CN104497633B - Nano calcium carbonate surface treatment method - Google Patents
Nano calcium carbonate surface treatment method Download PDFInfo
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- CN104497633B CN104497633B CN201410685319.2A CN201410685319A CN104497633B CN 104497633 B CN104497633 B CN 104497633B CN 201410685319 A CN201410685319 A CN 201410685319A CN 104497633 B CN104497633 B CN 104497633B
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- fatty acid
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 132
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004381 surface treatment Methods 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 10
- 230000005587 bubbling Effects 0.000 claims abstract description 10
- 239000004571 lime Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 29
- 239000000194 fatty acid Substances 0.000 claims description 29
- 229930195729 fatty acid Natural products 0.000 claims description 29
- 150000004665 fatty acids Chemical class 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 23
- 230000003750 conditioning effect Effects 0.000 claims description 23
- -1 hydroxyl phosphate ester Chemical class 0.000 claims description 21
- 235000021355 Stearic acid Nutrition 0.000 claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 18
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 18
- 239000008117 stearic acid Substances 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 17
- 239000010452 phosphate Substances 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000006071 cream Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000007127 saponification reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims 1
- 239000011833 salt mixture Substances 0.000 claims 1
- 239000004590 silicone sealant Substances 0.000 abstract description 21
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000011049 filling Methods 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 230000008859 change Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013464 silicone adhesive Substances 0.000 description 7
- LHJROESDWMXAKD-UHFFFAOYSA-N trihydroxysilicon Chemical compound O[Si](O)O LHJROESDWMXAKD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 239000012767 functional filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000021003 saturated fats Nutrition 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a nano calcium carbonate surface treatment method which is as follows: diluting lime milk which is refined and aged for 72h, and transferring to a bubbling carbonization column; introducing kiln gas with the flow rate of 6-10m<3> / h, when the reaction liquid pH drops to below 7.0, continuing to introduce the kiln gas for carbonization for 10min, and after carbonation reaction is completed, controlling the nano calcium carbonate slurry specific surface area to 23-30m<2> / g. The nano calcium carbonate slurry temperature is controlled at 80 to 90 DEG C, after even stirring, a surfactant is added, and the modification of nano calcium carbonate is completed by continuing stirring for 60 to 90min. The highly active nano calcium carbonate prepared by the method is used as a filler for filling silicone sealant, the reinforcing effect is significantly increased, adhesion properties and weathering stability of the silicone sealant can be greatly improved; the method has the advantages of simple process, easy operation, suitability for industrial production, and good economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of surface treatment method of nano-calcium carbonate, and in particular to one kind can give silicone sealant
The surface treatment method of the nano-calcium carbonate of good bonding performance and weather resistance.
Technical background
Single-component room temperature vulcanized type silicone rubber is met the moisture in air and is reacted change elastomer-forming, can play bonding work
With being widely used in the fields such as building, automobile, electronics because of its excellent performance.The silicone sealant that existing market is used
Bonding and weather resistance are poor.For building trade, silicone sealant plays important structure function in glass curtain wall, due to
It connects glass and glass, glass and aluminium, bears wind-force, geological process, deadweight and temperature change etc..Therefore, silicon should be improved
The bonding and weather resistance of ketone seal gum, it is to avoid the structural assembling failure that produced due to due to fluid sealant, building rain
The quality problems such as water seepage, so as to ensure durability and the safety of glass curtain wall.
We have found under study for action, the impact of functional filler and coupling agent to the cementability and weatherability of silicone sealant
Larger, functional filler mentioned here refers to that Jing organises the nano-calcium carbonate of surface treatment.For nano-calcium carbonate, shadow
The principal element for ringing filling silicone adhesive bonding and weatherability is size and surface treatment.To being usually used in calcium carbonate surface process
Fatty acid, its one end is carboxyl, can carry out chemical bond between Calcium Carbonate molecule, forms unimolecule active layer, reduces carbon
The surface energy of sour calcium particle, lumps so as to prevent calcium carbonate particle from reuniting, improves dispersion of the calcium carbonate particle in polymer phase
Property；But, for chemical reaction is not produced between chain alkyl, with polymer, active force is weak for the other end.Therefore, the nanometer handled by which
Calcium Carbonate can not give the preferable cementability of filling silicone sealant and weatherability.
A kind of preparation method of nano-material modified silicone adhesive, wherein institute are disclosed in 102898838 A of Chinese patent CN
With nano-calcium carbonate and Pulvis Talci that filler is non-surface treated.Although general nano material has skin effect, quantum chi
The characteristic such as very little effect and macro quanta tunnel effect, but the nano-calcium carbonate of non-surface treated is used as silicone adhesive filler dispersibility
Difference, strengthening action are little, and filling with sealant weather resistance is poor.
A kind of manufacture of the nano-calcium carbonate for being applied to high-grade silicone adhesive is disclosed in 101863503 A of Chinese patent CN
Method.The process of tri- subsurfaces of nano-calcium carbonate Jing, is crushed twice.Surface conditioning agent used includes：A, oils and fatss are in the basic conditions
Mix resulting solution with fatty acid after saponification；B, satisfied fatty acid and its salt；C, unsaturated fatty acid and its salt.Fatty acid
(salt) can carry out a certain degree of chemical reaction with calcium carbonate surface calcium ion, make calcium carbonate surface be changed into oleophylic by hydrophilic
Property, improve nano-calcium carbonate dispersibility and the compatibility with polymer.Although the process of tri- subsurfaces of nano-calcium carbonate Jing, it
Effect to improving filling silicone adhesive performance is not obvious, especially for cementability and weatherability.
A kind of preparation side of fire-retardant zinc stearate modified calcium carbonate filler is disclosed in 103772849 A of Chinese patent CN
Method.Surface conditioning agent used is zinc stearate, morpholine.A kind of glycerol stearate is disclosed in 103468027 A of Chinese patent CN
The method of ester modified nano-calcium carbonate.Surface conditioning agent used is also soap.
In sum, the process for treating surface of current Calcium Carbonate is difficult to while giving the excellent bonding of silicone sealant and resistance to
Wait performance.
The content of the invention
The main purpose of the present invention is to provide a kind of silicone sealant good bonding performance and weather resistance of can giving
The surface treatment method of nano-calcium carbonate.
Present invention is primarily based on following principle is realized：
Nano-calcium carbonate to particle diameter between 40～100nm carries out wet process surface treatment technique, using saturated fat
Acid and the phosphate ester salt containing silicone hydroxyl mixture according to a certain ratio is used as surface conditioning agent.Sodium hydroxide is added in the hot water
Or potassium hydroxide, adding satisfied fatty acid after fully dissolving carries out saponification, is eventually adding the phosphate ester salt containing silicone hydroxyl,
Surface conditioning agent is obtained final product after stirring certain hour.
Fatty acid can give nano-calcium carbonate preferable oleophilic drainage performance, and most polymers system is had well
The compatibility, but simple fatty acid modified it is difficult to the demand that satisfaction prepares high performance silicon ketone seal gum.The present invention is modified on surface
The phosphate ester salt of silicone hydroxyl is introduced in agent, the bound phosphate groups in its molecule can be reacted with the calcium ion of calcium carbonate surface, make
Which forms stronger chemisorbed between Calcium Carbonate.Silicone hydroxyl in its molecule may participate in the curing reaction of silicone adhesive.Namely
Say, one end of phosphate ester salt molecule links Calcium Carbonate, the other end links polymer, two ends are all chemical bond, active force is stronger.
Phosphate ester salt containing silicone hydroxyl substantially plays action of coupling agents.What Jing fatty acids and the phosphate ester salt containing silicone hydroxyl were surface-treated receives
Rice Calcium Carbonate, with good dispersibility, not only can improve Polymer Processing performance, also be remarkably improved the mechanics of silicone adhesive
Performance and weather resistance.
The above phosphate ester salt containing silicone hydroxyl is 3- (trihydroxy silicon substrate) the third methyl phosphorodithioate.Its molecular weight is
238.18；Molecular formula is C4H12NaO6PSi；Molecular structural formula is as follows：
Concrete technical scheme of the present invention is as follows：
A kind of surface treatment method of nano-calcium carbonate, it is characterised in that：Its technological operation is：
1. the preparation of nano-calcium carbonate：
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.050-1.065, controls temperature and is
20-25 DEG C, it is then delivered to the bubbling carbonizing tower with stirring；
(2) being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 6-10m3/ h, carbon dioxide body
Product
Content is 25-35%, when reactant liquor pH is dropped to below 7.0, continues to be passed through kiln gas and crosses carbonization 10min, carbonating
Instead
Should complete, nano-calcium carbonate serosity specific surface area is controlled to 23-30m2/g。
2. nano-calcium carbonate is modified：
Gained nano-calcium carbonate serosity after carbonization is delivered in surface processing trough, 80～90 DEG C of temperature is controlled, stirring is equal
It is even；Then the surface conditioning agent of the mass parts 2～4% in terms of Calcium Carbonate butt is added, 60～90min is persistently stirred and is completed nanometer
Calcium Carbonate it is modified.
Above-described surface conditioning agent is satisfied fatty acid and contains the mixture of the phosphate ester salt of silicone hydroxyl, saturated fat
Acid with the quality proportioning of phosphate ester salt for containing silicone hydroxyl is：1: 0.5～3, the dosage of surface conditioning agent is to account for by quality proportioning
The 2～4% of nano-calcium carbonate total amount.
Above-described satisfied fatty acid is the satisfied fatty acid that carbon atom number is 18～22, preferably stearic acid, flower
The satisfied fatty acid of one kind or wherein arbitrarily several any proportionings in raw acid, behenic acid.
The preparation method of the above surface conditioning agent, adds sodium hydroxide or hydroxide in 90～97 DEG C of hot water
Potassium, addition for satisfied fatty acid consumption 8～14% add fatty acid to carry out saponification, stir after fully dissolving
30min, is subsequently adding 3- (trihydroxy silicon substrate) the third methyl phosphorodithioate, obtains required surface conditioning agent after stirring 20min.
The present invention outstanding advantages and good effect be：
1st, this method adds the phosphate ester salt containing silicone hydroxyl that wet process surface treatment, gained high activity are carried out to nano-calcium carbonate
Nano-calcium carbonate fills silicone sealant as filler so that its reinforcing effect is significantly improved, the adhesive property of silicone sealant
And weather-stable performance is also greatly improved.
2nd, this preparation method process is simple, processing ease are suitable for commercial production, with preferable economic benefit and society
Benefit.
Specific embodiment
The specific embodiment of the invention will be described in detail below.It is intended to help reader to understand, it is impossible to constitute to this
The restriction of invention practical range.
Embodiment 1
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 24.1m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 3.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
Satisfied fatty acid used by the above surface conditioning agent is stearic acid, stearic acid and 3- (trihydroxy silicon substrate) the third methyl
The proportioning of phosphate ester is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is 10% that stearic acid content is accounted for by mass fraction.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
Embodiment 2
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 24.1m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 2.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
Satisfied fatty acid used by the above surface conditioning agent is stearic acid, stearic acid and 3- (trihydroxy silicon substrate) the third methyl
The proportioning of phosphate ester is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is 10% that stearic acid content is accounted for by mass fraction.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
Embodiment 3
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 27.3m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 3.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
Satisfied fatty acid used by the above surface conditioning agent is stearic acid, stearic acid and 3- (trihydroxy silicon substrate) the third methyl
The proportioning of phosphate ester is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is 10% that stearic acid content is accounted for by mass fraction.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
Embodiment 4
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 24.1m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 3.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
Satisfied fatty acid used by the above surface conditioning agent is stearic acid, stearic acid and 3- (trihydroxy silicon substrate) the third methyl
The proportioning of phosphate ester is 2:1.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is 10% that stearic acid content is accounted for by mass fraction.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
Comparative example 1
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 24.1m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 3.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
The above surface conditioning agent is single fat acid saponification liquor, and satisfied fatty acid used is stearic acid.Hot water temperature
For 95 DEG C, sodium hydroxide concentration is 10% that stearic acid content is accounted for by mass fraction.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
Comparative example 2
(1) lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then
It is transported to the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m3/
H, carbon dioxide volume content are 30%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonic acid
Change reaction to complete, ripe slurry specific surface area is 24.1m2/g
(2), during gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred.
(3) surface treatment of 3.5% (in terms of Calcium Carbonate butt) is added in nano-calcium carbonate serosity obtained by step (2)
Agent, persistently stirs 60min and completes the modified of nano-calcium carbonate.
The above surface conditioning agent is single 3- (trihydroxy silicon substrate) the third methyl phosphorodithioate.
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, be dried
Temperature is 110 DEG C, crushes, is classified, that is, obtains nano-calcium carbonate of the present invention.
The parameters such as the surface treatment agent content of each embodiment and comparative example, it is calculated by mass, it is shown in Table 1.
Table 1：The content of calcium carbonate surface inorganic agent in each embodiment and comparative example
In upper table, inorganic agent percentage composition presses Calcium Carbonate Mass Calculation, and it is total that fatty acid presses inorganic agent with phosphate ester proportion
Amount trisection isodisperse shared by which is calculated.
The application test of embodiment and comparative example product
Surface modified nano calcium carbonate product of each embodiment with comparative example is applied to into silicone sealant according to a conventional method
Filling, compares and verifies surface modification effect.
Products application is shown in Table 2 in silicone sealant Ju Ti Pei Fang.
Table 2：Silicone sealant formula table
In upper table, cross-linking agent used is methyl tributanoximo silane (D-30)；Coupling agent is gamma-aminopropyl-triethoxy
Silane (KH-550)；Catalyst is dibutyl tin laurate (D-80).
Each embodiment and silicone sealant performance obtained by comparative example, are shown in Table 3.
Table 3：Each embodiment and silicone sealant performance table obtained by comparative example
Silicone sealant performance test in upper table adopts GB 16776-2005 (structural silicone sealant for building) standard.
Can be seen that what is filled after being surface-treated to nano-calcium carbonate using phosphate ester salt by above Experimental comparison
The tensile bond intensity of silicone sealant and it is aging after tensile bond intensity will be far above using merely fatty acid or phosphoric acid
The silicone sealant filled by the nano-calcium carbonate of ester salt treatment.Product i.e. of the present invention can give silicone sealant good viscous
Connect performance and weather resistance.
Claims (3)
1. a kind of surface treatment method of nano-calcium carbonate, it is characterised in that：Its technological operation is：
The preparation of A, nano-calcium carbonate：
（1）Lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.050～1.065, temperature is controlled for 20～25
DEG C, it is then delivered to the bubbling carbonizing tower with stirring；
（2）Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 6～10m/h, and carbon dioxide volume contains
Measure as 25～35%, when reactant liquor pH is dropped to below 7.0, continue to be passed through kiln gas and cross carbonization 10min, carbonation reaction is completed, and is received
Rice calcium carbonate serosity specific surface area is controlled to 23～30m2/g；
B, nano-calcium carbonate it is modified：
Gained nano-calcium carbonate serosity after carbonization is delivered in surface processing trough, 80～90 DEG C of temperature is controlled, is stirred；So
The surface conditioning agent of the mass parts 2～4% in terms of Calcium Carbonate butt is added afterwards, is persistently stirred 60～90min and is completed nano-calcium carbonate
It is modified；
Described surface conditioning agent be satisfied fatty acid with containing silicone hydroxyl phosphate ester salt mixture, satisfied fatty acid with it is siliceous
The quality proportioning of the phosphate ester salt of hydroxyl is：1: 0.5～3, the dosage of surface conditioning agent is to account for nano-calcium carbonate by quality proportioning
The 2～4% of calcium total amount；
Described satisfied fatty acid is the one kind or wherein arbitrarily several in 18～22 satisfied fatty acid for carbon atom number
The satisfied fatty acid of any proportioning.
2. the surface treatment method of a kind of nano-calcium carbonate according to claim 1, it is characterised in that：The surface treatment
The preparation method of agent, adds sodium hydroxide or potassium hydroxide in 90～97 DEG C of hot water, and addition is satisfied fatty acid consumption
8～14%, add satisfied fatty acid to carry out saponification after fully dissolving, stir 30min, be subsequently adding 3-（Trihydroxy silicon
Base）Third methyl phosphorodithioate, obtains required surface conditioning agent after stirring 20min.
3. a kind of surface treatment method of nano-calcium carbonate, it is characterised in that its technological operation is：
（1）Lime cream after refined, ageing 72h is diluted, proportion is adjusted to 1.055, controls temperature for 23 DEG C, then conveys
To the bubbling carbonizing tower with stirring；Being passed through purification, the kiln gas after cooling carries out carbonation reaction, and kiln gas flow is 8m/h, and two
Carbonoxide volume content is 30%, when reactant liquor pH is dropped to below 7.0, continues to be passed through kiln gas and crosses carbonization 10min, and carbonating is anti-
Should complete, ripe slurry specific surface area is 24.1m2/g；
（2）During gained nano-calcium carbonate serosity adds reactor after being carbonized, 85 DEG C of temperature is controlled, is stirred；
（3）In step（2）The surface conditioning agent of Calcium Carbonate butt 3.5% is added in gained nano-calcium carbonate serosity, is persistently stirred
60min completes the modified of nano-calcium carbonate；
Modified nano-calcium carbonate serosity is carried out into filter-press dehydration process, is dried using chain belt drying machine, baking temperature
For 110 DEG C, crush, be classified, that is, obtain nano-calcium carbonate；
The surface conditioning agent is stearic acid and 3-（Trihydroxy silicon substrate）The mixture of the third methyl phosphorodithioate, stearic acid and 3-（Three
Hydroxyl silicon substrate）The proportioning of the third methyl phosphorodithioate is 1:2, preparation method is that sodium hydroxide, addition are added in 95 DEG C of hot water
For the 10% of stearic acid dosage, add fatty acid to carry out saponification after fully dissolving, stir 30min, be subsequently adding 3-（Three hydroxyls
Base silicon substrate）Third methyl phosphorodithioate, obtains required surface conditioning agent after stirring 20min.
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