CN105482163A - Microcapsule flame retardant with high heat resistance and preparation method of microcapsule flame retardant - Google Patents
Microcapsule flame retardant with high heat resistance and preparation method of microcapsule flame retardant Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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Abstract
The invention discloses a microcapsule flame retardant with high heat resistance and a preparation method of the microcapsule flame retardant. A core material adopts a flame retardant, a capsule material is a polyphosphazene cross-linked polymer obtained through a reaction of phosphonitrile with one or more of biphenyl polyamine, condensed aromatic polyamine and heterocyclic aromatic polyamine, and the mass ratio of the capsule material to the core material is (0.1:1)-(5:1). According to the preparation method, the flame retardant is dispersed in a solvent, phosphonitrile and one or more of biphenyl polyamine, condensed aromatic polyamine and heterocyclic aromatic polyamine are added, an acid-binding agent is added, the mixture reacts, and the microcapsule flame retardant is obtained. The capsule material contains a large quantity of aromatic structures, chemical weak bonds can be avoided, and the microcapsule flame retardant has higher heat resistance and good char forming performance; the capsule material contains a polyphosphazene cross-linked structure body with more nitrogen and phosphorus and imino groups, has the synergic nitrogen and phosphorus flame retarding characteristic and has a better time-sharing flame retarding effect with the core material; the aromatic structures contained in the capsule mateiral have good compatibility with a polymer matrix containing an aromatic ring on a main chain, the mechanical performance of the composite is excellent, and no remarkable dyeing effect is caused to the polymer matrix.
Description
Technical field
The invention belongs to fire retardant modification field, be specifically related to a kind of high heat-resisting microcapsule flame retardant and preparation method thereof.
Background technology
Microencapsulation technology refers to and utilizes coating material that is natural or synthesis, will be wrapped by material coated, and form a kind of minigel technology with closed cyst wall structure that diameter is 1 ~ 1000 μm.In field of fire-proof technology, fire retardant and the polymeric matrix of inner capsule-core separate, and the initial stage is not subject to external influence, and under suitable condition, cyst wall breaks and makes capsule-core directly act on polymeric matrix, and it is convenient and efficient to bring to controlled fire-retardant control that is fire-retardant and different flame mechanism.
The capsule material of current employing is thermosetting resin, as in patent CN1480253A, CN102229712A, CN101812305A, CN101376812, CN101362836A and CN101812186A, carry out coated with urea-formaldehyde resin, melamine/formaldehyde resin, melamine resin, epoxy resin and Silica hydrogel etc. to fire retardant mostly merely, obtain the fire-retardant powder of water tolerance and excellent in stability, compared with not coated fire retardant, the water-soluble obvious reduction of microcapsule flame retardant, flame retardant resistance and stability are also increased.But thermoset capsule material is easily extruded and partial rupture in the course of processing, affect covered effect, in addition, in adding procedure, there is the problems such as dispersed and consistency due to additive flame retardant, although these microcapsule flame retardant are improved in dispersiveness, but improve not obvious with the consistency of some matrixes, detrimentally affect is produced to the physical and mechanical properties of material, simultaneously, capsule material function singleness, certain cooperative flame retardant effect cannot be played with core, and poor heat resistance, be not adapted at using in the polymkeric substance compared with high processing temperature.
Summary of the invention
For overcoming above-mentioned technical problem, it is good that primary and foremost purpose of the present invention is to provide a seed capsules material covered effect, good with matrix phase capacitive, the heat-resisting microcapsule flame retardant of height of excellent fireproof performance.
Another object of the present invention is to the preparation method that the heat-resisting microcapsule flame retardant of above-mentioned height is provided.
The present invention is achieved by the following technical solutions:
A kind of high heat-resisting microcapsule flame retardant, the core of the heat-resisting microcapsule flame retardant of described height is fire retardant, capsule material is with the polyphosphonitrile cross-linked polymer of one or more reactions in phosphonitrile and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic hydrocarbon polyamines, the mass ratio of capsule material and core is 0.1:1 ~ 5:1, and preferred mass is than being 0.4:1 ~ 2:1.
Microcapsule flame retardant of the present invention is using a kind of high heat-resisting polyphosphonitrile cross-linked polymer as capsule material, the microcapsule flame retardant of a kind of nucleocapsid structure that coated traditional fire retardant is formed, the particle diameter of microcapsule flame retardant is 600-1600nm, if the particle diameter of microcapsule flame retardant is too large, when adding in polymeric matrix, the mechanical property of polymkeric substance can decline, therefore the preferred 800nm-1300nm of the particle diameter of microcapsule flame retardant.
There is no particular restriction for the kind of fire retardant of the present invention, includes but not limited to one or more in inorganic combustion inhibitor, organic silicon fibre retardant or phosphorus-nitrogenated flame retardant.
Wherein said inorganic combustion inhibitor can be aluminium hydroxide, magnesium hydroxide, zinc borate etc., preferred aluminium hydroxide;
Described organic silicon fibre retardant can be able to be cagelike silsesquioxane, polydimethylsiloxane, two for organo-siloxane
Ring young laying ducks in cage siloxanes etc., preferred cagelike silsesquioxane;
Described phosphorus-nitrogenated flame retardant can be melamine phosphate, ammonium polyphosphate, tetramethylolmethane melamine phosphate
Deng, preferred melamine phosphate.
The hydroperoxyl radical that melamine phosphate discharges in combustion can play the effect suppressing burning, the layer of charcoal produced in combustion processes mainly polymkeric substance becomes the porous layer of charcoal of charcoal, and cross-linked polymer (PNO) x in melamine phosphate combustion processes, can be converted into, layer of charcoal is made to increase solid reinforcement further, therefore the preferred melamine phosphate of the present invention.
Phosphonitrile of the present invention is one or more in ring phosphonitrile or linear polyphosphazene, preferred hexachlorocyclotriphosphazene;
Wherein said heteroaromatic polyamines be five-membered ring aromatic hydrocarbon polyamines or hexa-member heterocycle aromatic hydrocarbon polyamines one or more; Five-membered ring aromatic hydrocarbon polyamines can be one or more in thiophene polyamines class, furans polyamines class or pyrroles's polyamines class; Described hexa-member heterocycle aromatic hydrocarbon polyamines can be one or more in pyrimidine polyamines class, quinoline polyamines class or indoles polyamines class.
The preferred biphenyl polyamines of the present invention or polycyclic aromatic hydrocarbon polyamines, described biphenyl polyamines is one or more in benzidine, biphenyl tetramine, dimethyl diphenyl diamines or dihydroxybiphenyl diamines, is more preferably 3,3 ', 4,4 '-biphenyl tetramine; Described polycyclic aromatic hydrocarbon polyamines is one or more in naphthalene polyamines class, anthracene polyamines class or luxuriant and rich with fragrance polyamines class, more preferably 1,5-diaminonaphthalene.
The preferred hexachlorocyclotriphosphazene of capsule material of the present invention and 3,3 ', 4,4 '-biphenyl tetramine, hexachlorocyclotriphosphazene and 1, the polyphosphonitrile cross-linked polymer that the reaction of 5-diaminonaphthalene generates, this capsule material not only possesses higher thermotolerance, and owing to containing more nitrogen element and phosphoric in polyphosphonitrile cross-linked polymer, significantly can play nitrogen-phosphorus cooperative flame retardant effect.
Present invention also offers the preparation method of above-mentioned a kind of high heat-resisting microcapsule flame retardant, comprise the steps:
(1) utilize dispersion agent to be scattered in uniformly in solvent by fire retardant, obtain the dispersion liquid of fire retardant;
(2) in the dispersion liquid of the fire retardant obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state
Add one or more in phosphonitrile and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines, add acid binding agent simultaneously, and add weak acid adjust ph to neutral, pass into rare gas element simultaneously, react under making system be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white obtained for step (2) or faint yellow solid block are washed through vacuum filtration, then lyophilize, pulverize grinding, obtain pulverous high heat-resisting microcapsule flame retardant.
Wherein, the dispersion agent described in step (1) is one or more in polyvinyl alcohol, gelatin, sodium hexametaphosphate, tripoly phosphate sodium STPP, sodium laurylsulfonate, OP emulsifying agent or Perfluorocaprylic Acid;
Solvent described in step (1) is one in chloroform, dioxane, toluene, dimethylbenzene, acetone, butanone, formaldehyde, methyl alcohol, ethanol, methylene dichloride, butanols, butyleneglycol, N ' N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) or N ' dinethylformamide or complex solvent.
Acid binding agent described in step (2) is one or more of pyridine, triethylamine, salt of wormwood or sodium carbonate;
Weak acid described in step (2) be carbonic acid, acetic acid or hypochlorous one or more.
Phosphonitrile described in step (2) and and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines in one or more molar mass than for 1:1 ~ 1:6; In biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines, the mol ratio of one or more and acid binding agent is 1:2 ~ 1:4, and the time of reaction is 1-8h.
Washing described in step (3) refers to uses dioxane, tetrahydrofuran (THF), ethanol, deionized water successively washing 1-3 time.
The present invention compared with prior art, has following beneficial effect:
(1) the present invention adopts the polyphosphonitrile cross-linked polymer of one or more reaction generations in phosphonitrile and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines as capsule material, containing a large amount of aromatic hydrocarbon structure in coated capsule material, chemical weak bond can be avoided, the microcapsule flame retardant that coated fire retardant is formed has higher thermotolerance, carbon-forming performance is good, be applicable to preparing the higher ignition resistant polymeric composite of processing temperature by melt-blending process, and such capsule material all has good covered effect for different core, suitability is extremely wide;
(2) coated capsule material of the present invention contains nitrogen element and the more phosphonitrile crosslinking structural body of phosphoric and imino functionalities, certain nitrogen-phosphorus cooperative flame retardant effect can will be played in flame-retardant polymer process, and with inner core, there is good timesharing flame retardant effect, the aromatic hydrocarbon structure simultaneously contained in capsule material and main chain contain the polymeric matrix of aromatic nucleus, and especially consistency is good, the microcapsule flame retardant of preparation is added in matrix, prepared matrix material not only mechanical property has obvious lifting, and there is higher limiting oxygen index(LOI) and better vertical combustion performance, in addition, the microcapsule flame retardant powder of preparation, originally as white or faint yellow, effectively can shield the color of conventional flame retardant, not have obvious Color to polymeric matrix, contributes to keeping polymeric matrix idiochromatic,
(3) the whole technological process of the present invention facilitates controlled, and industrial applicability is strong.
Accompanying drawing explanation
Fig. 1 is the high power scanning electron microscopic picture of a kind of high heat-resisting microcapsule flame retardant prepared by embodiment 5.
Fig. 2 is the low power scanning electron microscopic picture of a kind of high heat-resisting microcapsule flame retardant prepared by embodiment 5.
Fig. 3 is the grain size distribution of a kind of high heat-resisting microcapsule flame retardant prepared by embodiment 5.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
Embodiment 1:
(1) in there-necked flask, add 10g aluminium hydroxide, add 200ml alcohol solvent, and add 10ml dispersion
Agent sodium laurylsulfonate, mechanical stirring 0.5h ~ 1h is prepared into aluminium hydroxide dispersion liquid;
(2) add hexachlorocyclotriphosphazene in the aluminium hydroxide dispersion liquid obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state, then add 3,3 ', 4,4 '-biphenyl tetramine, adds acid binding agent triethylamine simultaneously, wherein said hexachlorocyclotriphosphazene and 3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine is 2:3,3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine and acid binding agent triethylamine is 1:4, and the reaction times is 6h, and add acetic acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the microcapsule aluminium hydroxide fire retardant that size is 0.9 μm, wherein, the mass ratio of capsule material and core is 0.4:1.
Embodiment 2:
(1) in there-necked flask, add 10g cagelike silsesquioxane, add 200ml solvent acetone, and add 10ml polyethylene of dispersing agent alcohol, mechanical stirring 0.5h ~ 1h obtains cagelike silsesquioxane dispersion liquid;
(2) add hexachlorocyclotriphosphazene in the cagelike silsesquioxane dispersion liquid obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state, then add 3,3 ', 4,4 '-biphenyl tetramine, adds acid binding agent pyridine simultaneously, wherein said hexachlorocyclotriphosphazene and 3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine is 2:3,3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine and acid binding agent triethylamine is 1:4, and the reaction times is 6h, and add carbonic acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the microcapsule caged silsesquioxane fire retardant that size is 0.9 μm, wherein, the mass ratio of capsule material and core is 0.4:1.
Embodiment 3:
(1) in there-necked flask, add 10g melamine phosphate, add 200ml solvent xylene, and add 10ml pentasodium triphosphate of dispersing agent, mechanical stirring 0.5h ~ 1h is prepared into melamine phosphate dispersion liquid;
(2) add hexachlorocyclotriphosphazene in the melamine phosphate dispersion liquid obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state, then add 3,3 ', 4,4 '-biphenyl tetramine, adds acid binding agent triethylamine simultaneously, wherein said hexachlorocyclotriphosphazene and 3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine is 2:3,3,3 ', 4, the mol ratio of 4 '-biphenyl tetramine and acid binding agent triethylamine is 1:4, and the reaction times is 6h, and add hypochlorous acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the microcapsule melamine phosphate fire retardant that size is 0.9 μm, wherein, the mass ratio of capsule material and core is 0.4:1.
Embodiment 4:
(1) in there-necked flask, add 10g melamine phosphate, add 200ml etoh solvent, and add 10ml dispersion agent sodium laurylsulfonate, mechanical stirring 0.5h ~ 1h is prepared into melamine phosphate dispersion liquid;
(2) hexachlorocyclotriphosphazene is added in the melamine phosphate dispersion liquid obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state, then 1 is added, 5-diaminonaphthalene, adds acid binding agent pyridine simultaneously, wherein said hexachlorocyclotriphosphazene and 1, the mol ratio of 5-diaminonaphthalene is 1:3, the mol ratio of 1,5-diaminonaphthalene and acid binding agent is 1:2, and the reaction times is 6h, and add carbonic acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the micro encapsulation melamine phosphate fire retardant that size is 0.9 μm, wherein, the mass ratio of capsule material and core is 0.4:1.
Embodiment 5:
(1) in there-necked flask, add 10g melamine phosphate, add 200ml etoh solvent, and add 10ml dispersion agent sodium laurylsulfonate, mechanical stirring 0.5h ~ 1h is prepared into melamine phosphate dispersion liquid;
(2) in the melamine phosphate dispersion liquid of step (1), hexachlorocyclotriphosphazene is added in mechanical stirring under ultrasonic and room temperature state, then 1 is added, 5-diaminonaphthalene, adds acid binding agent pyridine simultaneously, wherein said hexachlorocyclotriphosphazene and 1, the mol ratio of 5-diaminonaphthalene is 1:4, the mol ratio of 1,5-diaminonaphthalene and acid binding agent is 1:2, and the reaction times is 7h, and add carbonic acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the microcapsule melamine phosphate fire retardant that size is 1.2 μm, wherein, the mass ratio of capsule material and core is 0.8:1.
As shown in Figure 1-2, high power and the low power scanning electron microscopic picture of the heat-resisting microcapsule flame retardant of height prepared by the present embodiment, as can be seen from Figure, when the mass ratio of capsule material and core is 0.8:1, core can carry out coated preferably by capsule material, and the surface compact of coating layer is with level and smooth, whole microcapsule are approximate sphericity, the comparatively strong not easily adhesion of independence each other.
As can be seen from the grain size distribution of Fig. 3, the heat-resisting microcapsule flame retardant even particle size distribution of height prepared by the present embodiment, because adopt more capsule material to carry out coated to core, the performed polymer that the various ingredients of capsule material is formed tend to the particle accumulation that surface tension is larger go forward side by side single step reaction be cross-linked, make the particle diameter trend of whole microcapsule evenly, size distribution also just narrows.
Embodiment 6:
(1) in there-necked flask, add 10g melamine phosphate, add 200ml etoh solvent, and add 10ml dispersion agent sodium laurylsulfonate, mechanical stirring 0.5h ~ 1h is prepared into melamine phosphate dispersion liquid;
(2) hexachlorocyclotriphosphazene is added in the melamine phosphate dispersion liquid obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state, then 1 is added, 5-diaminonaphthalene, adds acid binding agent pyridine simultaneously, wherein said hexachlorocyclotriphosphazene and 1, the mol ratio of 5-diaminonaphthalene is 1:5, the mol ratio of 1,5-diaminonaphthalene and acid binding agent is 1:2, and the reaction times is 8h, and add hypochlorous acid adjust ph to neutral, pass into N simultaneously
2, react under making entirety be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white step (2) obtained or faint yellow solid block are through vacuum filtration, successively wash 3 times with dioxane, tetrahydrofuran (THF), ethanol, deionized water, lyophilize again, pulverizing grinding, obtain the microcapsule melamine phosphate fire retardant that size is 1.5 μm, wherein, the mass ratio of capsule material and core is 1:1.
Comparative example:
Be 201110102975.1 prepared the coated melamine phosphate of a kind of melamine/formaldehyde resin with reference to Chinese invention patent application number, the size controlling microcapsule flame retardant is 0.9 μm, and the mass ratio of capsule material and core is 0.4:1.
Microcapsule flame retardant embodiment 1-6 and comparative example prepared carries out thermal weight loss performance test under nitrogen atmosphere, and test result is as shown in table 1.
The microcapsule flame retardant thermal weight loss performance under nitrogen atmosphere of table 1 embodiment and comparative example
As can be seen from the result of table 1, embodiment 1-3 adopts hexachlorocyclotriphosphazene and 3, 3 ', 4, the coated three kinds of different conventional flame retardant cores of the capsule material prepared of 4 '-biphenyl tetramine, find the beginning degradation temperature of microcapsule flame retardant, degraded 50%(massfraction) temperature and maximum weight loss rate temperature all than comparative example melamine/formaldehyde resin corresponding to beginning degradation temperature, degraded 50%(massfraction) temperature and maximum weight loss rate temperature want high, illustrate that the microcapsule flame retardant of preparation has obvious lifting in resistance toheat, and, be widely used in the coated preparation process of different types of conventional flame retardant.Meanwhile, as can be seen from embodiment 3 and embodiment 4, when the capsule material adopting hexachlorocyclotriphosphazene and 1,5-diaminonaphthalene to prepare microcapsule, the thermotolerance of fire retardant can be improved further.Can find after comparative example 4-6, when in capsule material component 1, the lifting of 5-diaminonaphthalene mole number, thicker capsule material can be formed, be prepared into the microcapsule flame retardant that particle diameter is larger, it is in thermotolerance, compare the thinner fire retardant of capsule material to have and promote significantly further, especially relative to comparative example, no matter prepared fire retardant is all have remarkable lifting in thermotolerance or on final carbon-forming performance, this is summed up as 1, 5-diaminonaphthalene itself possesses high heat resistance, and with hexachlorocyclotriphosphazene sufficient reacting, form the surface that more performed polymer is gathered in conventional flame retardant, and form the coated conventional flame retardant of capsule material of crosslinking structure further, simultaneously, polycyclic aromatic hydrocarbon itself possesses higher one-tenth charcoal, so, final one-tenth charcoal can be higher.
In summary, the thermotolerance of embodiment 1-6 and carbon left, apparently higher than comparative example, show that microcapsule flame retardant of the present invention has higher thermotolerance, and carbon-forming performance are good, are applicable to preparing the higher ignition resistant polymeric composite of processing temperature by melt-blending process.
The microcapsule flame retardant of embodiment 1-6 and comparative example is mixed by weight ratio shown in table 2 with polyethylene terephthalate (PET) at 230 DEG C-260 DEG C, by extruding pelletization in twin screw extruder, obtained flame retardance of polymer test sample and mechanical test sample, test its flame retardant properties and mechanical property, test result is as shown in table 2-3.
Table 2 does not add the pure PET sample of fire retardant and adds the flame retardant properties contrast of matrix material after microcapsule flame retardant
As can be seen from the result of table 2, the limiting oxygen index(LOI) adding the matrix material of the microcapsule flame retardant of embodiment 1-6 is large
In 30, but easily drip because PET itself is heated, so need to add a certain amount of anti-dripping agent, simultaneously, the phosphonitrile crosslinking structural body that Nitrogen element in capsule material, phosphoric are more and imino functionalities significantly can play nitrogen-phosphorus cooperative flame retardant effect, and PET is tested, compared with comparative example by the V-0 level of UL-94 vertical combustion, not only in limiting oxygen index(LOI), have more advantage, in vertical combustion, also show good flame retardant properties.
Table 3 is added with the mechanical property of the matrix material of microcapsule flame retardant
As can be seen from the result of table 3, embodiment 1-3 compares with comparative example, and when Microcapsules Size is basically identical, in tensile strength and notched Izod impact strength, some promotes the matrix material of preparation slightly; Embodiment 3 is compared with embodiment 4, adopts microcapsule that 1,5-diaminonaphthalene is prepared as cyst wall component than 3,3 ', 4, the consistency of the microcapsule that 4 '-biphenyl tetramine is prepared as cyst wall component and PET matrix is better, and its tensile strength and notched Izod impact strength promote all to some extent; Comparative example 4-6, when the thickness of microcapsule capsule material is along with 1, the increase of 5-diaminonaphthalene component and when increasing, microcapsule embody better consistency and dispersiveness in PET matrix, and mechanical property is promoted further, but, the excessive mechanical properties decrease that also can cause matrix material of particle diameter, because too large particle adds in matrix material, the defect causing fracture may be become, cause the decline of tensile strength and notched Izod impact strength.And relative to comparative example, the mechanical property of a kind of microcapsule flame retardant to matrix material prepared by interpolation the present invention has remarkable lifting, this shows the fire retardant coated relative to melamine/formaldehyde resin, especially consistency is good containing the polymeric matrix of aromatic nucleus for group of polyphosphazenes crosslinking structural body coating layer prepared by the present invention and main chain, and mechanical property is relatively better.
To sum up, fire retardant prepared by the present invention adds in PET matrix, prepared matrix material not only mechanical property has obvious lifting, and there is higher limiting oxygen index(LOI) and better vertical combustion performance, the more important thing is, fire retardant prepared by the present invention possesses higher thermotolerance, for the polymkeric substance that some processing temperatures are higher, fire retardant can be avoided to degrade in the blended course of processing of polymer melt and lost efficacy.
Performance test methods:
Particle diameter: get 1 ~ 3ml fire retardant ethanol (or deionized water) dispersion liquid, the fluctuation of light intensity is caused by the pedesis of dynamic light scattering-particle, Particles Moving speed is relevant to particle diameter, calculates particles size and distribution by light-intensity variation change and Intensity correlation function.
Thermal weight loss: each embodiment sample is placed in nitrogen atmosphere, temperature rise rate is 15 DEG C/min, test from room temperature to the thermogravimetric curve of 900 DEG C, and choose start weightless corresponding temperature, weightlessness reaches 50%(weight percentage) time multipair temperature, temperature corresponding to maximum weight loss rate of answering contrast as thermal characteristics index.
Carbon left: the massfraction namely behind thermal weight loss arrival stable region, carbon left is higher, represents that the carbon-forming performance of fire retardant itself is better.
Limiting oxygen index(LOI) (LOI): according to ASTMD2863, specimen size is 120mm*6.5mm*3.0mm, and every 10 groups of data are averaged as a net result.Oxygen index height represents that material is nonflammable, and the low expression material of oxygen index easily burns, and general oxygen index < 22 belongs to inflammable material, and oxygen index belongs to combustible matl between 22-27, and oxygen index > 27 belongs to nonflammable material.
Vertical combustion test (UL-94): according to ASTMD3801, specimen size is 127mm*12.7mm*1.6mm, and every 5 groups of data are averaged as a net result.The grade of UL-94 is divided into V-2, V-1, V-0, and its middle grade is that V-0 represents material excellent fireproof performance in vertical direction.
Claims (10)
1. a high heat-resisting microcapsule flame retardant, is characterized in that, the core of the heat-resisting microcapsule flame retardant of described height is fire retardant,
Capsule material is that the mass ratio of capsule material and core is 0.1:1 ~ 5:1 with the polyphosphonitrile cross-linked polymer of one or more reactions in phosphonitrile and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic hydrocarbon polyamines, and preferred mass is than being 0.4:1 ~ 2:1.
2. the high heat-resisting microcapsule flame retardant of one according to claim 1, is characterized in that, the particle diameter of the heat-resisting microcapsule flame retardant of described height is 600nm ~ 1600nm, preferred 800nm-1300nm.
3. the high heat-resisting microcapsule flame retardant of one according to claim 1, it is characterized in that, described fire retardant is one or more in inorganic combustion inhibitor, organic silicon fibre retardant or phosphorus-nitrogenated flame retardant, preferred aluminium hydroxide, organo-siloxane or melamine phosphate.
4. the high heat-resisting microcapsule flame retardant of one according to claim 1, is characterized in that, described phosphonitrile is one or more in ring phosphonitrile or linear polyphosphazene, preferred hexachlorocyclotriphosphazene.
5. the high heat-resisting microcapsule flame retardant of one according to claim 1, is characterized in that, described heteroaromatic polyamines be five-membered ring aromatic hydrocarbon polyamines or hexa-member heterocycle aromatic hydrocarbon polyamines one or more; Described biphenyl polyamines is one or more in benzidine, biphenyl tetramine, dimethyl diphenyl diamines or dihydroxybiphenyl diamines, is preferably 3,3 ', 4,4 '-biphenyl tetramine; Described polycyclic aromatic hydrocarbon polyamines is one or more in naphthalene polyamines class, anthracene polyamines class or luxuriant and rich with fragrance polyamines class, preferred 1,5-diaminonaphthalene.
6. the preparation method of a kind of high heat-resisting microcapsule flame retardant described in any one of claim 1-5, is characterized in that, comprise the steps:
(1) utilize dispersion agent to be scattered in uniformly in solvent by fire retardant, obtain the dispersion liquid of fire retardant;
(2) add in the dispersion liquid of the fire retardant obtained to step (1) in mechanical stirring and under ultrasonic and room temperature state
Enter one or more in phosphonitrile and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines, add acid binding agent simultaneously, and add weak acid adjust ph to neutral, pass into rare gas element simultaneously, react under making system be in anaerobic state, obtain a kind of white or faint yellow solid block;
(3) white obtained for step (2) or faint yellow solid block are washed through vacuum filtration, then lyophilize, pulverize grinding, obtain pulverous high heat-resisting microcapsule flame retardant.
7. the preparation method of a kind of high heat-resisting microcapsule flame retardant according to claim 6, it is characterized in that, the dispersion agent described in step (1) is one or more in polyvinyl alcohol, gelatin, sodium hexametaphosphate, tripoly phosphate sodium STPP, sodium laurylsulfonate, OP emulsifying agent or Perfluorocaprylic Acid; Described solvent is one in chloroform, dioxane, toluene, dimethylbenzene, acetone, butanone, formaldehyde, methyl alcohol, ethanol, methylene dichloride, butanols, butyleneglycol, N ' N-N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) or N ' dinethylformamide or complex solvent.
8. the preparation method of a kind of high heat-resisting microcapsule flame retardant according to claim 6, is characterized in that, acid binding agent described in step (2) is one or more of pyridine, triethylamine, salt of wormwood or sodium carbonate; Described weak acid be carbonic acid, acetic acid or hypochlorous one or more.
9. the preparation method of a kind of high heat-resisting microcapsule flame retardant according to claim 6, it is characterized in that, in the phosphonitrile described in step (2) and biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines, the molar mass of one or more is than being 1:1 ~ 1:6; In biphenyl polyamines, polycyclic aromatic hydrocarbon polyamines or heteroaromatic polyamines, the mol ratio of one or more and acid binding agent is 1:2 ~ 1:4, and the time of reaction is 1-8h.
10. the preparation method of a kind of high heat-resisting microcapsule flame retardant according to claim 6, is characterized in that, the washing described in step (3) refers to uses dioxane, tetrahydrofuran (THF), ethanol, deionized water successively washing 1-3 time.
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| CN110862620A (en) * | 2019-12-03 | 2020-03-06 | 中国科学技术大学 | Halogen-free flame-retardant filling material for nuclear power station cable and preparation method thereof |
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Effective date of registration: 20200713 Address after: Wanbao Industrial Park in Conghua District of Guangzhou City, Guangdong province 510935 City Ao Ao Town Road Patentee after: GUANGZHOU WANBAO ELECTRONIC MATERIAL Co.,Ltd. Address before: 510006 Panyu District, Guangzhou, Guangzhou University,, West Ring Road, No. 100 Patentee before: GUANGDONG University OF TECHNOLOGY |