CN104131463A - Metal ion-modified ammonium polyphosphate and its preparation method and use - Google Patents
Metal ion-modified ammonium polyphosphate and its preparation method and use Download PDFInfo
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Abstract
The invention discloses metal ion-modified ammonium polyphosphate and its preparation method and use. Ammonium polyphosphate is modified by a metal ion modification agent so that the metal ion-modified ammonium polyphosphate is prepared. The preparation method has simple processes, a low modification cost and a metal ion-modified ammonium polyphosphate finished product yield greater than or equal to 95%, and the product has solubility of 0.02-0.42g in water at a temperature of 25 DEG C and a moisture absorbing rate of 0.28-1.5%. LOI of the fabric subjected to metal ion-modified ammonium polyphosphate-based flame retardation treatment is 31%, and after water washing of the fabric 10 times, LOI still is greater than or equal to 25%. The polypropylene plastic subjected to metal ion-modified ammonium polyphosphate-based flame retardation treatment has LOI greater than or equal to 26.3%, UL94 vertical combustion level V-2 and a moisture absorbing rate less than or equal to 0.59%. The metal ion-modified ammonium polyphosphate has good flame resistance and slightly solubility, solves the problems of easy moisture absorption of ammonium polyphosphate and poor water resistance and can be widely used in fields of plastic, rubber, fireproof paint and textile coating flame retardation.
Description
Technical field
The present invention relates to APP modification technology field, disclose especially a kind of metallic ion modified polyphosphoric acid ammonium and its preparation method and application.
Background technology
APP (Ammonium Polyphosphate is called for short APP) is that a kind of phosphorus nitrogen content is high, do not produce the efficient phosphorus-nitrogen containing flame retardant of noxious material when Heat stability is good,, burning nontoxic without aldehyde Halogen, and it is widely used in extinguishing chemical, fireproof paint, coating is fire-retardant and the field such as macromolecular material fire retardant, expansion type flame retardant.Yet, because APP is a kind of inorganic macromolecule compound, there is hydrophily, while depositing in air, can absorb airborne moisture, easily the moisture absorption causes APP hydrolysis; And the compatibility of inorganic APP and high-molecular organic material is poor, in process, easily reunite and do not can be uniformly dispersed, often make mechanical property etc. can not reach instructions for use, do not affect other performances of material when can bring into play fire retardation, all need its modifying surface under many circumstances.
APP modification adopts two kinds of physical modification method and chemical modification methods conventionally.Wherein physical modification method has surfactant-modified and microencapsulation processing, and chemical modification method has surface active modification and coupling agent modified processing.For example, thank to the lucky star etc. delivers microencapsulation and the fire-retardant application > > report of < < APP and utilizes melamine formaldehyde resin to carry out Research of Microencapsulation to APP on < < fire proofing and technology > >, obtained good anti-flammability, water-soluble also significantly decline, but free formaldehyde and burst size of methanal all increase greatly.Also after having scholar that APP is at high temperature activated, utilize melamine, under different condition, APP is coated to processing, thereby greatly reduce the hygroscopicity of APP and water-soluble, but the consistency problem in high-molecular organic material is not settled properly to APP yet.
Along with the deep development of APP modification technology, there is increasing APP method of modifying.For example, patent CN101570325B discloses a kind of method of ammonium polyphosphate modifying, the mixed solution of modifier amino alkane and solvent acetone, absolute ethyl alcohol, absolute methanol, carrene, chloroform, benzinum, ether or benzene is poured in APP, stirring, static, continuation stirring again, obtain mixture, by mixture, in temperature, be to dry 1～3 hour under the condition of 100 ℃～250 ℃ again, obtain the APP of modification.Patent CN102618087A discloses a kind of preparation method of siliceous phosphonitrile ammonium polyphosphate modifying fire retardant, and it adds APP in APESP solution system to, except dry after desolventizing, obtains the ammonium polyphosphate flame retardant after modification.Patent CN103382267A discloses a kind of organic amine ammonium polyphosphate modifying and preparation method thereof: at room temperature first, any in alcohol compound mixed according to volume ratio 100:1～20 with water, then pass into inert gas, and under atmosphere of inert gases, APP and organic amine are joined in reaction vessel 10:1～10 in molar ratio, stirring is warming up to 70～90 ℃, reaction 2～5h, ethanol washing, oven dry.Patent CN103554999A discloses a kind of ammonium polyphosphate modifying and preparation method thereof, it adopts melamine and formalin to make performed polymer, again performed polymer is coated on to the APP that forms melamine resin modification in APP, and then the mixture that adds acrylic acid to form with at least one esters of acrylic acid reacts the ammonium polyphosphate modifying that forms double-coated with the APP of melamine resin modification.
Many metal phosphates, stable in properties, high temperature resistant, water insoluble, safe, have no adverse reaction and side effect, can make fire retardant and use, if ferric pyrophosphate is for the synthesis of fiber fireproof agent, aluminum phosphate is widely used in fireproof paint, trbasic zinc phosphate is generally used for the fire retardant of chlorinated rubber, synthesized polymer material, and magnesium phosphate, calcium phosphate etc. is also widely used in fire-proof additive.
Summary of the invention
The object of the present invention is to provide a kind of metallic ion modified polyphosphoric acid ammonium, it adopts metal ion-modified dose to APP, to carry out modification, make it have good anti-flammability, overcome the problems such as the easy moisture absorption of APP, compatibility be poor simultaneously, can obtain very good water-fast effect, and not halogen-containing and formaldehyde.
Another object of the present invention is to provide a kind of chemical modification method of new APP, and it adopts metal ion-modified dose with solvent, APP to be carried out to modification, and its preparation manipulation is simple, modification cost is low.
Another object of the present invention is to provide the application of metallic ion modified polyphosphoric acid ammonium as fire retardant, can be widely used in the fields such as plastics, rubber, fireproof paint and fabric coating.
The invention provides a kind of metallic ion modified polyphosphoric acid ammonium, it carries out modification with metal ion to APP, obtains metallic ion modified polyphosphoric acid ammonium.
Preferably, described metal ion is one or more in iron, magnesium, calcium, aluminium, zinc plasma.
Preferably, described APP is I-type APP or II-type APP, preferred, and described APP is that the degree of polymerization is 5～20 soluble poly ammonium phosphate, or the degree of polymerization insoluble APP that is 21～2000.
The present invention also provides a kind of method of preparing metallic ion modified polyphosphoric acid ammonium, and APP is scattered in solvent, adds metal ion saturated solution under stirring condition, fully, after hybrid reaction, makes metallic ion modified polyphosphoric acid ammonium.Its chemical equation is referring to accompanying drawing 1.
Preferably, APP is dispersed in solvent, under agitation adds the saturated solution of metal ion, fully, after hybrid reaction, precipitation, be heated to 60～180 ℃, except desolventizing and the crystallization water, cooling, pulverize, obtain metallic ion modified polyphosphoric acid ammonium product.
Preferably, described metal ion is (0.5～70) with the ratio of the amount of the phosphorus substance of APP: 100, be n (M): n (P)=(0.5:70)～100, be preferably (5～50): 100, more preferably (0.8～40): 100, further preferred (1～20): 100, (2～25): 100, or (3～30): 100, but be not limited to this.
Preferably, described metal ion saturated solution is slaine saturated solution, wherein said metal ion be iron, magnesium, calcium, aluminium, zinc isoionic one or more.
Preferably, described APP is I-type APP or II-type APP, preferred, and described APP is that the degree of polymerization is 5～20 soluble poly ammonium phosphate, or the degree of polymerization insoluble APP that is 21～2000.
Preferably, described solvent is one or more combinations in distilled water, acetone, ethanol, DMF.
The invention provides the application in fields such as plastics, rubber, fireproof paint and fabric coatings as fire retardant of above-mentioned metallic ion modified polyphosphoric acid ammonium.
Beneficial effect of the present invention has:
1, by metal ion-modified dose, with APP generation chemical reaction, APP is carried out to modification, its preparation method is simple to operate, modification cost is low, yield >=95% of metallic ion modified polyphosphoric acid ammonium product.
2, the metallic ion modified polyphosphoric acid ammonium of modification has good anti-flammability and slightly solubility, and has overcome the problems such as the easy moisture absorption of APP, poor water resistance; Can be widely used in the fields such as plastics, rubber, fireproof paint and fabric coating be fire-retardant.
3, metallic ion modified polyphosphoric acid ammonium of the present invention can obtain well fire-retardant, water-fast effect, and not halogen-containing and formaldehyde.
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Accompanying drawing explanation
Fig. 1 is the chemical equation of metallic ion modified polyphosphoric acid ammonium of the present invention.
Fig. 2 is the FTIR collection of illustrative plates of AlAPP of the present invention.
Fig. 3 is the FTIR collection of illustrative plates of APP of the present invention.
Fig. 4 is the FTIR collection of illustrative plates of ZnAPP of the present invention.
Fig. 5 is the FTIR collection of illustrative plates of MgAlAPP of the present invention
Fig. 6 is the FTIR collection of illustrative plates of FeAPP of the present invention
Fig. 7 is the FTIR collection of illustrative plates of CaAPP of the present invention
The specific embodiment
By specific embodiments of the invention given below and comparing embodiment, can further be well understood to the present invention, but they not limitation of the invention.The part not describing in detail in specific embodiment and comparing embodiment is to adopt prior art, known technology means and industry standard to obtain.
Except as otherwise noted, the percentage adopting in the present invention is percetage by weight.
Fourier's infrared spectrum (FTIR) of metal ion-modified APP finished product, hot property, fire-retardant dilatancy, moisture absorption, compatibility and solubility adopt following method of testing to carry out corresponding performance test.
FTIR test: sample is carried out to infrared spectrum analysis, pressing potassium bromide troche with Nicolet6700 type Fourier's infrared spectrophotometer (Thermo Nicolet, Waltham, MA).
Hot analytical test: with STA449C type simultaneous thermal analysis instrument (German NETZSCH), sample is carried out to thermal performance analysis, nitrogen flow 45mL/min takes 5～7mg sample in aluminium crucible, is warming up to 590 ℃ with 10 ℃/min from 40 ℃.
Fire-retardant dilatancy test: after the ratio of press amount of substance evenly mixes MAPP:MA:PEO=10:4:4, the fire retardant that takes out 1mL is put in asbestos gauge, uses alcohol blast burner calcination, observation is fuming, residue pattern after expansion height and expanding volume, expansion.The measuring method of volumetric expansion multiple: residue after expanding is put in the graduated cylinder of 2000mL, and from another fills the graduated cylinder of 2000mL fine sand, take out fine sand and join gradually in the graduated cylinder that is placed with residue, and constantly shake graduated cylinder, fill fine and close, and making it just cover residue, the horizontal reading of sand face is V
2mL, the volume that takes out fine sand is V
1mL.After expanding, residue volume is V
2～V
1mL, the volume multiple calculate expanding by formula (1), parallel determination three times, averages as the volumetric expansion multiple (N) of the anti-flammability of sample.
N＝V
2～V
1.....................(1)
Moisture absorption test: moisture absorption is that the quality that increases because of the moisture absorption with fire retardant mass percent when dry with it represents.APP by after 10gAPP or 10g modification dry processing, is evenly laid in 100cm
2in the glass plate of known exact mass, put into after the dry 4h of processing of baking oven of (50 ± 2 ℃), take out and weigh immediately its quality (m
0g), be accurate to 0.01g, in the climatic chamber that then sample to be placed on to temperature (40 ± 2 ℃), relative humidity be (80 ± 5%), after 24h, 48h, 72h, take out and weigh (m
xg), by formula (2), calculate moisture absorption ratio, parallel determination three times, averages as the moisture absorption ratio (Δ G) of sample.
Solubility test: solubility is with at 25 ℃, and the quality of dissolving APP in 100mL distilled water represents.15gAPP sample is suspended in the distilled water of 100mL, at 25 ℃ and 60 ℃, constant temperature stirs 60min respectively.Then use the centrifugal 20min of centrifuge, make not dissolve APP sample and fall to bottom.Supernatant liquor is proceeded in the evaporating dish of known quality, the quality of liquid is (m
1), dry at 120 ℃, the residue quality of weighing, the quality of residue is (m
2).By formula (3), can calculate APP after the modification solubility (S) in water.
Water-fastness test: the fabric after arrangement is washed 15min at the aqueous wash medium of 0.5% (w/w) sodium carbonate of 40 ℃, is then washed to neutrality, naturally dries.Adhesion amount add～on (%) computing formula of fire retardant is as follows:
Wherein, w
oand w
tthe quality that represents respectively T/C textile finishing front and back.
Limited oxygen index test (LOI): with HC～2C type oxygen index measurer (meta analysis instrument company in Nanjing of China), flame-retardant textile is tested according to GB/T5454～1997 regulation, and flame retardant plastics is tested according to ASTM D2863～08 standard.
Vertical combustion test: with CZF～2 type vertical combustion instrument (Chinese Jiangning county analytical instrument factory), flame-retardant textile is tested according to GB/T5455～1997 regulation, flame retardant plastics is tested according to UL 94 ISBN 0～7629～0082～2 standards, and specimen size is 127mm * 12.7mm * 3.2mm.
Mechanics Performance Testing: according to GB/T1040～1992, adopt DXLL～electronic tension tester (the outstanding machinery equipment of upper Heiden), rate of extension 25mm/min, 25 ℃ of test temperatures.
embodiment 1
5 parts of insoluble I-type APP (I-APP) are dispersed in the acetone and water mixed liquid (solvent ratios does not have a significant effect to product quality) of 15-100 part, under agitation add 0.5 part of aluminium chloride saturated solution (Al
3+saturated solution), be fully uniformly mixed after reaction, filter, dry, then be crushed to the particulate of 25 μ m, obtain insoluble I-type APP (AlAPP) finished product of modification, yield is 96%.
As shown in Figure 1, the FTIR of products A lAPP (KBr, cm
-1): 3176,1664,1621,1403,1111,616,483.
As shown in Figure 2, the FTIR of APP (KBr, cm
-1): 3211,3055,1440,1251,1075,1016,993,799,558,472.
According to preceding method, test respectively the variation of the hot property of metal ion-modified I-type APP and unmodified I-type APP, fire-retardant dilatancy, moisture absorption and solubility, result respectively correspondence is listed in table 1, table 2, table 3 and table 4.
It is as shown in table 1 that the heat of products A lAPP is analyzed TGA key data.As seen from table: the initial decomposition temperature (T of AlAPP
on) be 205 ℃, than the T of APP
on(162 ℃) have improved 43 ℃.AlAPP has three significant thermal cracking stages, and first zero-g period, maximum decomposition temperature was 246 ℃ at 205 ℃～272 ℃, weightlessness 6.8%, second stage is at 272 ℃～364 ℃, and maximum decomposition temperature is 314 ℃, weightlessness 12%, the phase III, maximum decomposition temperature was 456 ℃ at 367 ℃～460 ℃, weightlessness 43%, in the time of 300 ℃, remaining quality is 88.3%, than APP, improved 25.1%, in the time of 500 ℃, remaining quality is 35.1%, than APP, has reduced by 18.5%.Fire retardant AlAPP is described thus, and 300 ℃ of more difficult decomposition below degree, heat endurance significantly improves, and more than 400 ℃, decomposes rapidly, and flame retardant effect is obvious.Therefore, the obvious rising of AlAPP temperature of initial decomposition can improve the processing temperature of fire proofing, and high temperature flame-proof performance significantly improves, and this is the character that many fire retardants do not have.
The contrast of table 1 aluminium ion ammonium polyphosphate modifying (AlAPP) hot property
The fire-retardant volumetric expansion performance key data of products A lAPP is as shown in table 2.As shown in Table 2: the expansion height in fire proofing of AlAPP is 53mm, more lower slightly than the expansion height of unmodified APP, but its volumetric expansion multiple is 231 times, suitable with the volumetric expansion multiple of unmodified APP.Therefore the introducing of Al, does not obviously reduce the fire-retardant expansion character of APP, and makes its fire-retardant residue finer and close, micropore number increases.
The fire-retardant volumetric expansion performance comparison of table 2 aluminium ion ammonium polyphosphate modifying (AlAPP)
The moisture absorption key data of products A lAPP is as shown in table 3.As seen from table: the moisture absorption of AlAPP, along with the prolongation moisture absorption ratio variation of time is very little, is less than 0.35%, and surpasses after 72 hours, and substantially saturated, moisture absorption ratio no longer increases.And the moisture absorption of unmodified I-type APP enlarges markedly over time, surpass 20.8%, be because unmodified APP is easily at the laggard one-step hydrolysis of the moisture absorption, the moisture absorption is unreachable to saturated, and the moisture absorption of unmodified I-type APP is the more than 7 times of modification I-type APP.
The variation of the moisture absorption ratio of table 3 aluminium ion ammonium polyphosphate modifying (AlAPP)
The solubility key data of products A lAPP is as shown in table 4.As seen from table: the solubility of AlAPP is very little, be only 1/170 of unmodified APP solubility, when its temperature is increased to 60 ℃, its solubility is only 1.04g, still very little, and very large with the solubility of unmodified I-type APP, and temperature rising, becomes easy tolerant matter.
The variation of table 4 aluminium ion ammonium polyphosphate modifying (AlAPP) solubility
embodiment 2
25 parts of solubility I-type APP (I-APP) are dispersed in the acetone water mixed liquid of 15-100 part, under agitation add 1 part of zinc chloride saturated solution (Zn
2+saturated solution), be fully uniformly mixed after reaction, filter, dry, then be crushed to the particulate of 25 μ m, obtain insoluble I-type APP (ZnAPP) finished product of modification, yield is 97%.
As shown in Figure 3, the FTIR of APP (KBr, cm
-1): 3211,3055,1440,1251,1075,1016,993,799,558,472.
As shown in Figure 4, the FTIR of product ZnAPP (KBr, cm
-1): 3416,3153,3049,1657,1621,1405,1051,616,537,463.
According to preceding method, test respectively the variation of the hot property of modification I-type APP and unmodified I-type APP, fire-retardant dilatancy, moisture absorption and solubility, result respectively correspondence is listed in table 5, table 6, table 7 and table 8.
It is as shown in table 5 that the heat of product ZnAPP is analyzed TGA key data.As seen from table: the initial decomposition temperature (T of ZnAPP
on) be 211 ℃, than the T of APP
on(162 ℃) have improved 49 ℃.ZnAPP has three significant thermal cracking stages, and first zero-g period, maximum decomposition temperature was 176 ℃ at 151 ℃～203 ℃, weightlessness 3%, second stage is at 218 ℃～294 ℃, and maximum decomposition temperature is 276 ℃, weightlessness 15%, the phase III, maximum decomposition temperature was 330 ℃ at 367 ℃～460 ℃, weightlessness 12%, in the time of 300 ℃, remaining quality is 82%, than APP, improved 19%, in the time of 500 ℃, remaining quality is 65.1%, than APP, has improved 11.4%.Fire retardant ZnAPP is described thus, and at 300 ℃, below degree and 400 ℃ of all more difficult decomposition above, heat endurance significantly improves.Therefore, the obvious rising of ZnAPP temperature of initial decomposition can improve the processing temperature of fire proofing.
The contrast of table 5 zinc ion ammonium polyphosphate modifying (ZnAPP) hot property
The fire-retardant volumetric expansion performance key data of product ZnAPP is as shown in table 6.As seen from table: the expansion height in fire proofing of ZnAPP is 42mm, lower than the expansion height of unmodified APP, but its volumetric expansion multiple is 224 times, less by 16 than the volumetric expansion multiple of unmodified APP.Therefore the introducing of Zn ion, makes its fire-retardant residue finer and close, reduce the fire-retardant expansion character of APP, but the hardening of charcoal layer is difficult for destroyed.
The fire-retardant volumetric expansion performance comparison of table 6 zinc ion ammonium polyphosphate modifying (ZnAPP)
The moisture absorption key data of product ZnAPP is as shown in table 7.As shown in Table 7: the moisture absorption of ZnAPP, along with the prolongation moisture absorption ratio variation of time is very little, is less than 1.42%, and surpasses after 72 hours, and substantially saturated, moisture absorption ratio no longer increases.And the moisture absorption of unmodified I-type APP enlarges markedly over time, surpass 22.6%, be because unmodified APP is easily at the laggard one-step hydrolysis of the moisture absorption, the moisture absorption is unreachable to saturated, and the moisture absorption of unmodified I-type APP is the more than 16 times of ZnAPP.
The variation of the moisture absorption ratio of table 7 zinc ion ammonium polyphosphate modifying (ZnAPP)
The solubility key data of product ZnAPP is as shown in table 8.As seen from table: the solubility of ZnAPP is very little, be only 1/500 of unmodified APP solubility, when its temperature is increased to 60 ℃, its solubility is only 1.67g, still very little, and very large with the solubility of unmodified I-type APP, and temperature rising, it is large that solubility becomes.
The variation of table 8 zinc ion ammonium polyphosphate modifying (ZnPP) solubility
embodiment 3
30 parts of insoluble II-type APP (II-APP) are dispersed in the DMF and water mixed liquid of 15-100 part, under agitation add 10 parts of magnesium chloride saturated liquid (Mg
2+saturated solution) and 5 parts of aluminium chloride saturated solution (Al
3+saturated solution), be fully uniformly mixed after reaction, filter, dry, then be crushed to the particulate of 25 μ m, obtain insoluble II-type APP (MgAlAPP) finished product of modification, yield is 96%.
As shown in Figure 3, the FTIR of APP (KBr, cm
-1): 3211,3055,1440,1251,1075,1016,993,799,558,472.
As shown in Figure 5, the FTIR of product MgAlAPP (KBr, cm
-1): 3415,3196,1665,1622,1442,1403,1157,1119,732,901,491,557.
According to preceding method, test respectively the variation of the hot property of modification II-type APP and unmodified II-type APP, fire-retardant dilatancy, moisture absorption and solubility, result respectively correspondence is listed in table 9, table 10, table 11 and table 12.
It is as shown in table 9 that the heat of product MgAPP is analyzed TGA key data.As seen from table: the initial decomposition temperature (T of MgAlAPP
on) be 208 ℃, than the T of APP
on(162 ℃) have improved 46 ℃.MgAlAPP has three significant thermal cracking stages, first zero-g period is at 174 ℃～213 ℃, maximum decomposition temperature is 205 ℃, weightlessness 8%, second stage is at 218 ℃～308 ℃, and maximum decomposition temperature is 284 ℃, weightless 15%, phase III, maximum decomposition temperature was 345 ℃ at 309 ℃～376 ℃, weightless 16%.In the time of 300 ℃, remaining quality is 75%, than APP, has improved 12%, and in the time of 500 ℃, remaining quality is 59%, than APP, has improved 6%.Fire retardant MgAlAPP is described thus, and at 300 ℃, below degree and 400 ℃ of all more difficult decomposition above, heat endurance significantly improves.Therefore, the obvious rising of MgAPP temperature of initial decomposition can improve the processing temperature of fire proofing.
The contrast of table 9 magnesium aluminium ion ammonium polyphosphate modifying (MgAlAPP) hot property
The fire-retardant volumetric expansion performance key data of product MgAlAPP is as shown in table 10.As seen from table: the expansion height in fire proofing of MgAlAPP is 57mm, more lower slightly than the expansion height of unmodified APP, but its volumetric expansion multiple is 231 times, suitable with the volumetric expansion multiple of unmodified APP.Therefore the introducing of Mg ion and Al ion, makes its fire-retardant residue finer and close, reduce the fire-retardant expansion character of APP, but the hardening of charcoal layer is difficult for destroyed.
The fire-retardant volumetric expansion performance comparison of table 10 magnesium aluminium ion ammonium polyphosphate modifying (MgAlAPP)
The moisture absorption key data of product MgAlAPP is as shown in table 11.As shown in Table 11: the moisture absorption of MgAPP, along with the prolongation moisture absorption ratio variation of time is very little, is less than 1.54%, and surpasses after 72 hours, and substantially saturated, moisture absorption ratio no longer increases.And the moisture absorption of unmodified II-type APP enlarges markedly over time, surpass 22.6%, be because unmodified APP is easily at the laggard one-step hydrolysis of the moisture absorption, the moisture absorption is unreachable to saturated, and the moisture absorption of unmodified II-type APP is the more than 14 times of MgAlAPP.
The variation of the moisture absorption ratio of table 11 magnesium aluminium ion ammonium polyphosphate modifying (MgAlAPP)
The solubility key data of product MgAlAPP is as shown in table 12.As shown in Table 12: the solubility of MgAPP is very little, be only 1/48 of unmodified APP solubility, when its temperature is increased to 60 ℃, its solubility is only 1.85g, still very little, and very large with the solubility of unmodified II～type APP, and temperature rising, it is large that solubility becomes.
The variation of table 12 magnesium aluminium ion ammonium polyphosphate modifying (MgAlAPP) solubility
embodiment 4
40 parts of solubility I-type APP (I-APP) are dispersed in the ethanol and water mixed liquid of 15-100, under agitation add 35 parts of ferric nitrate saturated solution (Fe
3+saturated solution), be fully uniformly mixed after reaction, filter, dry, then be crushed to the particulate of 25 μ m, obtain insoluble I-type APP (FeAPP) finished product of modification, yield is 98%.
As shown in Figure 3, the FTIR of APP (KBr, cm
-1): 3211,3055,1440,1251,1075,1016,993,799,558,472.
As shown in Figure 6, the FTIR of product F eAPP (KBr, cm
-1): 3442,3168,1657,1621,1403,1072,903,575,544.
According to preceding method, test respectively the variation of the hot property of modification I-type APP and unmodified I-type APP, fire-retardant dilatancy, moisture absorption and solubility, result respectively correspondence is listed in table 13, table 14, table 15 and table 16.
It is as shown in table 13 that the heat of product F eAPP is analyzed TGA key data.As shown in Table 13: the initial decomposition temperature (T of FeAPP
on) be 177 ℃, than the T of APP
on(162 ℃) have improved 15 ℃.FeAPP has two significant thermal cracking stages, and first zero-g period, maximum decomposition temperature was 226 ℃ at 177 ℃～255 ℃, weightless 19%, second stage is at 255 ℃～353 ℃, and maximum decomposition temperature is 312 ℃, and weightless 34%, in the time of 300 ℃, remaining quality is 75%, has improved 12%, than APP in the time of 500 ℃, remaining quality is 41%, than APP, has reduced by 12%.Fire retardant FeAPP is described thus, at 255 ℃, below degree, than unmodified APP, divides and solve slightly slowly, and 330 ℃ above than the more difficult decomposition of unmodified APP, and heat endurance significantly improves.Therefore, the temperature of initial decomposition of FeAPP and unmodified APP differs less, but first catabolic phase can play the good fire retardation that plays.
The contrast of table 13 iron ion ammonium polyphosphate modifying (FeAPP) hot property
The fire-retardant volumetric expansion performance key data of product F eAPP is as shown in table 14.As shown in Table 14: the expansion height in fire proofing of FeAPP is 60mm, lower than the expansion height of unmodified APP, but its volumetric expansion multiple is 228 times, suitable with the volumetric expansion multiple of unmodified APP.Therefore the introducing of Fe ion, makes its fire-retardant residue finer and close, has improved the flame retarding efficiency of APP, and the hardening of charcoal layer, is difficult for destroyed.
The fire-retardant volumetric expansion performance comparison of table 14 iron ion ammonium polyphosphate modifying (FeAPP)
The moisture absorption key data of product F eAPP is as shown in Table 15.As seen from table: the moisture absorption of FeAPP, along with the prolongation moisture absorption ratio variation of time is very little, is less than 1.59%, and surpasses after 48 hours, and substantially saturated, moisture absorption ratio no longer obviously increases.And the moisture absorption of unmodified I-type APP enlarges markedly over time, surpass 22.6%, be because unmodified APP is easily at the laggard one-step hydrolysis of the moisture absorption, the moisture absorption is unreachable to saturated, and the moisture absorption of unmodified I-type APP is the more than 14 times of FeAPP.
The variation of the moisture absorption ratio of table 15 iron ion ammonium polyphosphate modifying (FeAPP)
The solubility key data of product F eAPP is shown in table 16.As seen from table: the solubility of FeAPP is very little, be only 1/155 of unmodified APP solubility, when its temperature is increased to 60 ℃, its solubility is only 2.54g, still very little, and very large with the solubility of unmodified I～type APP, and temperature rising, it is large that solubility becomes.
The variation of table 16 iron ion ammonium polyphosphate modifying (FeAPP) solubility
embodiment 5
50 parts of insoluble II-type APP (II-APP) are dispersed in the DMF and water mixed liquid of 15-100 part, under agitation add 70 parts of calcium chloride saturated solution (Ca
2+saturated solution), be fully uniformly mixed after reaction, filter, dry, then be crushed to the particulate of 25 μ m, obtain insoluble II-type APP (CaAPP) finished product of modification, yield is 97%.
As shown in Figure 3, the FTIR of APP (KBr, cm
-1): 3211,3055,1440,1251,1075,1016,993,799,558,472.
As shown in Figure 7, the FTIR of products C aAPP (KBr, cm
-1):, 3198,3054,2879,1663,1450,1397,1126,1076,1020,911,881,731,563,492.
According to preceding method, test respectively the variation of the hot property of modification II-type APP and unmodified II-type APP, fire-retardant dilatancy, moisture absorption and solubility, result respectively correspondence is listed in table 17, table 18, table 19 and table 20.
It is shown in table 17 that the heat of products C aAPP is analyzed TGA key data.As shown in Table 17: the initial decomposition temperature (T of CaAPP
on) be 208 ℃, than the T of APP
on(162 ℃) have improved 46 ℃.CaAPP has three significant thermal cracking stages, first zero-g period is at 174 ℃～213 ℃, maximum decomposition temperature is 205 ℃, weightlessness 8%, second stage is at 218 ℃～308 ℃, and maximum decomposition temperature is 284 ℃, weightless 15%, phase III, maximum decomposition temperature was 345 ℃ at 309 ℃～376 ℃, weightless 16%.In the time of 300 ℃, remaining quality is 75%, than APP, has improved 12%, and in the time of 500 ℃, remaining quality is 59%, than APP, has improved 6%.Fire retardant CaAPP is described thus, and at 300 ℃, below degree and 400 ℃ of all more difficult decomposition above, heat endurance significantly improves.Therefore, the obvious rising of CaAPP temperature of initial decomposition can improve the processing temperature of fire proofing.
The contrast of table 17 calcium ion modification APP (CaAPP) hot property
The fire-retardant volumetric expansion performance key data of products C aAPP is shown in table 18.As shown in Table 18: the expansion height in fire proofing of CaAPP is 53mm, more lower slightly than the expansion height of unmodified APP, but its volumetric expansion multiple is 221 times, low by 9% with the volumetric expansion multiple of unmodified APP.Therefore the introducing of Ca ion and Al ion, makes its fire-retardant residue finer and close, reduce the fire-retardant expansion character of APP, but the hardening of charcoal layer is difficult for destroyed.
The fire-retardant volumetric expansion performance comparison of table 18 calcium ion modification APP (CaAPP)
The moisture absorption key data of products C aAPP is shown in table 19.As shown in Table 19: the moisture absorption of CaAPP, along with the prolongation moisture absorption ratio variation of time is very little, is less than 1.47%, and surpasses after 72 hours, and substantially saturated, moisture absorption ratio no longer increases.And unmodified II-type APP is because it is easily at the laggard one-step hydrolysis of the moisture absorption, the moisture absorption is unreachable to saturated, and moisture absorption enlarge markedly over time, surpass 22.6%, the moisture absorption of unmodified II-type APP is the more than 15 times of CaAPP.
The variation of the moisture absorption ratio of table 19 calcium ion modification APP (CaAPP)
The solubility key data of products C aAPP is shown in table 20.As seen from table: the solubility of CaAPP is very little, only 1/57 of unmodified APP solubility, when its temperature is increased to 60 ℃, its solubility is only 1.02g, be only 1/9 of unmodified APP solubility, still very little, and significantly become large with the solubility of unmodified II-type APP, and temperature is higher, solubility is larger.
The variation of table 20 calcium ion modification APP (CaAPP) solubility
application Example 1
The AlAPP that 25 parts of embodiment 1 are prepared joins in 100 parts of aqueous acrylic emulsions, add tackifier, regulating pH is 9～10, with scraper blade coating, in terylene cloth cover, for the first time after blade coating, 7min is dried at 90 ℃, take out again blade coating once, at 90 ℃, 7min is dried, and bakes 2min at 160 ℃, obtains one side flame retardant coating cloth.
According to preceding method, test respectively flame retardant coating cloth and not limited oxygen index, the vertical combustion performance of fire-retardant cloth specimen, the variation of moisture absorption and resistance to water, result correspondence is listed in table 21.
The fire resistance key data of the sample of process AlAPP flame treatment is shown in table 21.As seen from table: fabric is after flame treatment, and its LOI reaches 29%, and vertical combustion is increased to B1 level.After 1～10 water-based, its LOI obviously reduces, and after washing times surpasses more than 5 times, the fire resistance of sample is substantially constant, its LOI remains on 25%, when vertical combustion is tested, without the fire-retardant cloth specimen washing, can reach from fire from putting out, after washing once, its fire resistance declines, its after flame time is 2s, when combustion testing, has no and glows.Above, illustrate that AlAPP fire retardant has good fire resistance, and its water resistance is also better.
Table 21 is processed the fire resistance of woven dacron through aluminium ion ammonium polyphosphate modifying (AlAPP)
application Example 2
30 parts of FeAPP are joined in 90 parts of oiliness polyaminoester emulsions, add tackifier adjusting viscosity, then use scraper blade coating in terylene cloth cover, for the first time after blade coating, 5min is dried at 100 ℃, takes out blade coating once again, at 100 ℃, 5min is dried, and bakes 3min at 150 ℃, obtains one side flame retardant coating cloth.
According to preceding method, test respectively flame retardant coating cloth and not limited oxygen index, the vertical combustion performance of fire-retardant cloth specimen, the variation of moisture absorption and resistance to water, result correspondence is listed in table 22.
The fire resistance key data of the sample of process FeAPP flame treatment is shown in table 22.As seen from table: fabric is after flame treatment, and its LOI reaches 31%, and vertical combustion is increased to B1 level.After 1～10 water-based, its LOI obviously reduces, and after washing times surpasses more than 5 times, the fire resistance of sample is substantially constant, its LOI remains on 26%, when vertical combustion is tested, without the fire-retardant cloth specimen washing, can reach from fire from putting out, after washed twice, its fire resistance declines, its after flame time is 2s, when combustion testing, has no and glows.Above, illustrate that FeAPP fire retardant has good fire resistance, and its water resistance is also better.
Table 22 is processed the fire resistance of woven dacron through iron ion ammonium polyphosphate modifying (FeAPP)
application Example 3
The ratio that is 30:70 according to mass ratio by the sour ammonium Fe～APP of the modified polyphosphoric acid of above-mentioned preparation fire retardant, polypropylene S1003 is composite, add again mass ratio and be 0.1% 1010 antioxidant and 0.2% 168 antioxidant, extrusion temperature is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 175 ℃, injection temperature is 190 ℃, 195 ℃, 190 ℃, 185 ℃, 180 ℃, obtains flame-retardant polypropylene plastics test sample.
According to preceding method, test: oxygen index (OI) is that 26.6%, UL94 vertical combustion is V～2 grade, and TENSILE STRENGTH is 25.5MPa, moisture absorption ratio 0.57%.
application Example 4
The ratio that is 25:70 according to mass ratio by the sour ammonium CaAPP of the modified polyphosphoric acid of above-mentioned preparation fire retardant, polypropylene S1003 is composite, add again mass ratio and be 0.1% 1010 antioxidant and 0.2% 168 antioxidant, extrusion temperature is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 175 ℃, injection temperature is 190 ℃, 195 ℃, 190 ℃, 185 ℃, 180 ℃, obtains flame-retardant polypropylene plastics test sample.
According to preceding method, test: oxygen index (OI) is that 26.3%, UL94 vertical combustion is V～2 grade, and TENSILE STRENGTH is 25.1Mpa, moisture absorption ratio 0.59%.
application Example 5
The ratio that is 30:70 according to mass ratio by the sour ammonium MgAlAPP of the modified polyphosphoric acid of above-mentioned preparation fire retardant, polypropylene S1003 is composite, add again mass ratio and be 0.1% 1010 antioxidant and 0.2% 168 antioxidant, extrusion temperature is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 175 ℃, injection temperature is 190 ℃, 195 ℃, 190 ℃, 185 ℃, 180 ℃, obtains flame-retardant polypropylene plastics test sample.
According to preceding method, test: oxygen index (OI) is that 26.8%, UL94 vertical combustion is V～2 grade, and TENSILE STRENGTH is 25.8Mpa, moisture absorption ratio 0.53%.
comparative example
The ratio that is 30:70 according to mass ratio by unmodified polyphosphonic acid ammonium APP fire retardant, polypropylene S1003 is composite, add again mass ratio and be 0.1% 1010 antioxidant and 0.2% 168 antioxidant, extrusion temperature is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 180 ℃, 175 ℃, injection temperature is 190 ℃, 195 ℃, 190 ℃, 185 ℃, 180 ℃, obtains flame-retardant polypropylene plastics test sample.
According to preceding method, test: oxygen index (OI) is that 25.7%, UL94 vertical combustion is V～2 grade, and TENSILE STRENGTH is 25.2MPa, moisture absorption ratio 1.31%.
Above disclosed is only the preferred embodiments of the present invention, certainly can not limit with this interest field of the present invention, and the equivalent variations of therefore doing according to the present patent application the scope of the claims, still belongs to the scope that the present invention is contained.
Claims (9)
1. a metallic ion modified polyphosphoric acid ammonium, is characterized in that: with metal ion, APP is carried out to modification, obtain metallic ion modified polyphosphoric acid ammonium.
2. metallic ion modified polyphosphoric acid ammonium according to claim 1, is characterized in that: described metal ion is one or more in iron, magnesium, calcium, aluminium, zinc ion.
3. metallic ion modified polyphosphoric acid ammonium according to claim 1, it is characterized in that: described APP is I-type APP or II-type APP, preferably, described APP is that the degree of polymerization is 5～20 soluble poly ammonium phosphate, or the degree of polymerization insoluble APP that is 21～2000.
4. a method of preparing metallic ion modified polyphosphoric acid ammonium, is characterized in that: APP is scattered in solvent, adds metal ion saturated solution under stirring condition, fully, after hybrid reaction, make metallic ion modified polyphosphoric acid ammonium.
5. method according to claim 4, is characterized in that: the phosphorus in described metal ion and described APP with the ratio of amount of substance be (0.5～70): 100.
6. according to the method described in claim 4 or 5, it is characterized in that: described metal ion is one or more in iron, magnesium, calcium, aluminium, zinc ion.
7. according to the method described in claim 4 or 5, it is characterized in that: described APP is I-type APP or II-type APP, preferably, described APP is that the degree of polymerization is 5～20 soluble poly ammonium phosphate, or the degree of polymerization insoluble APP that is 21～2000.
8. according to the method described in claim 4 or 5, it is characterized in that: described solvent is one or more combinations in distilled water, acetone, ethanol, DMF.
9. the application as fire retardant according to the metallic ion modified polyphosphoric acid ammonium described in any one in claims 1 to 3 or the metallic ion modified polyphosphoric acid ammonium prepared according to the method described in any one in claim 4 to 8.
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| CN109251556A (en) * | 2018-08-15 | 2019-01-22 | 什邡市太丰新型阻燃剂有限责任公司 | A kind of ammonium polyphosphate and preparation method thereof of the resistance to precipitation of migration resistance under acrylic emulsion spinning coating high temperature super-humid conditions |
| CN112778237A (en) * | 2020-12-31 | 2021-05-11 | 广州大学 | Synthesis method of piperazine pyrophosphate metal salt |
| CN112853753A (en) * | 2019-11-28 | 2021-05-28 | 天津工业大学 | Phosphorus-aluminum-nitrogen synergistic phosphorus-nitrogen expansion halogen-free flame retardant and preparation technology thereof |
| CN112898231A (en) * | 2021-01-29 | 2021-06-04 | 杭州捷尔思阻燃化工有限公司 | Preparation method and application of metal ion modified polyphosphoric acid piperazine |
| CN114958139A (en) * | 2022-05-20 | 2022-08-30 | 中国科学技术大学先进技术研究院 | Flame retardant, preparation method, coating containing flame retardant and explosion-proof battery box containing flame-retardant coating |
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| CN101942227A (en) * | 2009-07-07 | 2011-01-12 | 佛山市金戈消防材料有限公司 | Method for improving water resistance of ammonium polyphosphate |
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| CN1733778A (en) * | 2005-08-10 | 2006-02-15 | 东北林业大学 | Metallic ion modified polyphosphoric acid melamine salt and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105133295A (en) * | 2015-10-09 | 2015-12-09 | 北京德成嘉化工科技有限责任公司 | Inorganic polymer modification insoluble halogen-free flame retardant and preparation method and application thereof |
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| CN112853753A (en) * | 2019-11-28 | 2021-05-28 | 天津工业大学 | Phosphorus-aluminum-nitrogen synergistic phosphorus-nitrogen expansion halogen-free flame retardant and preparation technology thereof |
| CN112778237A (en) * | 2020-12-31 | 2021-05-11 | 广州大学 | Synthesis method of piperazine pyrophosphate metal salt |
| CN112898231A (en) * | 2021-01-29 | 2021-06-04 | 杭州捷尔思阻燃化工有限公司 | Preparation method and application of metal ion modified polyphosphoric acid piperazine |
| CN114958139A (en) * | 2022-05-20 | 2022-08-30 | 中国科学技术大学先进技术研究院 | Flame retardant, preparation method, coating containing flame retardant and explosion-proof battery box containing flame-retardant coating |
| CN114958139B (en) * | 2022-05-20 | 2023-09-12 | 中国科学技术大学先进技术研究院 | Flame retardant, preparation method, coating containing flame retardant and explosion-proof battery box containing flame retardant coating |
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Application publication date: 20141105 |