CN102585845B - Inorganic mineral composite flame retardant and preparation method thereof - Google Patents
Inorganic mineral composite flame retardant and preparation method thereof Download PDFInfo
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- CN102585845B CN102585845B CN201010618309.9A CN201010618309A CN102585845B CN 102585845 B CN102585845 B CN 102585845B CN 201010618309 A CN201010618309 A CN 201010618309A CN 102585845 B CN102585845 B CN 102585845B
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- China
- Prior art keywords
- hydrotalcite
- preparation
- linking agent
- flame retardant
- stablizer
- Prior art date
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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 35
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 60
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 41
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000136 polysorbate Polymers 0.000 claims description 9
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 8
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- HVUMOYIDDBPOLL-UHFFFAOYSA-N 2-(3,4-Dihydroxyoxolan-2-yl)-2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)C1OCC(O)C1O HVUMOYIDDBPOLL-UHFFFAOYSA-N 0.000 claims description 6
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 6
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000002632 lipids Chemical class 0.000 claims description 6
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 6
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 6
- 229950008882 polysorbate Drugs 0.000 claims description 6
- 229940113124 polysorbate 60 Drugs 0.000 claims description 6
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 5
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 claims 1
- 150000002888 oleic acid derivatives Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 2
- 239000003381 stabilizer Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002889 oleic acids Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- IQUCNXSZNHPPML-UHFFFAOYSA-N 2-chloro-n-[(4-chlorophenyl)-phenylmethyl]acetamide Chemical compound C=1C=C(Cl)C=CC=1C(NC(=O)CCl)C1=CC=CC=C1 IQUCNXSZNHPPML-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009866 aluminium metallurgy Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QVMHUALAQYRRBM-UHFFFAOYSA-N [P].[P] Chemical compound [P].[P] QVMHUALAQYRRBM-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing an inorganic mineral composite flame retardant. The method is characterized by sequentially comprising the following steps of: 1) mixing hydrotalcite and ionized water, and uniformly stirring to form hydrotalcite suspension; 2) standing the hydrotalcite suspension for precipitating, adding a cross-linking agent into a precipitate, and uniformly stirring; and 3) adding a stabilizer, uniformly stirring, heating to the temperature of between 60 and 80 DEG C, and keeping the constant temperature for 1 to 3 hours, wherein the mass ratio of the hydrotalcite to the cross-linking agent to the stabilizer is (3-50):(3-10):(2-10). The inorganic mineral composite flame retardant has flame-retardant, smoke suppression and filling functions, is halogen-free, non-toxic and low-smoke, has a good flame-retardant effect, and is low in preparation cost.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, relate in particular to a kind of inorganic mineral composite flame retardant and preparation method thereof.
Background technology
Fire retardant is stop material to be ignited and suppress the class additive that flame is further propagated.In the especially synthetic polymer materials of multiple material, be widely used.The additive flame retardant using at present can be divided into organic type and the large class of inorganic type two.Organic type fire retardant comprises phosphorus system, halogen-phosphorus system and phosphorus-phosphorus system etc.; Inorganic combustion inhibitor can be divided into antimony system, phosphorus system and boron system etc.Although these fire retardants have good flame retardant resistance, but also there are many problems, as not good enough in the dispersiveness in material, undesirable etc. with the intermiscibility of material, it is mainly the element such as oil-containing halogen, phosphorus, antimony in organic fire-retardant, once material is ignited, will discharge a large amount of has poison gas and to human body and the harmful residue of environment.
Summary of the invention
Object of the present invention is exactly the problem existing in order to overcome above-mentioned prior art, a kind of inorganic mineral composite flame retardant is provided, that this inorganic mineral composite flame retardant has is fire-retardant, eliminate smoke, fill 3 kinds of functions, and Halogen, nontoxic, low cigarette, good flame retardation effect, and preparation cost is low.
For realizing object of the present invention, provide following technical scheme:
An inorganic mineral composite flame retardant, is characterized in that comprising raw material: hydrotalcite, linking agent, stablizer.
Wherein, the weight part proportioning of raw material is: hydrotalcite 3～50, linking agent 3～10, stablizer 2～10.
Particularly, linking agent is epoxy resin and/or polypentaerythritol; Stablizer is that glycerin fatty acid ester, lipid acid sorb are smooth, one or more in polysorbate or fatty alcohol-polyoxyethylene ether.
Particularly, glycerin fatty acid ester is nine contracting ten glycerine four oleic acid esters, a kind of in two triglycerol monostearates or two triglycerol monoleates; Lipid acid sorb smooth (being sapn) is span 40 or sorbester p18; A kind of in polysorbas20, polysorbate60 or tween 80 of polysorbate (being tween).
Wherein, the step that hydrotalcite carries out is in the following order prepared from:
A) successively will be containing CO
3 2-, Al
3+inorganic salt and divalent-metal ion inorganic salt mix with ionized water, or will be containing OH
-alkali, containing Al
3+inorganic salt and divalent-metal ion inorganic salt mix with ionized water, form mixing solutions, wherein, described divalent-metal ion is Mg
2+, Zn
2+or Cr
2+in one or more;
B) add red mud, stir, temperature of charge remains on 60-85 ℃.
Wherein, step a) described in containing CO
3 2-inorganic salt select sodium carbonate or salt of wormwood; Described containing Al
3+inorganic salt select AlCl
36H
2o; Described containing Mg
2+inorganic salt select MgCl
26H
2o; Containing Zn
2+inorganic salt select ZnCl
26H
2o; Described containing Cr
2+inorganic salt select CrCl
26H
2o; Described containing OH
-alkali select one or more in sodium hydroxide, potassium hydroxide or calcium hydroxide.
Particularly, CO in the mixing solutions that step a) makes
3 2-, Al
3+, the mol ratio of divalent-metal ion is 1～3: 3～5: 6～8 or/OH
--, Al
3+, the mol ratio of divalent-metal ion is 1～3: 3～5: 6～8.
Wherein, described step b), red mud comprises the raw material of following mole of proportioning:
Al
2O
3 5～7
SiO
2 19～22
CaO 44～48
Fe
2O
3 8～12
Na
2O 2～2.5
TiO
2 2～2.5
K
2O 2～2.5
Particularly, the component of described red mud is the waste of aluminium metallurgy factory.
The present invention also provides a kind of preparation method of inorganic mineral composite flame retardant on the other hand, comprises as follows step in sequence:
1) hydrotalcite is mixed with ionized water, stir, form hydrotalcite suspension liquid;
2) after hydrotalcite suspension liquid staticly settles, in precipitation, add linking agent, stir;
3) add stablizer, stir and be warming up to 60～80 ℃ simultaneously, keep constant temperature 1～3 hour.
Wherein, hydrotalcite is one or more in Mg-Al hydrotalcite, Zn-Al hydrotalcite, Cr-Al hydrotalcite; The quality proportioning of described hydrotalcite and linking agent, stablizer is 3～50: 3～10: 2～10.
Particularly, described linking agent is epoxy resin and/or polypentaerythritol; Described stablizer is that glycerin fatty acid ester, lipid acid sorb are smooth, one or more in polysorbate or fatty alcohol-polyoxyethylene ether.
Particularly, glycerin fatty acid ester is nine contracting ten glycerine four oleic acid esters, a kind of in two triglycerol monostearates or two triglycerol monoleates; Lipid acid sorb smooth (being sapn) is span 40 or sorbester p18; A kind of in polysorbas20, polysorbate60 or tween 80 of polysorbate (being tween).
Wherein, the step that hydrotalcite carries out is in the following order prepared from:
A) successively will be containing CO
3 2-, Al
3+inorganic salt and divalent-metal ion inorganic salt mix with ionized water, or will be containing OH
-alkali, containing Al
3+inorganic salt and divalent-metal ion inorganic salt mix with ionized water, form mixing solutions, wherein, described divalent-metal ion is Mg
2+, Zn
2+or Cr
2+in one or more;
B) add red mud, stir, temperature of charge remains on 60-85 ℃.
Wherein, step a) described in containing CO
3 2-inorganic salt select sodium carbonate or salt of wormwood; Described containing Al
3+inorganic salt select AlCl
36H
2o; Described containing Mg
2+inorganic salt select MgCl
26H
2o; Containing Zn
2+inorganic salt select ZnCl
26H
2o; Described containing Cr
2+inorganic salt select CrCl
26H
2o; Described containing OH
-alkali select one or more in sodium hydroxide, potassium hydroxide or calcium hydroxide.
Particularly, CO in the mixing solutions that step a) makes
3 2-, Al
3+, the mol ratio of divalent-metal ion is 1～3: 3～5: 6～8 or/OH
--, Al
3+, the mol ratio of divalent-metal ion is 1～3: 3～5: 6～8.
Wherein, described step b), red mud comprises the raw material of following mole of proportioning:
Al
2O
3 5～7
SiO
2 19～22
CaO 44～48
Fe
2O
3 8～12
Na
2O 2～2.5
TiO
2 2～2.5
K
2O 2～2.5
Particularly, the component of described red mud is the waste of aluminium metallurgy factory.
Beneficial effect of the present invention embodies in the following areas:
1, inorganic mineral composite flame retardant of the present invention is nontoxic, is more conducive to reduce the injury to human body;
2, inorganic mineral composite flame retardant of the present invention has had the advantage of the fire retardants such as aluminium hydroxide, magnesium hydroxide, inorganic phosphorus, borate concurrently, has overcome again their deficiencies separately, have fire-retardant, eliminate smoke, fill 3 kinds of functions;
3, the raw materials cost that the preparation of inorganic mineral composite flame retardant of the present invention adopts is low;
4, inorganic mineral composite flame retardant of the present invention can be applied to exterior wall finishing, can add in cloth, composite plastic, composite floor board, road bitumen, is widely used.
Embodiment
1, the preparation of hydrotalcite
(1) apolegamy of red mud
Select the Al of 5mol
2o
3, 19mol SiO
2, the CaO of 44mol is, the Fe of 8mol
2o
3, 2mol Na
2the TiO of O, 2mol
2and the K of 2mol
2o uniform mixture, is mixed with red mud, standby.
(2) adopt AlCl
36H
2o, MgCl
26H
2o, NaCO
3for raw material, according to mol ratio n (Mg
2+): n (Al
3+): n (CO
3 2-)=6: 2: 1 take raw material;
(3) ionized water of 2000kg is joined in stainless steel stirring reaction axe, be heated to while stirring 60 ℃, in temperature, remain under the condition of 60 ℃, add sodium carbonate (60kg) stirring and dissolving even, then add AlCl
36H
2o (483kg), stirs; Then add MgCl
26H
2o (1218kg), stirs, and wherein stir speed (S.S.) is 800 revs/min;
(4) under temperature remains the condition of 60 ℃, the red mud (300kg) of preparation in step (1) is added in stainless steel stirring reaction axe, continue to stir 40 minutes, form the cotton-shaped suspension liquid of canescence;
(5) stop stirring, staticly settle, cool to room temperature, filter supernatant liquid, use again ionized water washing precipitate 2 times, then use absolute ethanol washing throw out 2 times, by throw out after 100 ℃ of oven dry, and 100 ℃ calcining 24 hours, make inorganic mineral Mg-Al hydrotalcite of the present invention.
2, the preparation of inorganic mineral fire retardant
(1) first, by following proportioning, take raw material:
Mg-Al hydrotalcite 15kg
Polypentaerythritol 5kg
Nine contracting ten glycerine four oleic acid ester 7kg
(2) Mg-Al hydrotalcite is placed in to the reaction ax that fills 800kg ionized water, under normal pressure, stir 2 hours, whipping temp is 80 ℃, stirring velocity is 60 revs/min, forms cotton-shaped white suspension liquid, until suspension liquid precipitation, cooling after, filter supernatant liquid, in reactor, add polypentaerythritol 5kg, at the uniform velocity stir 25 minutes, stirring velocity is 60 revs/min.
(3) add nine contracting ten glycerine four oleic acid ester 7kg in stainless steel stirred autoclave, at the uniform velocity stir 30 minutes, stirring velocity is 60 revs/min, and warming while stirring, when temperature arrives 80 ℃, keeps constant temperature 2 hours.
The present invention is prepared in hydrotalcite process except NaCO
3can also adopt NaOH, KOH, K outward,
2cO
3, Ca (OH)
2, CaCO
3deng being raw material;
Stablizer, except nine contracting ten glycerine four oleic acid esters, can also adopt two triglycerol monoleates.
Embodiment bis-
1, the preparation of hydrotalcite
(1) outfit of red mud
Select the Al of 6mol
2o
3, 20mol SiO
2, the CaO of 45mol is, the Fe of 10mol
2o
3, 2mol Na
2the TiO of O, 2mol
2and the K of 2mol
2o uniform mixture, is mixed with red mud, standby.
(2) adopt AlCl
36H
2o, ZnCl
26H
2o, NaOH are raw material, according to mol ratio n (Zn
2+): n (Al
3+): n (OH
-)=7: 4: 2 take raw material;
(3) ionized water of 2000kg is joined in stainless steel stirring reaction axe, be heated to while stirring 70 ℃, in temperature, be under 70 ℃ of conditions, to add sodium hydroxide NaOH (80kg) stirring and dissolving even, then add AlCl
36H
2o (966kg), stirs; Then add ZnCl
26H
2o (1638kg), stirs, and wherein, stirring velocity is 1000 revs/min;
(4) in temperature, remain under 70 ℃ of conditions, the red mud of preparation in step (1) is taken to 350kg and add in stainless steel stirring reaction axe, continue to stir 50 minutes, form the cotton-shaped suspension liquid of canescence;
(7) stop stirring, staticly settle, cool to room temperature, filter supernatant liquid, use again ionized water washing precipitate 3 times, then use absolute ethanol washing throw out 3 times, by throw out after 100 ℃ of oven dry, and 100 ℃ calcining 24 hours, make inorganic mineral Zn-Al hydrotalcite of the present invention.
2, the preparation of inorganic mineral fire retardant
(1) first, by following proportioning, take raw material:
Zn-Al hydrotalcite 50kg
Linking agent 10kg
Stablizer 10kg
Wherein, linking agent:
Epoxy resin 8kg
Polypentaerythritol 2kg
Stablizer:
Two triglycerol monostearate 5kg
Span 40 5kg
(2) Zn-Al hydrotalcite 50kg is placed in to the reaction ax that fills 800kg ionized water, under normal pressure, stir 2 hours, whipping temp is 85 ℃, stirring velocity is 80 revs/min, forms cotton-shaped white suspension liquid, until suspension liquid precipitation, cooling after, filter supernatant liquid, in reactor, add linking agent epoxy resin 8kg, polypentaerythritol 2kg to add, at the uniform velocity stir 30 minutes, stirring velocity is 80 revs/min.
(3) add span 40 to weigh 5kg, two triglycerol monostearate 5kg in reactor, at the uniform velocity stir 30 minutes, stirring velocity is 80 revs/min, and warming while stirring, when temperature arrives 80 ℃, keeps constant temperature 2.5 hours.
In the present invention, in stablizer, except using span 40, can also be sorbester p18.
Embodiment tri-
1, the preparation of hydrotalcite
(1) outfit of red mud
Select the Al of 7mol
2o
3, 22mol SiO
2, the CaO of 48mol is, the Fe of 12mol
2o
3, 2.5mol Na
2the TiO of O, 2.5mol
2and the K of 2.5mol
2o uniform mixture, is mixed with red mud, standby.
(2) adopt AlCl
36H
2o, CrCl
26H
2o, K
2cO
3for raw material, according to mol ratio n (Cr
2+): n (Al
3+): n (CO
3 2-)=8: 5: 3 take raw material;
(3) ionized water of 2000kg is joined in stainless steel stirring reaction axe, be heated to while stirring 85 ℃, in temperature, remain under the condition of 85 ℃, add K
2cO
3(354kg) stirring and dissolving is even, then adds AlCl
36H
2o (1207.5kg), stirs; Then add CrCl
26H
2o (1768kg), stirs, and wherein, stirring velocity is 1200 revs/min;
(4) under the condition of 85 ℃ of temperature holding positions, the red mud of preparation in step (1) is taken to (400kg) and add in stainless steel stirring reaction axe, continue to stir 55 minutes,, form the cotton-shaped suspension liquid of canescence;
(5) stop stirring, quiescent setting, cool to room temperature, filter supernatant liquid, use again ionized water washing precipitate 2 times, then use absolute ethanol washing throw out 3 times, by throw out after 100 ℃ of oven dry, and 100 ℃ calcining 24 hours, make inorganic mineral Cr-Al hydrotalcite of the present invention.
2, the preparation of inorganic mineral fire retardant
(1) first, by following proportioning, take raw material:
Cr-Al hydrotalcite 3kg
Epoxy resin 3kg
Sorbester p18 1kg
Polysorbate60 1kg
In the present invention, except using described polysorbate60 as stablizer, can also use polysorbas20, tween 80.
(2) Cr-Al hydrotalcite is placed in to the reaction ax that fills 800kg ionized water, under normal pressure, stir 1 hour, whipping temp is 75 ℃, stirring velocity is 100 revs/min, forms cotton-shaped white suspension liquid, until suspension liquid precipitation, cooling after, filter supernatant liquid, in reactor, add linking agent epoxy resin 3kg, at the uniform velocity stir 40 minutes, stirring velocity is 100 revs/min.
(3) add sorbester p18 to weigh 1kg, polysorbate60 weighing 1kg in reactor, at the uniform velocity stir 45 minutes, stirring velocity is 100 revs/min, and warming while stirring, when temperature arrives 60 ℃, keeps constant temperature 1 hour.
Inorganic mineral composite flame retardant prepared by the present invention can be widely used in exterior wall finishing, inorganic mineral composite flame retardant of the present invention can also be added in cloth, composite plastic, composite floor board, road bitumen, play a part fire-retardant, the injury and the impact that to reduce the generation of fire, to people, cause, when inorganic mineral composite flame retardant of the present invention adds in road road bitumen, its limiting oxygen index(LOI) is 36, while adding in polymkeric substance, its limiting oxygen index(LOI) is greater than 40.
Claims (6)
1. a preparation method for inorganic mineral composite flame retardant, is characterized in that, comprises as follows step in sequence:
1) hydrotalcite is mixed with ionized water, stir, form hydrotalcite suspension liquid;
2) after hydrotalcite suspension liquid staticly settles, in precipitation, add linking agent, stir;
3) add stablizer, stir and be warming up to 60～80 ℃ simultaneously, keep constant temperature 1～3 hour;
Wherein, the quality proportioning of described hydrotalcite and linking agent, stablizer is 3～50:3～10:2～10;
Wherein, described linking agent is epoxy resin and/or polypentaerythritol; Stablizer is that glycerin fatty acid ester, lipid acid sorb are smooth, one or more in polysorbate or fatty alcohol-polyoxyethylene ether;
Wherein, the preparation of described hydrotalcite comprises the steps:
A) successively will be containing CO
3 2-, Al
3+, Mg
2+or Zn
2+or Cr
2+inorganic salt mix with ionized water, or will be containing OH
-alkali, containing Al
3+, Mg
2+or Zn
2+or Cr
2+inorganic salt mix with ionized water, form mixing solutions;
B) red mud is added in above-mentioned solution, stir, temperature of charge remains on 60-85 ℃;
Wherein, the component of described red mud and mole proportioning thereof are:
2. preparation method as claimed in claim 1, is characterized in that, described hydrotalcite is one or more in Mg-Al hydrotalcite, Zn-Al hydrotalcite, Cr-Al hydrotalcite.
3. preparation method as claimed in claim 1, is characterized in that, described glycerin fatty acid ester is nine contracting ten glycerine four oleic acid esters, a kind of in two triglycerol monostearates or two triglycerol monoleates; Lipid acid sorbose smooth (being sapn) is span 40 or sorbester p18; A kind of in polysorbas20, polysorbate60 or tween 80 of polysorbate (being tween).
4. preparation method as claimed in claim 1, is characterized in that, CO in the mixing solutions that described step a) makes
3 2-/ OH
-, Al
3+, Mg
2+or Zn
2+or Cr
2+mol ratio be 1～3:3～5:6～8.
5. an inorganic mineral composite flame retardant, is characterized in that comprising raw material: hydrotalcite, linking agent, stablizer, wherein, described hydrotalcite prepares according to the arbitrary described preparation method of claim 1-4.
6. inorganic mineral composite flame retardant as claimed in claim 5, is characterized in that, the quality proportioning of described hydrotalcite and linking agent, stablizer is 3～50:3～10:2～10.
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| DE102013001520B4 (en) * | 2013-01-22 | 2015-11-12 | Fluorchemie Gmbh Frankfurt | Novel inorganic, halogen-free flame retardant based on chemically modified recarbonized red mud, its production and use as well as a fire-protected material system |
| CN107267161A (en) * | 2016-04-07 | 2017-10-20 | 黑龙江宇威消防设备有限公司 | A kind of environment friendly flame retardant |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184969A (en) * | 1978-08-04 | 1980-01-22 | Bhat Industries, Inc. | Fire- and flame-retardant composition |
| US5079203A (en) * | 1990-05-25 | 1992-01-07 | Board Of Trustees Operating Michigan State University | Polyoxometalate intercalated layered double hydroxides |
| CN1435467A (en) * | 2002-01-29 | 2003-08-13 | 北京化工大学 | Super-fine high smoke-suppressing flame retardant and preparing method thereof |
| WO2004080896A1 (en) * | 2003-03-14 | 2004-09-23 | Beijing University Of Chemical Technology | The borate-intercalated layered double hydroxides, the process for preparing it and using it as fire retardant |
| CN1570023A (en) * | 2004-04-26 | 2005-01-26 | 浙江大学 | Inorganic combustion inhibitor and its preparation method |
| CN1600690A (en) * | 2004-10-13 | 2005-03-30 | 浙江大学 | Method for preparing oxide of bimetal and hydrotalcite by using Bayer red mud as raw material |
| CN1644508A (en) * | 2004-12-16 | 2005-07-27 | 浙江大学 | Production of acqueous talc from brine |
| AU2004222753A1 (en) * | 2004-10-21 | 2006-05-11 | Ji Shanshan | Process for synthesis of layered double oxides (LDO) and layered double hydroxides (LDH) using red mud produced from the Bayer process of alumina production |
| JP2008214127A (en) * | 2007-03-05 | 2008-09-18 | Tayca Corp | Layered double hydroxide delaminated in water, and method for producing the same |
| CN101914384A (en) * | 2010-07-23 | 2010-12-15 | 浙江大学 | Orthothioantimonate intercalated hydrotalcite and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10130831A1 (en) * | 2001-06-27 | 2003-01-16 | Bayer Ag | Flame retardant polyester molding compounds with hydrotalcite, red phosphorus and melamine cyanurate |
| CN1934190B (en) * | 2004-03-30 | 2010-11-24 | 住友电木株式会社 | Epoxy resin composition for the encapsulation of semiconductors and semiconductor devices |
-
2010
- 2010-12-31 CN CN201010618309.9A patent/CN102585845B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184969A (en) * | 1978-08-04 | 1980-01-22 | Bhat Industries, Inc. | Fire- and flame-retardant composition |
| US5079203A (en) * | 1990-05-25 | 1992-01-07 | Board Of Trustees Operating Michigan State University | Polyoxometalate intercalated layered double hydroxides |
| CN1435467A (en) * | 2002-01-29 | 2003-08-13 | 北京化工大学 | Super-fine high smoke-suppressing flame retardant and preparing method thereof |
| WO2004080896A1 (en) * | 2003-03-14 | 2004-09-23 | Beijing University Of Chemical Technology | The borate-intercalated layered double hydroxides, the process for preparing it and using it as fire retardant |
| CN1570023A (en) * | 2004-04-26 | 2005-01-26 | 浙江大学 | Inorganic combustion inhibitor and its preparation method |
| CN1600690A (en) * | 2004-10-13 | 2005-03-30 | 浙江大学 | Method for preparing oxide of bimetal and hydrotalcite by using Bayer red mud as raw material |
| AU2004222753A1 (en) * | 2004-10-21 | 2006-05-11 | Ji Shanshan | Process for synthesis of layered double oxides (LDO) and layered double hydroxides (LDH) using red mud produced from the Bayer process of alumina production |
| CN1644508A (en) * | 2004-12-16 | 2005-07-27 | 浙江大学 | Production of acqueous talc from brine |
| JP2008214127A (en) * | 2007-03-05 | 2008-09-18 | Tayca Corp | Layered double hydroxide delaminated in water, and method for producing the same |
| CN101914384A (en) * | 2010-07-23 | 2010-12-15 | 浙江大学 | Orthothioantimonate intercalated hydrotalcite and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| Chun-Hao Tseng,et al..Effect of reactive layered double hydroxides on the thermal and mechanical properties of LDHs/epoxy nanocomposites.《Composites Science and Technology》.2007,第67卷(第11-12期), |
| Effect of reactive layered double hydroxides on the thermal and mechanical properties of LDHs/epoxy nanocomposites;Chun-Hao Tseng,et al.;《Composites Science and Technology》;20070131;第67卷(第11-12期);2350-2362 * |
| Preparation of clay/epoxy nanocomposites by layered-double-hydroxide initiated self-polymerization;Ying-Nan Chan,et al.;《Polymer》;20080916;第49卷(第22期);4796-4801 * |
| Ying-Nan Chan,et al..Preparation of clay/epoxy nanocomposites by layered-double-hydroxide initiated self-polymerization.《Polymer》.2008,第49卷(第22期), |
| 纳米LDH对环氧树脂燃烧的抑烟作用;赵芸等;《应用化学》;20021025;第19卷(第10期);954-957 * |
| 翁腾飞等.镁铝水滑石的制备及其表面改性.《应用化工》.2009,第38卷(第9期), |
| 赵芸等.纳米LDH对环氧树脂燃烧的抑烟作用.《应用化学》.2002,第19卷(第10期), |
| 镁铝水滑石的制备及其表面改性;翁腾飞等;《应用化工》;20090928;第38卷(第9期);1355-1360 * |
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