CN1045426C - Process for producing aqueous antimony oxide sol - Google Patents
Process for producing aqueous antimony oxide sol Download PDFInfo
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- CN1045426C CN1045426C CN94119303A CN94119303A CN1045426C CN 1045426 C CN1045426 C CN 1045426C CN 94119303 A CN94119303 A CN 94119303A CN 94119303 A CN94119303 A CN 94119303A CN 1045426 C CN1045426 C CN 1045426C
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- sol
- water
- weisspiessglanz
- concentration
- antimony oxide
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- 229910000410 antimony oxide Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 47
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- -1 aliphatic polyols Chemical class 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 229920005862 polyol Polymers 0.000 claims abstract description 5
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 145
- 230000003647 oxidation Effects 0.000 claims description 34
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 23
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 38
- 239000011734 sodium Substances 0.000 description 32
- 238000002834 transmittance Methods 0.000 description 30
- 238000001035 drying Methods 0.000 description 17
- 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 description 15
- 239000003063 flame retardant Substances 0.000 description 15
- 239000000499 gel Substances 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 229960004418 trolamine Drugs 0.000 description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 150000001339 alkali metal compounds Chemical class 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 229910052728 basic metal Inorganic materials 0.000 description 8
- 150000003818 basic metals Chemical class 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000207961 Sesamum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A process for producing high concentration aqueous antimony oxide sol, antimony trioxide is allowed to react. with 0.8-2.5mol hydrogen peroxide based on 1mol antimony trioxide in water to prepare a sol of low concentration antimony oxide [Sb2O3+x (0<x<=2)] having a low concn. and an inorg. acid or ammonium salt is added to the sol by <=1wt.% of the amt. of the antimony oxide. The resulting antimony oxide gel is separated and washed and at least one kind of compd. selected from among alkanolamines, alkanolamine salts, aliphatic alpha-hydroxycarboxylic acids and aliphatic polyols is added as a dispersant to the washed gel by 1-50wt.% of the amt. of the antimony oxide.
Description
The invention relates to the manufacture method of aqueous antimony oxide sol, in more detail, is that manufacturing makes weisspiessglanz be dispersed into the manufacture method of the particulate high density oxidation antimony water-sol about cheapness.
Weisspiessglanz [chemical formula: Sb
2O
3+X(0＜X≤2)] the water-sol, mainly be to add the resin emulsion that contains halogen to and be added with in the resin emulsion of halogen flame retardant, and be coated on the processing object, as using fire-retardantization of resin emulsion or pay the flame retardant of processing object flame retardant resistance, and extensively utilized.
In addition, the feature that this aqueous antimony oxide sol has is, because the particle dia of weisspiessglanz is very little, the transparency is fine, in the time of on being coated in the processing object, does not injure the color of processing object substrate.
As the manufacture method of this aqueous antimony oxide sol, roughly knowing has: (1) is with antimonous oxide (Sb
2O
3) usefulness hydrogen peroxide (H in water
2O
2) oxidation style, the method that the dispergation of stibnate is decomposed in (2) acid.
And, the antimonous oxide of above-mentioned (1) is used in the hydrogen peroxide oxidation process, have and do not add any additive and make antimonous oxide with the oxidation style of hydrogen peroxide oxidation be added with inorganic or organic additive, make the oxidation style of antimonous oxide with hydrogen peroxide oxidation.
The above-mentioned additive that do not add, with the antimonous oxide hydrogen peroxide oxidation process, for obtaining the aqueous antimony oxide sol of high density, under high density, during with the hydrogen peroxide oxidation antimonous oxide, the particle dia that generates colloidal sol becomes big, adds man-hour in the resin emulsion and add to as flame retardant, easily damages the transparency of machining object part.For this reason, guarantee the good transparency, the particle dia that guarantees weisspiessglanz is wanted hour, and the limit that can obtain concentration is the water-sol about 25% (in this manual, about concentration, when not having certain illustrated, % is weight %).
Yet, in the aqueous antimony oxide sol of the low what 25% of concentration, when adding in the resin emulsion as flame retardant, because latex concentration is reduced, cause coating to wait processing characteristics also significantly to reduce, thereby must add tackifier, this has just brought other problem, that is, must limit the addition of the additive of paying other characteristic.
For this reason, the water-sol of lower concentration is evaporated its moisture, it is concentrated, when becoming the high liquid degree water-sol of the big what 50% of concentration, just have viscosity excessive, processing characteristics is reduced, and bring, make the problem of cost increases because of increasing concentrated engineering.
Therefore, only utilize the hydrogen peroxide oxidation antimonous oxide, can not make the water-sol that the weisspiessglanz of sening as an envoy to is dispersed into particulate high density at an easy rate.
For this reason,, repay examination and using the hydrogen peroxide oxidation stage, add inorganic or organic additive, obtain the water-sol of high density as aforementioned.
In above-mentioned method with hydrogen peroxide oxidation stage interpolation additive, have as the method for adding inorganics, Japanese patent application is announced clear 57-11848 communique, flat 3-35248 communique, flat 4-29610 communique, the clear 60-108466 communique of Japanese Patent Application Publication, disclosed method in the flat 2-174929 communique.
Yet,, can use the oxyhydroxide of basic metal or alkaline-earth metal, inorganic salts, inorganic silicic acid compound etc. as the inorganics that adds.
For example, accuse in the clear 57-11848 communique in the patent application of above-mentioned Japan, the manufacture method of the colloid solution of weisspiessglanz is disclosed, this method is with antimonous oxide, potassium hydroxide and hydrogen peroxide, roughly react, make it generate potassium antimonate, then remove ion by 1: 2.1: 2 mol ratio.
But the problem that exists with regard to aforesaid method also is, can not obtain the water-sol of high density, and when transpiring moisture concentrates, when improving concentration, dissolved adhesiveness increases and becomes and be difficult to handle, and owing to increased concentrated expense, whole expense has also been increased.
In addition, announce the manufacture method that discloses the colloidal weisspiessglanz in the flat 4-29610 communique in Japan's patent application.This method, when antimonous oxide and hydroperoxidation, make the mol ratio of antimonous oxide and hydrogen peroxide be decided to be 1: 1.25～1.8, and, at antimonous oxide, in reaction system, add 1.5～30% moles alkali metal hydroxide, carry out oxidizing reaction.
Yet the problem that this method exists is, sneaked into alkali metal compound in the colloid of weisspiessglanz, and this alkali metal compound has reduced the flame retardant effect that weisspiessglanz had.
In addition, as adding organic method, have in Japan's patent application and announce disclosed method in the clear 61-24330 communique in the hydrogen peroxide oxidation stage.
The manufacture method of aqueous antimony oxide sol is disclosed in clear 61-24330 communique.This method, in the presence of water-soluble stablizers such as alkanolamine, alkanolamine salt, aliphatics alpha-hydroxy carboxylic acid compounds, aliphatic polyol, with the granular antimony component of hydrogen peroxide oxidation, perhaps, at least after making a part change into the colloidal particle of water and weisspiessglanz, add above-mentioned water-soluble stablizer again, to make aqueous antimony oxide sol.
Yet the problem that aforesaid method exists also is, for the collosol property that obtains, can only make the colloidal sol of lower concentration, and thus, when by concentrating when improving concentration, viscosity has also increased, and owing to additionally increase the expense of concentrating, and make the whole cost increase.
In addition, disclose in Japan's patent application and to disclose a kind of method of making weisspiessglanz in the clear 63-310726 communique, rather than the manufacture method of the water-sol, this method will contain the stablizer antimony water-sol and carry out spraying drying, make and contain 8-13% moisture, the weisspiessglanz powder composition that its redispersibility is good.
Yet, existing problem is, the weisspiessglanz powder composition that obtains with aforesaid method can produce weisspiessglanz concentration at the high density oxidation antimony water-sol more than 50%, but the moisture when being difficult to control spraying drying, stable manufacturing is also difficult, and be accompanied by to pay and add spray-dired expense, and whole cost is improved.
Moreover, the composition that after Japan's patent application discloses the oxide treatment that discloses in the clear 60-108466 communique at antimonous oxide, carries out alkaline purification, this situation also is that basic metal or the alkaline earth metal compounds that will use in processing are blended in the composition, so reduced the flame retardant effect that weisspiessglanz had.
As the dispergation method that stibnate is decomposed in above-mentioned (2) acid, have in Japan's patent application announce flat 4-4980 communique, Japan's patent application discloses clear 61-227918 communique, disclosed method in the clear 62-182116 communique.
For example, announce the manufacture method that discloses a kind of antimony oxide sol in the flat 4-4980 communique in the patent application of above-mentioned Japan, this method is with stoichiometric ratio, make the monovalence or the divalence inorganic salt reaction of metaantimmonic acid alkali and 0.7～5 times of amount generate the weisspiessglanz gel, with this gel separation, after the washing, carry out dispergation with organic bases.
Yet, the existing problem of dispergation method that stibnate is decomposed in the acid of above-mentioned (2) is, which kind of situation no matter, used metaantimmonic acid alkali by what, after acid is decomposed, even with gel separation as raw material, clean with pickling, also can not remove basic metal fully, and, make the flame retardant effect that weisspiessglanz had reduce owing to remaining in the water-sol that generates basic metal arranged.
As above-mentioned, the manufacture method of the water-sol of the weisspiessglanz in past has all weak points.
For example, do not adding the method with the hydrogen peroxide oxidation antimonous oxide of additive, under high density during oxidation, it is big that the sol particles diameter that generates becomes, adding in the resin emulsion, add man-hour, very the transparency of easy damaged processing object as flame retardant.For this reason, guarantee the good transparency, under the state that keeps the small-particle diameter, obtain the water-sol, the highlyest can only obtain 25% low concentration of water colloidal sol.
Yet, the problem of bringing with the water-sol of lower concentration is, when adding in the resin emulsion, owing to reduced the concentration of latex, make coating wait processing characteristics significantly to reduce, thereby, originally can add tackifier, but must add this moment, perhaps, must place restrictions on the addition of the additive of paying other characteristic.
In addition, with the water-sol of this lower concentration, transpiring moisture is condensed into when being higher than high concentration water's colloidal sol of 50%, has increased viscosity, adds concentrated expense but also brought owing to paying, and whole cost is improved.
Thereby, only use hydrogen peroxide oxidation three hydrogenations two antimony, can not produce high density at an easy rate, be dispersed into particulate aqueous antimony oxide sol.
For this reason, the method of alkali metal compound etc. is added in employing in the hydrogen peroxide oxidation stage, because remaining in the water-sol that generates have an above-mentioned alkali metal compound, and reduced the effect of weisspiessglanz institute inherent flame retardant, so must carry out ion-exchange or extra filtration etc., so that remove metal ion, be accompanied by the employing of these engineerings, add the increase that funds bring whole cost because of paying.
In addition, in dispergation method with mineral acid treatment metaantimmonic acid alkali, though can make the water-sol of high density,, after acid is decomposed, even to gel separation, acid elution still has a part of basic metal in the raw material metaantimmonic acid alkali to enter into the structure of weisspiessglanz, and the result is with respect to weisspiessglanz, have the basic metal of several % to remain in the water-sol, these remaining basic metal will make the flame retardant effect of weisspiessglanz reduce greatly.
Therefore, for the processing characteristics that does not make resin emulsion reduces, do not damage the color of processing object simultaneously yet, and be desirable to provide the high density oxidation antimony water-sol that to give full play to weisspiessglanz institute inherent flame retardant effect.
Present inventors are according to above-mentioned hope, through conscientiously research, found that and use the hydrogen peroxide oxidation antimonous oxide, generate the aqueous antimony oxide sol of lower concentration, when interpolation mineral acid or ammonium salt carry out gelation in the above-mentioned water-sol, the weisspiessglanz gel that is obtained can be easy to separate by methods such as filtrations.
And then present inventors in surprise the hair cut according to above-mentioned resulting separation coagulate the degree filter also, condense with faint cohesive force, utilize the dispersion agent dispergation ability of trolamine etc., be easy to disperse dispergation, become the weisspiessglanz colloidal sol of high density.
Therefore, present inventors combine above-mentioned two kinds of opinions, do not contain the metallic compound beyond the weisspiessglanz, and weisspiessglanz are dispersed into microgranular, and the successfully cheap aqueous antimony oxide sol that produces high density is so finished the present invention.
That is, main points of the present invention are to make antimonous oxide in water, to the hydrogen peroxide of 1 mole weisspiessglanz with the 0.8-2.5 mole, make its reaction, generate the weisspiessglanz [(chemical formula: Sb of lower concentration
2O
3+X(0＜X≤2)] the water-sol, subsequently, above-mentioned weisspiessglanz is added 1% (weight) above mineral acid or ammonium salt, generate above-mentioned weisspiessglanz gel, separate, after the washing, from alkanolamine, alkanolamine salt, aliphatics alpha-hydroxy carboxylic acid compounds and aliphatic polyol, select at least a dispersion agent, add the dispersion agent of 1-50% (weight) at above-mentioned weisspiessglanz, and carry out the manufacture method that dispergation is the high density oxidation antimony water-sol of feature.
According to the present invention, owing to use the hydrogen peroxide oxidation antimonous oxide under lower concentration, it is big that the particle dia of weisspiessglanz can not become.Therefore, add to add in the resin emulsion can not damage man-hour processing object color.
And, replace with the transpiring moisture concentrating low-concentration water-sol, carry out frozen glueization, and separate it, utilize dispersion agent to carry out dispergation, concentration is uprised, thereby can not produce the viscosity increase when concentrating because of transpiring moisture.Therefore, when adding in the resin emulsion, the processing characteristics of resin emulsion is reduced.And, owing to be high density, the concentration of latex is significantly reduced.
In addition, owing to do not need dry and concentrated engineering such as spraying drying, or ion-exchange, metal ions such as additional filtration removal engineering is so can produce the high density oxidation antimony water-sol at an easy rate.
Below will describe enforcement of the present invention in detail.
At first, with the hydrogen peroxide oxidation antimonous oxide time, the concentration of antimonous oxide is preferably 5%-25%, and wherein 10%-20% is good especially.The concentration of antimonous oxide is lower than 5% o'clock production performance and reduces.When the concentration of antimonous oxide was higher than 25%, it is big that the weisspiessglanz particle dia after the oxidation becomes, the danger that has the transparency to reduce.
Amount of hydrogen peroxide when the antimonous oxide oxidation be that the 0.8-2.5 mole is comparatively suitable to 1 mole of antimonous oxide of what, and the 1.4-2.2 mole is good especially.To 1 mole of antimonous oxide of what, during 0.8 mole of the low what of amount of hydrogen peroxide, can not generate the good antimony oxide sol of the transparency.To 1 mole of antimonous oxide of what, during 2.5 moles of big whats of amount of hydrogen peroxide, increase unreacted hydrogen peroxide, be uneconomic.
This oxidizing reaction temperature is generally 80-105 ℃, and the reaction times is generally 0.5-3 hour.
Use the weisspiessglanz of hydrogen peroxide oxidation antimonous oxide generation as described above, with chemical formula Sb
2O
3+X(0＜X≤2) expression.Weisspiessglanz in the present invention means it is with this Sb all
2O
3+XThe oxide compound of (0＜X≤2) expression.As the main example that belongs to this weisspiessglanz, can enumerate, as Sb
2O
4, Sb
6O
13, Sb
2O
5Deng.Weisspiessglanz in most cases, generates as their mixture, perhaps as their hydrate, and the mixture of hydrate, the mixture of their oxide compound and hydrate etc. generates, and this will depend on the mol ratio of what peroxidation hydrogen to antimonous oxide.And as above-mentioned the aqueous antimony oxide sol of acquisition, the same with the situation of past technology, be lower concentration equally, said this lower concentration means low what 25%, preferably 10-20% usually.
Mineral acid as the aqueous antimony oxide sol gelation that above-mentioned oxidation is generated can use the monovalence of example hydrochloric acid, sulfuric acid, nitric acid etc. or the big mineral acid of strength of acid of divalence, but good especially be hydrochloric acid, sulfuric acid etc.
As the ammonium salt of the aqueous antimony oxide sol gelation that above-mentioned oxidation is generated, can enumerate as ammonium chloride, ammonium sulfate, ammonium acetate, brometo de amonio, ammonium nitrate, volatile salt, bicarbonate of ammonia etc., but ammonium chloride, ammonium acetate, ammonium sulfate etc. are good especially.
For making the mineral acid that above-mentioned aqueous antimony oxide sol gelation adds or the amount of ammonium salt, must be at weisspiessglanz more than 1%, best more than 2%.
To the what weisspiessglanz, during the few what 1% of the addition of mineral acid or ammonium salt, can not generate good gel, can miss and separate or increase disengaging time and uneconomical.The addition of mineral acid or ammonium salt even also can not produce specific question very greatly, after the separation, needs a large amount of water lotions for removing these, thereby preferably an amount of, the what weisspiessglanz is preferably reached 10% degree.
Except above-mentioned mineral acid or ammonium salt, also can use alkali metal compounds such as sodium-chlor, sodium sulfate, as the additive that makes the aqueous antimony oxide sol gelation, but when using these alkali metal compounds, make basic metal enter into the structure of weisspiessglanz, the flame retardant effect of weisspiessglanz is reduced.
As the separation method that generates gel, available filtration, centrifugation etc. are set out by easy and simple to handle, preferably use and filter.
After the separation, wash with the water yield that can not solation again.Usually, the water-sol cumulative volume at before separating is 10-30 (volume) %.
As making the weisspiessglanz gel that separates acquisition filter the also dispersion agent of dispergation, can enumerate alkanolamine as trolamine, diethanolamine, thanomin, tripropanol amine, N-ethamine thanomin etc.
Except above-mentioned alkanolamine, also can use the alkanolamine salt of trolamine phosphoric acid salt with dispergation ability etc., the aliphatic polyols of the aliphatics alpha-hydroxy carboxylic acid compounds of tartrate etc., glycerine etc. etc. are as dispersion agent, but above-mentioned alkanolamine is best.
As the addition of dispersion agents such as above-mentioned alkanolamine, must be 1-50% (weight) to the what weisspiessglanz, be preferably 3-30% (weight), and 3-15% (weight) is better.To the what weisspiessglanz, when the addition of dispersion agents such as alkanolamine lacked what 1 weight %, the dispergation situation was bad, can not generate the good colloidal sol of the transparency.To the what weisspiessglanz, during the big what 50 weight % of the addition of dispersion agents such as alkanolamine, can produce baneful influence to the characteristic of latex in the time of in adding the random glue of resin to.In addition, the concentration of weisspiessglanz preferably will be more than 40% in the water-sol.
The concentration of weisspiessglanz in the water-sol behind the dispergation, depend on what filter and throttle rate and the interpolation water yield during dispergation, usually as 65% when following, can make the water-sol of various concentration as weisspiessglanz concentration as required.The present invention is suitable for the what manufacturing than concentration height in the past, and the aqueous antimony oxide sol of the high density of promptly high what 25% particularly obtains more than 40%, especially during the water-sol of 45% above high density, is especially significantly giving play to its effect.
With the dispersion agent dispergation time, for example can adopt stirring-type dispersion, diffusion type dispersion, the dispersion of spraying formula etc., this does not have special stipulation.
When the dry water-sol, the weisspiessglanz specific surface area that is obtained in the water-sol is generally 50-90m
2/ g.And when the water-sol that obtains was diluted to 0.5% concentration, total light transmittance and Bayes (ヘ イ ズ) rate was respectively 45-80% and 5-35% usually.And then, the quinquevalence antimony of the weisspiessglanz in the water-sol that is obtained with antimonious than (Sb
5/ Sb
+ 3) usually more than 2.Work as Sb
+ 5/ Sb
+ 32 when above,, make the effect that improves the right property of resistance have the tendency of increase because weisspiessglanz has good reaction tendency to halogen.Simultaneously, owing to have the tendency that the particle diameter that generates weisspiessglanz is diminished, also just has the tendency that the water-sol transparency is improved.
If according to the present invention, can make the particulate aqueous antimony oxide sol of being dispersed into of high density at an easy rate.
Therefore, aqueous antimony oxide sol owing to the concentration height, when adding in the resin emulsion as flame retardant, owing to do not reduce the concentration of resin emulsion significantly, just can not reduce the processing characteristics of resin emulsion yet made in accordance with the present invention.Simultaneously, because weisspiessglanz is a finely particulate, thereby just can not damage the color of processing object.Moreover, the excellent stability of colloidal sol.
In addition, above-mentioned aqueous antimony oxide sol is owing to the metallic compound that is substantially devoid of outside the weisspiessglanz, so also just do not reduce the effect of weisspiessglanz institute inherent flame retardant.
Embodiment
Then enumerate embodiment and be described more specifically the present invention.But the present invention has more than and is limited to these embodiment.
In addition, in following embodiment and comparative example, physical property measurement is undertaken by following.
1. viscosity
Under 25 ℃, the single cylinder revolution viscometer PVC ス Na ト ロ Application type VS-A1 that utilizes sesame pumping system (シ ス テ system) society to make measures.
2.Sb
+ 5/ Sb
+ 3(quinquevalence antimony and antimonious ratio)
In the molten what hydrochloric acid of test portion (water-sol), with the total amount of aas determination Sb.Then, with the Sb in the test portion
+ 5, at normal temperatures, with the potassiumiodide reduction, the iodine that is generated with the Sulfothiorine titration is measured Sb with this again
+ 5Amount.Be calculated as follows out Sb from these measured values
+ 5/ Sb
+ 3
Sb
+ 5/ Sb
+ 3=Sb
+ 5Amount/(total Sb amount-Sb
+ 5Amount)
3. specific surface area
With dry 12 hours of the water-sol, the マ Le チ ソ-ズ 12 (full-automatic 12 corpse or other object for laboratory examination and chemical testing surface area test devices) that makes with the shallow ア イ of soup オ ニ Network ス society measured the specific surface area of dry thing under 95 ℃.
4. total light transmittance and Bayes lead (ヘ イ ズ leads)
With the concentration dilution to 0.5% of the water-sol, in the quartz cell of the wide 1cm that packs into, direct-reading Bayes computer (ヘ イ ズ コ Application PVC ュ--) the HGM-2DP type mensuration total light transmittance and the Bayes that make with ス ガ trier society lead.
Embodiment 1
561ml water is packed in the container of 1 liter of volume, stir on one side, add 114g antimonous oxide powder on one side, then add 35% aquae hydrogenii dioxidi 60.8g.The ratio of the relative what antimonous oxide of hydrogen peroxide is the corresponding 1.6 moles of hydrogen peroxide of 1 mole of antimonous oxide.
The suspension limit heating that obtains is stirred on the limit, is warming up to boiling in 15 minutes, and boiling state was kept 1 hour, obtained aqueous antimony oxide sol.
Aqueous antimony oxide sol cooling with obtaining remains on 80 ℃, to wherein adding 3.0g ammonium chloride (to what weisspiessglanz about 2.6%), stirs 15 minutes, obtains the weisspiessglanz hydrogel.
With the weisspiessglanz hydrogel that obtains, use the strainer of the diameter 19.5cm of liner 2 (the N0.5C filter paper of Japan filter paper society system), carry out suction filtration, after the liquid on the strainer disappears, directly append 100ml water, proceed suction filtration.After filtering end, the wet weisspiessglanz that takes out on the filter paper is filtered also.
With the wet filter of weisspiessglanz and the 10g that obtain, drying is 4 hours under 100 ℃, measures wet filter water ratio also, and water ratio is 38.3% as a result.
The wet filter of the weisspiessglanz that 120g is obtained is also put into the 200ml beaker, adds 7.2g ion exchanged water and 7.4g trolamine (the what weisspiessglanz is about 10 weight %), stirs 1 hour, obtains concentration and be 52.6% aqueous antimony oxide sol.
The water-sol pH that obtains is 7.95, and viscosity is 11cp, Na in the water-sol
2The concentration of O and Cl is as follows respectively, Na
2O is below 0.01%, and Cl is 80ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.
In addition, with water-sol drying, the weisspiessglanz specific surface area that obtains is 66m
2/ g can confirm that from big like this specific surface area the average particle diameter of weisspiessglanz is very little the water-sol.
And then total light transmittance is 64%, and it is 17% that Bayes leads, and can confirm that the resulting water-sol is the water-sol with transparent feel.
And, with the water-sol of above-mentioned such acquisition,, do not find that viscosity increases even under 30 ℃ of room temperatures, preserved 30 days yet.
Embodiment 2
When aqueous antimony oxide sol is transformed into gel, except that replacing the ammonium chloride used in the example 1, carry out the processing identical with embodiment 1 with the hydrochloric acid (hydrogenchloride to the what weisspiessglanz is about 2.6%) of 8.6g 35%, the weisspiessglanz that obtains wetting is filtered also.
Utilize and embodiment 1 identical method when measuring also water ratio of this wet filter, its water ratio is 36.3%.
Based on above-mentioned water ratio data, with the filter of 120g weisspiessglanz also, 11g ion exchanged water, 7.64g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1, obtain concentration and be 51.9% the weisspiessglanz aqueous solution.
The water-sol pH that is obtained is 7.4, and viscosity is 10cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is below 0.01%, and Cl is 110ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 4.0.And, with the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 63m
2/ g, total light transmittance: 66%, Bayes leads: 16%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, do not find that viscosity increases yet.
Embodiment 3
When aqueous antimony oxide sol is transformed into gel, used ammonium chloride addition is increased to 30g (to the what weisspiessglanz, the amount of this ammonium chloride is about 26%), with gel-filtration, water yield during washing is increased to 600ml, in addition, carry out the processing identical with embodiment 1, the wet filter that obtains weisspiessglanz also.
Utilize with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 39.5%.
Based on above-mentioned water ratio data, with the filter of 120g weisspiessglanz also, 4.7g ion exchanged water, 7.26g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1, obtain concentration and be 52.3% aqueous antimony oxide sol.
The water-sol pH that is obtained is 7.7, and viscosity is 13cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is below 0.01%, and Cl is 90ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.And, with this water-sol drying, the weisspiessglanz specific surface area that obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 65m
2/ g, total light transmittance are 63%, and it is 19% that Bayes leads, and can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, do not find that viscosity increases yet.
Embodiment 4
Except the amount of the antimonous oxide powder being carried out 35% hydrogen peroxide of oxidation reduces to the 53.2g, carry out the processing identical with embodiment 1, obtain the wet filter of weisspiessglanz also.To the ratio of the hydrogen peroxide of what antimonous oxide is 1 mole of antimonous oxide to 1.4 moles hydrogen peroxide.
Adopt with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 36.8%.
With above-mentioned water ratio data is the basis, and with the filter of 120g weisspiessglanz also, 10g ion exchanged water, 7.58g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1, obtains concentration and be 52.8% aqueous antimony oxide sol.
Resulting water-sol pH is 7.1, and viscosity is 11cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is below 0.01%, and Cl is 90ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 2.3.And, with the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 86m
2/ g, total light transmittance: 77%, Bayes leads: 9%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, there is not the viscosity of discovery to increase yet.
Embodiment 5
Except the amount with 35% hydrogen peroxide of antimonous oxide powder is increased to the 83.6g, carry out the processing identical with embodiment 1, obtain the wet filter of weisspiessglanz also.To the ratio of the hydrogen peroxide of what antimonous oxide is 1 mole of antimonous oxide to 2.2 moles hydrogen peroxide.
Adopt with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 37.2%.
With above-mentioned water ratio data is the basis, and with the filter of 120g weisspiessglanz also, 10g ion exchanged water, 7.54g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1, obtains concentration and be 52.7% aqueous antimony oxide sol.
Resulting water-sol pH is 7.1, and viscosity is 16cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is below 0.01%, and Cl is 95ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 8.8.And, with the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 58m
2/ g, total light transmittance: 57%, Bayes leads: 25%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, there is not the viscosity of discovery to increase yet.
In addition, the weisspiessglanz of present embodiment owing to increase for the mol ratio of the hydrogen peroxide of antimonous oxide, can infer that the resultant major part is Sb
2O
5(antimony peroxide) measures the X ray picture and the known Sb of the dry thing of above-mentioned weisspiessglanz
2O
5X ray picture relatively, both are unanimous on the whole.
Embodiment 6
Carry out the processing identical with embodiment 1, the wet filter that obtains water ratio and be 37.1% weisspiessglanz also.
As the basis, with the filter of 120g weisspiessglanz also, 22g ion exchanged water, 11.32g trolamine phosphoric acid salt (the what weisspiessglanz is about 15 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 47.8% aqueous antimony oxide sol.
Resulting water-sol pH:3.1, viscosity: 15cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:95ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.And, with the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 64m
2/ g, total light transmittance: 55%, Bayes leads: 27%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, there is not the viscosity of discovery to increase yet.
Embodiment 7
Carry out the processing identical with embodiment 1, the wet filter that obtains water ratio and be 37.6% weisspiessglanz also.
As the basis, with the filter of 120g weisspiessglanz also, 19g ion exchanged water, 11.23g tartrate (the what weisspiessglanz is about 15 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 47.8% aqueous antimony oxide sol.
The water-sol pH:1.2 that acquires, viscosity: 19cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:110ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 4.0.With the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 66m
2/ g, total light transmittance: 52%, Bayes leads: 29%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, there is not the viscosity of discovery to increase yet.
Embodiment 8
Carry out the processing identical with embodiment 1, the wet filter that obtains water ratio and be 37.9% weisspiessglanz also.
As the basis, with the filter of 120g weisspiessglanz also, 18g ion exchanged water, 11.18g glycerine (the what weisspiessglanz is about 15 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 48.3% aqueous antimony oxide sol.
Resulting water-sol pH:1.4, viscosity: 25cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:90ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 4.0.With the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 65m
2/ g, total light transmittance: 50%, Bayes leads: 31%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was at room temperature preserved 30 days, there is not the viscosity of discovery to increase yet.
Embodiment 9
Carry out the processing identical with embodiment 1, the wet filter that obtains water ratio and be 34.5% weisspiessglanz also.
As the basis, with the filter of 120g weisspiessglanz also, 4.7g ion exchanged water, 23.6g trolamine (the what weisspiessglanz is about 30 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 50.2% aqueous antimony oxide sol.
The water-sol pH:7.4 that obtains, viscosity: 12cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:115ppm, and the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.With the weisspiessglanz specific surface area that this water-sol drying obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 67m
2/ g, total light transmittance: 63%, Bayes leads: 18%, can confirm that the resulting water-sol is the water-sol with transparent feel.
In addition, even the water-sol of above-mentioned such acquisition was preserved 30 days down at 30 ℃, there is not the viscosity of discovery to increase yet.
Comparative example 1
205ml water is packed in the container of 1 liter of volume, and except oxidation under high density, other carries out identical processing with embodiment 1, obtains water ratio and be 38.2% the wet filter of weisspiessglanz also.
As the basis, with the filter of 120g weisspiessglanz also, 20g ion exchanged water, 7.42g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 46.6% aqueous antimony oxide sol.
Resulting water-sol pH:7.6, viscosity: 26cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:90ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 4.0.With this water-sol drying, the weisspiessglanz specific surface area that obtains, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 39m
2/ g, total light transmittance: 33%, Bayes leads: 64%, the water-sol that obtains is the opaque water-sol.This water-sol, specific surface area are 39m
2/ g compares for a short time as can be known with embodiment, can think that by oxidation under high density it is big that the particle dia of weisspiessglanz will become.
Comparative example 2
The amount of 35% aquae hydrogenii dioxidi that adds is reduced to 22.8g, and except the consumption of hydrogen peroxide exceeds the present invention, other carries out the processing identical with embodiment 1, obtains the wet filter of weisspiessglanz also.To the ratio of the hydrogen peroxide of what antimonous oxide is 1 mole of antimonous oxide to 0.6 mole hydrogen peroxide.The amount of hydrogen peroxide is littler than the scope (1 mole of antimonous oxide is to 0.8～2.5 mole of hydrogen peroxide) of this bright middle regulation.
Utilize with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 60.7%.
As the basis, with the filter of 120g weisspiessglanz also, 32.5g ion exchanged water, 4.72g trolamine (the what weisspiessglanz is about 10 weight %) carry out the processing identical with embodiment 1 with above-mentioned water ratio data, obtain concentration and be 27.6% aqueous antimony oxide sol.
Resulting water-sol pH:8.0, viscosity: 38cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:100ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 0.4.The specific surface area of the weisspiessglanz that this water-sol drying is obtained, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 67m
2/ g, total light transmittance: 25%, Bayes leads: 90%, the resulting water-sol is the opaque water-sol.Can think this water-sol, because the relative what antimonous oxide of hydrogen peroxide consumption very little, and it is very firm to make that the interparticle cohesion of weisspiessglanz becomes, even redispersion can not disperse, therefore just can not obtain to have and lures bright the water-sol.
Comparative example 3
In comparative example 3, for clearly,, to carry out moisture evaporation and concentrate low concentration of water colloidal sol, the problem that is produced when improving concentration is carried out following experiment.
Promptly, 561ml water is packed in the container of 1 liter of volume, stir on one side, add 114g antimonous oxide powder on one side, add the aquae hydrogenii dioxidi of 60.8g 35% subsequently, the suspension that heating while stirring obtains was warming up to boiling in 15 minutes, keep boiling state 1 hour, and obtained weisspiessglanz concentration and be 16.5% the water-sol.Ratio for the hydrogen peroxide of antimonous oxide is that 1 mole of antimonous oxide is to 1.6 moles of hydrogen peroxide.
Low concentration of water colloidal sol with obtaining concentrates with rotatory evaporator, obtains weisspiessglanz concentration and be 40.9% the water-sol.
Resulting water-sol pH:2.6, viscosity: 1100cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O is lower than 0.01%, Cl:10ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.The specific surface area of the weisspiessglanz that this water-sol drying is obtained, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 61m
2/ g, total light transmittance: 62%, Bayes leads: 22%, can confirm that the resulting water-sol is the opaque water-sol, but concentrate owing to carry out transpiring moisture, viscosity is increased to above-mentioned 1100cp, and viscosity is high to making the significantly reduced degree of processing characteristics (more than about 1000cp).
Comparative example 4
In comparative example 4, for clearly when the water-sol is transformed into gel, the problem that is produced when using alkali metal compound is carried out following experiment.
That is, when the water-sol was transformed into gel, except the ammonium chloride that replaces with 3g sodium-chlor (the what weisspiessglanz is about 2.6 weight %) using among the embodiment 1, other carried out the processing identical with embodiment 1, obtains the wet filter of weisspiessglanz also.
Utilize with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 40.2%.
Based on above-mentioned water ratio data, with the filter of 120g weisspiessglanz also, 4g ion exchanged water, 7.18g trolamine (is 10 weight % to the what weisspiessglanz) carry out the processing identical with embodiment 1, obtain concentration and be 52.7% aqueous antimony oxide sol.
Resulting water-sol pH:8.3, viscosity: 17cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O:0.64%, Cl:120ppm.And the Sb of weisspiessglanz in the water-sol
+ 5/ Sb
+ 3Be 3.9.The specific surface area of the weisspiessglanz that this water-sol drying is obtained, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 61m
2/ g, total light transmittance: 61%, Bayes leads: 19%, can confirm that the resulting water-sol is the water-sol with transparent feel, but because sodium-chlor produces gel, the Na of alkali metal compound
2O exists 0.64%, residual Na
2O has reached the degree (about more than 0.5%) that reduces the weisspiessglanz flame-retarding characteristic.
Comparative example 5
In comparative example 5,, carry out following experiment in order clearly stibnate to be carried out the problem that produces when dispergation is decomposed in acid.
That is, the 120g sodium antimonate is dispersed in the 400ml water, adds the hydrochloric acid of 70g 35% while stirring, subsequently, be warmed to 40 ℃ of reactions 4 hours.
Then, the weisspiessglanz gel that generates is carried out suction filtration, wash, obtain the wet filter of weisspiessglanz also with 80ml water.
Utilize with embodiment 1 identical method and measure this wet filter water ratio also, its water ratio is 36.4%.
Based on the data of above-mentioned water ratio, add the filter of 120g weisspiessglanz also, the 25g ion exchanged water, 7.63g trolamine (is 10 weight % to the what weisspiessglanz) after the mixing, is warmed to 75 ℃, carries out disperseing in 5 hours, obtains concentration and be 48.0% aqueous antimony oxide sol.
Resulting water-sol pH:8.7, viscosity: 16cp, the Na in the water-sol
2The concentration of O and Cl, as follows respectively, Na
2O:2.4%, Cl:1610ppm.And weisspiessglanz in this water-sol, all Sb nearly all is Sb
+ 5, do not detect Sb
+ 3, also just can not obtain Sb
+ 5/ Sb
+ 3Ratio.With the dry resulting weisspiessglanz specific surface area of this water-sol, total light transmittance, Bayes leads, and is as follows respectively, specific surface area: 71m
2/ g, total light transmittance: 61%, Bayes leads: 24%, can confirm that the resulting water-sol is to have the transparent water-sol, as the stibnate of initial material, carries out acid to it and decomposes, with dispergation, this just is related to, and has 2.4% alkali metal compound Na in the aqueous antimony oxide sol that obtains
2O.
Claims (3)
1. manufacture method that concentration is the 40-65 weight % high density oxidation antimony water-sol is characterized in that it comprises:
Make antimonous oxide in water with hydrogen peroxide, in reacting, to generate the Sb that consists of of lower concentration with respect to the ratio of 0.8～2.5 mole of hydrogen peroxide of 1 mole of antimonous oxide
2O
3+XThe water-sol of weisspiessglanz, 0＜X in the formula≤2,
Then, adding with respect to above-mentioned weisspiessglanz to it is the ammonium salt of 1-26 weight %, makes it to generate above-mentioned colloidal antimony oxide,
Described colloid is separated by filtration, and described colloid is washed,
Then, add the dispersion agent of 1-50 weight % with respect to above-mentioned weisspiessglanz, carry out dispergation, described dispersion agent is to be selected from least a in alkanolamine, alkanolamine salt, aliphatics alpha-hydroxy carboxylic acid compounds and the aliphatic polyol.
2. method according to claim 1, wherein, described dispersion agent is an alkanolamine.
3. method according to claim 1, wherein, in the aqueous antimony oxide sol by antimonous oxide and hydroperoxidation generation, the concentration of weisspiessglanz is below 25 weight %.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30089293A JP2671099B2 (en) | 1993-11-05 | 1993-11-05 | Method for producing antimony oxide aqueous sol |
| JP300892/93 | 1993-11-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109900A CN1109900A (en) | 1995-10-11 |
| CN1045426C true CN1045426C (en) | 1999-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94119303A Expired - Fee Related CN1045426C (en) | 1993-11-05 | 1994-11-04 | Process for producing aqueous antimony oxide sol |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2671099B2 (en) |
| CN (1) | CN1045426C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101205231B1 (en) * | 2004-08-17 | 2012-11-28 | 닛산 가가쿠 고교 가부시키 가이샤 | Method for producing metal oxide sol |
| CN104030354B (en) * | 2014-06-27 | 2015-08-19 | 锡矿山闪星锑业有限责任公司 | Hydrophobicity antimony peroxide organosol and raw powder's production technology |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6124330B2 (en) * | 1975-08-18 | 1986-06-10 | Rooreru Ind Inc | |
| JPH03285825A (en) * | 1990-03-30 | 1991-12-17 | Mitsubishi Materials Corp | Singly dispersible antimony pentoxide powder and production thereof |
-
1993
- 1993-11-05 JP JP30089293A patent/JP2671099B2/en not_active Expired - Lifetime
-
1994
- 1994-11-04 CN CN94119303A patent/CN1045426C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6124330B2 (en) * | 1975-08-18 | 1986-06-10 | Rooreru Ind Inc | |
| JPH03285825A (en) * | 1990-03-30 | 1991-12-17 | Mitsubishi Materials Corp | Singly dispersible antimony pentoxide powder and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1109900A (en) | 1995-10-11 |
| JP2671099B2 (en) | 1997-10-29 |
| JPH07133113A (en) | 1995-05-23 |
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