet light stability.
due to containing triazine ring cross-linked polymer, have Heat stability is good, with the feature such as polymeric matrix consistency is good, if will combine with microencapsulation technology containing the synthetic of triazine ring cross-linked polymer, to as capsule material, wrap up inorganic hypophosphite containing triazine ring cross-linked polymer, should be able to improve the problem that in prior art, inorganic hypophosphite exists as fire retardant, obtain the good microencapsulation inorganic Hypophosporous Acid, 50 of class fire retardant.
Summary of the invention
the present invention is intended to overcome the deficiencies in the prior art, and the microencapsulation inorganic hypophosphite fire retardant that a kind of thermostability is better, be difficult for spontaneous combustion is provided.
another object of the present invention is to provide the preparation method of above-mentioned microencapsulation inorganic hypophosphite fire retardant.
for solving above technical problem, the technical scheme that the present invention takes is:
a microencapsulation inorganic hypophosphite fire retardant, its core is inorganic hypophosphite, capsule material is for containing triazine ring cross-linked polymer, and the per-cent that capsule material accounts for described microencapsulation inorganic hypophosphite fire retardant total mass is in 5% ~ 50% scope.
preferably, described capsule material is melamine cyanurate cross-linked polymer, pentaerythritol phosphate melamine salt cross-linked polymer, three (tribromo phenyl) cyanurate cross-linked polymer or three (penta-bromophenyl) cyanurate cross-linked polymers.
preferably, described core is inorganic hypo-aluminum orthophosphate, inorganic magnesium hypophosphite, inorganic Hypophosporous Acid, 50 lanthanum, inorganic Hypophosporous Acid, 50 yttrium or inorganic cerous hypophosphite.
the preparation method of above-mentioned microencapsulation inorganic hypophosphite fire retardant, comprises the steps:
(1), utilize dispersion agent that inorganic hypophosphite is dispersed in solvent, obtain inorganic hypophosphite dispersion liquid;
(2), in the inorganic hypophosphite dispersion liquid of step (1) gained, add the substrate of preparing capsule material, in described substrate, have at least in a kind of molecular structure of substrate and contain triazine ring, be the building-up reactions that contains triazine ring cross-linked polymer under neutral condition maintaining reaction system pH, and then obtain milk sap or thickness paste;
(3), the milk sap for preparing of step (2) or thickness paste again through dehydration, dry, pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
the present invention using being wrapped in the surface of inorganic hypophosphite containing triazine ring cross-linked polymer as capsule material, has obtained microencapsulation inorganic hypophosphite fire retardant by microencapsulation technology, and its tool has the following advantages: 1, thermostability significantly improves, and is difficult for spontaneous combustion; 2, better with the consistency of polymeric matrix, can improve the over-all properties of material; 3, when with polymeric matrix hybrid process, can improve fluidity of molten, improve Drawing abillity; 4, capsule material contains triazine ring cross-linked polymer itself as a kind of nitrogenated flame retardant, can form the compound flame-retardant system of nitrogen-phosphorus with the inorganic hypophosphite of core, by the cooperative flame retardant effect of performance nitrogen-phosphorus, can further improve the flame retardant resistance of microencapsulation inorganic hypophosphite fire retardant of the present invention.
in addition, preparation method of the present invention also has advantages of that technique is simple, easy handling.
Accompanying drawing explanation
fig. 1 is the infrared comparison diagram of inorganic hypo-aluminum orthophosphate and embodiment 1 gained microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product.
Embodiment
below the specific embodiment of the present invention is described, and the present invention will be further described in detail in conjunction with the accompanying drawings and embodiments, but be not limited to these embodiment.
the core that the preferred a kind of embodiment of the present invention is microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, and capsule material is melamine cyanurate; Concrete preparation process comprises the steps:
(1) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 80 ℃ ~ 100 ℃, agitation condition, described inorganic hypophosphite is dispersed in described solvent, obtains inorganic hypophosphite dispersion liquid;
(2) to the tricyanic acid that adds 0.1 ~ 25 weight part in the inorganic hypophosphite dispersion liquid of step (1) gained, stir, then in reaction system, add respectively the trimeric cyanamide of 0.1 ~ 25 weight part and the phenyl-trichloro-silicane of 0.1 ~ 10 weight part; By pH adjusting agent, maintain the pH of whole reaction system in 6 ~ 8 scope, and at 80 ~ 120 ℃ stirring reaction 2 ~ 12 hours, obtain milk sap or thickness paste;
(3) milk sap or the thickness paste of step (2) gained are filtered, centrifugation, dry and pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
wherein, in step (2), trimeric cyanamide and phenyl-trichloro-silicane are several times, alternately add in reaction system.So-called " alternately adding in reaction system several times, " refers to and first in reaction system, adds a certain amount of trimeric cyanamide, then add a certain amount of phenyl-trichloro-silicane, add again after a certain amount of trimeric cyanamide, continue to add a certain amount of phenyl-trichloro-silicane ... so circulation, until all add the trimeric cyanamide of all formula ratios and phenyl-trichloro-silicane.Certainly, add first order the no requirement (NR) of trimeric cyanamide and phenyl-trichloro-silicane, can be optionally both one of first add in reaction system, but first to add trimeric cyanamide for well.
another is preferred embodiment that the core of microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite for the present invention, and capsule material is pentaerythritol phosphate melamine salt; Concrete preparation process comprises the steps:
(1) prepare pentaerythritol phosphate: by a certain amount of phosphoric acid at 60 ℃ ~ 80 ℃ after preheating, in this phosphoric acid, add the tetramethylolmethane that accounts for described phosphoric acid quality 33% ~ 50%, be warming up to again 115 ℃ ~ 125 ℃, under agitation condition, react 4 ~ 6 hours, obtain thick liquid, be pentaerythritol phosphate;
(2) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 60 ℃ ~ 100 ℃, agitation condition, inorganic hypophosphite is dispersed in solvent, obtains inorganic hypophosphite dispersion liquid;
(3) to the trimeric cyanamide that adds 0.1 ~ 20 weight part in the inorganic hypophosphite dispersion liquid of step (2) gained, stir, then in reaction system, add the prepared pentaerythritol phosphate of 1 ~ 40 weight part step (1), at 60 ℃ ~ 100 ℃, stirring reaction is 2 ~ 8 hours, obtains milk sap or thickness paste;
(4) milk sap or the thickness paste of step (3) gained are filtered, centrifugation, dry and pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
the present invention is another is preferred embodiment that the core of microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, and capsule material is three (tribromo phenyl) cyanurate; Concrete preparation process comprises the steps:
(1) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 40 ℃ ~ 50 ℃, agitation condition, inorganic hypophosphite is dispersed in solvent, obtains inorganic hypophosphite dispersion liquid;
(2) to the cyanuric chloride that adds 0.1 ~ 20 weight part in the inorganic hypophosphite dispersion liquid of step (1) gained, stir, then to the tribromophenol that adds 1 ~ 50 weight part in reaction system, by pH adjusting agent, maintain the pH of whole reaction system in 6 ~ 8 scope, at 70 ℃ ~ 80 ℃, stirring reaction is 2 ~ 4 hours, obtains milk sap or thickness paste;
(3) milk sap or the thickness paste of step (2) gained are filtered, centrifugation, dry and pulverize, obtain described microencapsulation inorganic hypophosphite fire retardant.
the microencapsulation inorganic hypophosphite fire retardant that is melamine cyanurate at above-mentioned capsule material, capsule material are in the preparation process of microencapsulation inorganic hypophosphite fire retardant of three (tribromo phenyl) cyanurate, in step (2), also in reaction system, added pH buffer reagent.The effect that adds pH buffer reagent is to guarantee that reaction system is in all the time a pH and is neutral state.PH buffer reagent can be when adding tricyanic acid, or when adding cyanuric chloride, add in reaction system, and described pH buffer reagent can be selected conventional sodium carbonate or sodium bicarbonate etc.
in above-mentioned preparation process, pH adjusting agent used is mainly conventional sodium hydroxide or potassium hydroxide etc.
in above-mentioned preparation process, dispersion agent used can be selected one or more the combination in calcium stearate, hexenyl bis-stearamides, tripoly phosphate sodium STPP, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum and fatty acid polyglycol ester.
embodiment 1
the inorganic hypo-aluminum orthophosphate that adds 9.0kg in reactor, 0.6kg calcium stearate and 100kg water, stirring makes it dispersed, add subsequently the tricyanic acid of 0.5kg and the sodium carbonate of 0.1kg, and the temperature of reactor is elevated to 80 ℃, tricyanic acid is dissolved, after 20 minutes, the phenyl-trichloro-silicane of 0.55kg trimeric cyanamide and 0.1kg is alternately slowly joined in reactor several times, the pH that controls reaction system by dropping sodium hydroxide solution in this process is in the scope of 6-8, to be addedly temperature of reaction is increased to 100 ℃ after complete, remain at this temperature and continue to stir, react 10 hours, obtain thickness paste, after filtration, dry, after pulverizing, make pulverous microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product.
the charateristic avsorption band that all contains hypo-aluminum orthophosphate in the infrared spectrum of the microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product that as shown in Figure 1, the present embodiment makes (i.e. parcel hypo-aluminum orthophosphate in figure) and inorganic hypo-aluminum orthophosphate pure sample: corresponding to the 2385cm of P-H key
-1
, corresponding to the 1193cm of P=O key
-1
, corresponding to the 1078cm of P-O key
-1
.And in the infrared line of the microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product of the present embodiment, wave number is at 3392 cm
-1
there is a strong absorption peak at place, for-NH
2
the charateristic avsorption band of key; Wave number is at 3232 cm
-1
there is a strong absorption peak at place, is the hydrogen bond charateristic avsorption band in melamine cyanurate; Wave number is at 1778 cm
-1
there is a weak absorption peak at place, is the charateristic avsorption band of C=O key; Wave number is at 1735 cm
-1
with 1662 cm
-1
a strong absorption peak and a weak absorption peak at place, for-NH
2
charateristic avsorption band; Wave number is at 1536 cm
-1
with 1450 cm
-1
two strong absorption peaks at place correspond respectively to the charateristic avsorption band of C=N key and C-N key.The above results shows, the melamine cyanurate microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor of the present embodiment is successfully prepared.In the present embodiment, use phenyl-trichloro-silicane and play the effect that promotes that crosslinking polymerization network forms.
the microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product that the present embodiment is made is placed under the environment of 300 ℃, in 10 minutes, dieseling does not occur, and than the spontaneous combustion in 2 minutes of inorganic hypo-aluminum orthophosphate, thermostability is improved largely.
the microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product that the present embodiment is made adds in nylon 6, prepares fire-retardant level nylon 6.When fire retardant addition is 20% time, material reaches UL94 V-0 rank, and the oxygen index LOI of obtained flame-retardant level nylon 6 material reaches 28.5.
embodiment 2
in reactor, add 1.2kg phosphoric acid, at 80 ℃ of temperature, preheating is 10 minutes, then slowly adds 0.4kg tetramethylolmethane, is warming up to 120 ℃, opens and stirs, and reacts and obtains light yellow viscous liquid after 4 hours, and this is pentaerythritol phosphate.
separately get a reactor, the inorganic hypo-aluminum orthophosphate that adds 8.0kg, 0.5kg hexenyl bis-stearamides and 80kg water, stirring makes inorganic hypo-aluminum orthophosphate dispersed, the trimeric cyanamide that adds subsequently 0.4kg, and the temperature of reactor is elevated to 80 ℃, trimeric cyanamide is dissolved, after 20 minutes, the approximately 1.6kg pentaerythritol phosphate being successfully prepared is slowly added drop-wise in reactor, after dripping, temperature of reaction is increased to 100 ℃, remain at this temperature and continue to stir, react 6 hours, the thickness paste obtaining after filtration, dry, after pulverizing, make Powdered microencapsulation inorganic hypo-aluminum orthophosphate combustion inhibitor product.
embodiment 3
the inorganic magnesium hypophosphite that adds 8kg in reactor, 0.5kg tripoly phosphate sodium STPP and 80kg ethyl acetate, stirring makes inorganic magnesium hypophosphite dispersed, add subsequently 0.3kg cyanuric chloride and 0.2kg sodium carbonate, stir, and the temperature of reactor is elevated to 40 ℃, cyanuric chloride is dissolved, after 10 minutes, 1.7kg tribromophenol is slowly added drop-wise in reactor, drip sodium hydroxide solution keeps the pH value of system in the scope of 6-8 simultaneously, after dripping, tribromophenol temperature of reaction is increased to 70 ℃, remain at this temperature and continue to stir, react 4 hours, the thickness paste obtaining after filtration, dry, after pulverizing, make Powdered microencapsulation inorganic magnesium hypophosphite flame retardant products.
above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. a microencapsulation inorganic hypophosphite fire retardant, it is characterized in that: the core of described microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, capsule material is for containing triazine ring cross-linked polymer, and the per-cent that capsule material accounts for described microencapsulation inorganic hypophosphite fire retardant total mass is in 5% ~ 50% scope.
2. microencapsulation inorganic hypophosphite fire retardant according to claim 1, is characterized in that: described capsule material is melamine cyanurate cross-linked polymer, pentaerythritol phosphate melamine salt cross-linked polymer, three (tribromo phenyl) cyanurate cross-linked polymer or three (penta-bromophenyl) cyanurate cross-linked polymers.
3. microencapsulation inorganic hypophosphite fire retardant according to claim 1, is characterized in that: described core is inorganic hypo-aluminum orthophosphate, inorganic magnesium hypophosphite, inorganic Hypophosporous Acid, 50 lanthanum, inorganic Hypophosporous Acid, 50 yttrium or inorganic cerous hypophosphite.
4. the preparation method of the microencapsulation inorganic hypophosphite fire retardant described in any one in claim 1 ~ 3, is characterized in that: comprise the steps:
(1), utilize dispersion agent that inorganic hypophosphite is dispersed in solvent, obtain inorganic hypophosphite dispersion liquid;
(2), in the inorganic hypophosphite dispersion liquid of step (1) gained, add the substrate of preparing capsule material, in described substrate, have at least in a kind of molecular structure of substrate and contain triazine ring, be the building-up reactions that contains triazine ring cross-linked polymer under neutral condition maintaining reaction system pH, and then obtain milk sap or thickness paste;
(3), the milk sap for preparing of step (2) or thickness paste again through dehydration, dry, pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
5. the preparation method of microencapsulation inorganic hypophosphite fire retardant according to claim 4, is characterized in that: the core of described microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, and capsule material is melamine cyanurate; Concrete preparation process comprises the steps:
(1) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 80 ℃ ~ 100 ℃, agitation condition, described inorganic hypophosphite is dispersed in described solvent, obtains inorganic hypophosphite dispersion liquid;
(2) to the tricyanic acid that adds 0.1 ~ 25 weight part in the inorganic hypophosphite dispersion liquid of step (1) gained, stir, then in reaction system, add respectively the trimeric cyanamide of 0.1 ~ 25 weight part and the phenyl-trichloro-silicane of 0.1 ~ 10 weight part; By pH adjusting agent, maintain the pH of whole reaction system in 6 ~ 8 scope, and at 80 ~ 120 ℃ stirring reaction 2 ~ 12 hours, obtain milk sap or thickness paste;
(3) milk sap or the thickness paste of step (2) gained are filtered, centrifugation, dry and pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
6. the preparation method of microencapsulation inorganic hypophosphite fire retardant according to claim 5, is characterized in that: in step (2), trimeric cyanamide and phenyl-trichloro-silicane are several times, alternately add in reaction system.
7. the preparation method of microencapsulation inorganic hypophosphite fire retardant according to claim 4, is characterized in that: the core of described microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, and capsule material is pentaerythritol phosphate melamine salt; Concrete preparation process comprises the steps:
(1) prepare pentaerythritol phosphate: by a certain amount of phosphoric acid at 60 ℃ ~ 80 ℃ after preheating, in this phosphoric acid, add the tetramethylolmethane that accounts for described phosphoric acid quality 33% ~ 50%, be warming up to again 115 ℃ ~ 125 ℃, under agitation condition, react 4 ~ 6 hours, obtain thick liquid, be pentaerythritol phosphate;
(2) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 60 ℃ ~ 100 ℃, agitation condition, inorganic hypophosphite is dispersed in solvent, obtains inorganic hypophosphite dispersion liquid;
(3) to the trimeric cyanamide that adds 0.1 ~ 20 weight part in the inorganic hypophosphite dispersion liquid of step (2) gained, stir, then in reaction system, add the prepared pentaerythritol phosphate of 1 ~ 40 weight part step (1), at 60 ℃ ~ 100 ℃, stirring reaction is 2 ~ 8 hours, obtains milk sap or thickness paste;
(4) milk sap or the thickness paste of step (3) gained are filtered, centrifugation, dry and pulverize, obtain pulverous described microencapsulation inorganic hypophosphite fire retardant.
8. the preparation method of microencapsulation inorganic hypophosphite fire retardant according to claim 4, is characterized in that: the core of described microencapsulation inorganic hypophosphite fire retardant is inorganic hypophosphite, and capsule material is three (tribromo phenyl) cyanurate; Concrete preparation process comprises the steps:
(1) dispersion agent of the solvent of the inorganic hypophosphite of 5 ~ 50 weight parts, 30 ~ 400 weight parts and 0.1 ~ 5 weight part is added in reaction vessel, under 40 ℃ ~ 50 ℃, agitation condition, inorganic hypophosphite is dispersed in solvent, obtains inorganic hypophosphite dispersion liquid;
(2) to the cyanuric chloride that adds 0.1 ~ 20 weight part in the inorganic hypophosphite dispersion liquid of step (1) gained, stir, then to the tribromophenol that adds 1 ~ 50 weight part in reaction system, by pH adjusting agent, maintain the pH of whole reaction system in 6 ~ 8 scope, at 70 ℃ ~ 80 ℃, stirring reaction is 2 ~ 4 hours, obtains milk sap or thickness paste;
(3) milk sap or the thickness paste of step (2) gained are filtered, centrifugation, dry and pulverize, obtain described microencapsulation inorganic hypophosphite fire retardant.
9. according to the preparation method of the microencapsulation inorganic hypophosphite fire retardant described in claim 5 or 6 or 8, it is characterized in that: in step (2), also in reaction system, added pH buffer reagent.
10. according to the preparation method of the microencapsulation inorganic hypophosphite fire retardant described in any one in claim 5 ~ 8, it is characterized in that: described dispersion agent is one or more the combination in calcium stearate, hexenyl bis-stearamides, tripoly phosphate sodium STPP, triethyl hexyl phosphoric acid, methyl amyl alcohol, derivatived cellulose, polyacrylamide, guar gum and fatty acid polyglycol ester.
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| CN104448948A (en) * | 2014-12-10 | 2015-03-25 | 山东川君化工股份有限公司 | Preparation method of modified aluminium hypophosphite |
| CN105582863A (en) * | 2015-07-20 | 2016-05-18 | 珠海市金浓霖化工科技有限公司 | Biological nanometer capsule, biological micron capsule, beta-cyclodextrin-matrix micro-nano multidimensional blank ball and silicon dioxide micron capsule |
| CN108676427A (en) * | 2018-04-26 | 2018-10-19 | 武汉工程大学 | A kind of aqueous microencapsulation super-thin steel structure fire-proof paint and preparation method thereof |
| CN108676427B (en) * | 2018-04-26 | 2020-07-28 | 武汉工程大学 | Water-based microencapsulated ultra-thin steel structure fireproof coating and preparation method thereof |
| CN110565393A (en) * | 2019-07-15 | 2019-12-13 | 宁波东方席业有限公司 | Weather-proof, moisture-proof and fireproof multifunctional mat and preparation method thereof |
| CN110615936A (en) * | 2019-10-09 | 2019-12-27 | 江苏万纳普新材料科技有限公司 | Special halogen-free flame-retardant synergistic functional master batch for modifying styrene resin and preparation method thereof |
| CN110615936B (en) * | 2019-10-09 | 2022-12-27 | 江苏万纳普新材料科技有限公司 | Special halogen-free flame-retardant synergistic functional master batch for modifying styrene resin and preparation method thereof |
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