CN104497633A - Nano calcium carbonate surface treatment method - Google Patents
Nano calcium carbonate surface treatment method Download PDFInfo
- Publication number
- CN104497633A CN104497633A CN201410685319.2A CN201410685319A CN104497633A CN 104497633 A CN104497633 A CN 104497633A CN 201410685319 A CN201410685319 A CN 201410685319A CN 104497633 A CN104497633 A CN 104497633A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- nano
- surface treatment
- treatment agent
- saturated fatty
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 127
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004381 surface treatment Methods 0.000 title claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000005587 bubbling Effects 0.000 claims abstract description 9
- 239000012756 surface treatment agent Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 235000021355 Stearic acid Nutrition 0.000 claims description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 16
- 239000008117 stearic acid Substances 0.000 claims description 16
- -1 phosphate ester salt Chemical class 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 150000002632 lipids Chemical class 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 8
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 5
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 235000021357 Behenic acid Nutrition 0.000 claims description 2
- 229940116226 behenic acid Drugs 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000004590 silicone sealant Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 5
- 238000011049 filling Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000004571 lime Substances 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
- 238000001035 drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 239000013464 silicone adhesive Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000012767 functional filler Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-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
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000005728 strengthening Methods 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
- 238000009736 wetting Methods 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, be specifically related to a kind of surface treatment method can giving the nano-calcium carbonate of silicone sealant good bonding performance and weather resistance.
Technical background
The single-component room temperature vulcanized type silicon rubber moisture of meeting in air reacts and becomes elastomerics, can play bonding effect, be widely used in the fields such as building, automobile, electronics because of the performance of its excellence.Bonding and the weather resistance of the silicone sealant that existing market uses is poor.For building trade, silicone sealant plays important structure function in glass curtain wall, because it connects glass and glass, glass and aluminium, bears wind-force, earthquake action, deadweight and temperature variation etc.Therefore, the bonding of silicone sealant and weather resistance should be improved, avoid producing due to the reason of seal gum structurally to assemble unsuccessfully, the quality problems such as buildings rain leakage, thus ensure weather resistance and the security of glass curtain wall.
We find under study for action, and the impact on the cementability of silicone sealant and weathering resistance of functional filler and coupling agent is comparatively large, and functional filler mentioned here refers to through the surface-treated nano-calcium carbonate that organises.For nano-calcium carbonate, it is size and surface treatment that silicone adhesive principal element that is bonding and weathering resistance is filled in impact.To the lipid acid being usually used in calcium carbonate surface process, its one end is carboxyl, can and calcium carbonate molecule between carry out Chemical bond, form unit molecule active coating, reduce the surface energy of calcium carbonate particles, thus prevent calcium carbonate particles reunion caking, improve the dispersiveness of calcium carbonate particles in polymer phase; But the other end is chain alkyl, and does not produce chemical reaction between polymkeric substance, and reactive force is weak.Therefore, the nano-calcium carbonate handled by it can not be given and fill the desirable cementability of silicone sealant and weathering resistance.
Disclose a kind of preparation method of nano-material modified silicone adhesive in Chinese patent CN 102898838 A, wherein filler used is not surface treated nano-calcium carbonate and talcum powder.Although general nano material has the characteristics such as surface effects, quantum size effect and macro quanta tunnel effect, not surface treated nano-calcium carbonate is poor as silicone adhesive fillers dispersed, and strengthening action is little, and filling with sealant weather resistance is poor.
A kind of manufacture method being applied to the nano-calcium carbonate of high-grade silicone adhesive is disclosed in Chinese patent CN 101863503 A.Nano-calcium carbonate through three subsurface process, twice pulverizing.Surface treatment agent used comprises: A, grease in the basic conditions after saponification reaction with lipid acid mixing gained solution; B, saturated fatty acid and salt thereof; C, unsaturated fatty acids and salt thereof.The chemical reaction that lipid acid (salt) can carry out to a certain degree with calcium carbonate surface calcium ion, makes calcium carbonate surface change lipophilicity into by wetting ability, improve nano-calcium carbonate dispersed and with the consistency of polymkeric substance.Although nano-calcium carbonate is through three subsurface process, it is to improving the effect of filling silicone adhesive performance and not obvious, especially for cementability and weathering resistance.
A kind of preparation method of fire-retardant Zinic stearas modified calcium carbonate filler is disclosed in Chinese patent CN 103772849 A.Surface treatment agent used is Zinic stearas, morpholine.A kind of method of stearin modified nano calcium carbonate is disclosed in Chinese patent CN 103468027 A.Surface treatment agent used is also soap.
In sum, the process for treating surface of current calcium carbonate is difficult to give silicone sealant excellent bonding and weather resistance simultaneously.
Summary of the invention
The main object of the present invention is to provide a kind of surface treatment method can giving the nano-calcium carbonate of silicone sealant good bonding performance and weather resistance.
The present invention mainly realizes based on following principle:
Wet process surface treatment technique is carried out to the nano-calcium carbonate of particle diameter between 40 ~ 100nm, uses saturated fatty acid and the phosphate ester salt containing silicone hydroxyl mixture according to a certain ratio as surface treatment agent.Add sodium hydroxide or potassium hydroxide in the hot water, add saturated fatty acid again after fully dissolving and carry out saponification reaction, finally add the phosphate ester salt containing silicone hydroxyl, after stirring certain hour, namely obtain surface treatment agent.
Lipid acid can give nano-calcium carbonate good oleophilic drainage performance, has good consistency to most polymers system, but simple fatty acid modified being difficult to meets the demand preparing high performance silicon ketone seal gum.The present invention introduces the phosphate ester salt of silicone hydroxyl in surface-modifying agent, and the bound phosphate groups in its molecule can be reacted with the calcium ion of calcium carbonate surface, makes to form stronger chemisorption between itself and calcium carbonate.Silicone hydroxyl in its molecule can participate in the curing reaction of silicone adhesive.That is, one end of phosphate ester salt molecule links calcium carbonate, and the other end links polymkeric substance, and two ends are all Chemical bond, and reactive force is stronger.Phosphate ester salt containing silicone hydroxyl plays action of coupling agents in fact.Through lipid acid and the phosphate ester salt surface-treated nano-calcium carbonate containing silicone hydroxyl, there is good dispersiveness, not only can improve polymer processing performance, also can significantly improve mechanical property and the weather resistance of silicone adhesive.
The above phosphate ester salt containing silicone hydroxyl is 3-(trihydroxy-is silica-based) third methyl phosphorodithioate.Its molecular weight is 238.18; Molecular formula is C
4h
12naO
6pSi; Molecular structural formula is as follows:
The concrete technical scheme of the present invention is as follows:
A surface treatment method for nano-calcium carbonate, is characterized in that: its technological operation is:
1. the preparation of nano-calcium carbonate:
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.050-1.065, and control temperature is 20-25 DEG C, is then transported to the bubbling carbonizing tower with stirring;
(2) pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 6-10m
3/ h, carbonic acid gas volume
Content is 25-35%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonating is anti-
Should complete, nano-calcium carbonate slurries specific surface area controls as 23-30m
2/ g.
2. the modification of nano-calcium carbonate:
Be delivered in surface processing trough by gained nano-calcium carbonate slurries after carbonization, control temperature 80 ~ 90 DEG C, stirs; And then add in the surface treatment agent of calcium carbonate butt mass parts 2 ~ 4%, Keep agitation 60 ~ 90min completes the modification of nano-calcium carbonate.
Above-described surface treatment agent is the mixture of saturated fatty acid and the phosphate ester salt containing silicone hydroxyl, saturated fatty acid with the quality proportioning of the phosphate ester salt containing silicone hydroxyl is: 1: 0.5 ~ 3, and the dosage of surface treatment agent is account for 2 ~ 4% of nano-calcium carbonate total amount by quality proportioning.
Above-described saturated fatty acid to be carbon atom number be 18 ~ 22 saturated fatty acid, be preferably the saturated fatty acid of a kind of or wherein several arbitrarily any proportioning in stearic acid, eicosanoic acid, behenic acid.
The preparation method of the above surface treatment agent, sodium hydroxide or potassium hydroxide is added in the hot water of 90 ~ 97 DEG C, add-on is 8 ~ 14% of saturated fatty acid consumption, add lipid acid after abundant dissolving and carry out saponification reaction, stir 30min, then add 3-(trihydroxy-is silica-based) third methyl phosphorodithioate, after stirring 20min, obtain required surface treatment agent.
Outstanding advantages of the present invention and positively effect are:
1, the phosphate ester salt that present method adds containing silicone hydroxyl carries out wet process surface treatment to nano-calcium carbonate, gained high-activity nano calcium carbonate fills silicone sealant as filler, its reinforcing effect is significantly improved, and adhesiveproperties and the weather-stable performance of silicone sealant are also greatly improved.
2, this preparation method technique is simple, and processing ease, is suitable for industrial production, has good economic benefit and social benefit.
Embodiment
To be described in detail the specific embodiment of the invention below.Be intended to help reader understanding, the restriction to the scope of the present invention can not be formed.
Embodiment 1
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 24.1m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 3.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent saturated fatty acid used is stearic acid, and the proportioning of stearic acid and 3-(trihydroxy-is silica-based) third methyl phosphorodithioate is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is account for 10% of stearic acid content by massfraction.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
Embodiment 2
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 24.1m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 2.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent saturated fatty acid used is stearic acid, and the proportioning of stearic acid and 3-(trihydroxy-is silica-based) third methyl phosphorodithioate is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is account for 10% of stearic acid content by massfraction.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
Embodiment 3
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 27.3m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 3.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent saturated fatty acid used is stearic acid, and the proportioning of stearic acid and 3-(trihydroxy-is silica-based) third methyl phosphorodithioate is 1:2.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is account for 10% of stearic acid content by massfraction.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
Embodiment 4
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 24.1m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 3.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent saturated fatty acid used is stearic acid, and the proportioning of stearic acid and 3-(trihydroxy-is silica-based) third methyl phosphorodithioate is 2:1.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is account for 10% of stearic acid content by massfraction.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
Comparative example 1
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 24.1m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 3.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent is single fat acid saponification liquor, and saturated fatty acid used is stearic acid.Hot water temperature is 95 DEG C, and sodium hydroxide concentration is account for 10% of stearic acid content by massfraction.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
Comparative example 2
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.055, and control temperature is 23 DEG C, is then transported to the bubbling carbonizing tower with stirring; Pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 8m
3/ h, carbonic acid gas volume content is 30%, and when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and ripe slurry specific surface area is 24.1m
2/ g
(2) add in reactor by gained nano-calcium carbonate slurries after carbonization, control temperature 85 DEG C, stirs.
(3) in step (2) gained nano-calcium carbonate slurries, add the surface treatment agent of 3.5% (in calcium carbonate butt), Keep agitation 60min completes the modification of nano-calcium carbonate.
The above surface treatment agent is single 3-(trihydroxy-is silica-based) third methyl phosphorodithioate.
Modified nano-calcium carbonate slurries are carried out filter-press dehydration process, and usage chain band drying machine is dried, and drying temperature is 110 DEG C, and pulverizing, classification, namely obtain nano-calcium carbonate of the present invention.
The parameters such as the surface treatment agent content of each embodiment and comparative example, calculate, in mass in table 1.
Table 1: the content of calcium carbonate surface treatment agent in each embodiment and comparative example
In upper table, treatment agent percentage composition presses calcium carbonate Mass Calculation, and lipid acid and phosphoric acid ester proportion are pressed treatment agent total amount trisection isodisperse shared by it and calculated.
The application test of embodiment and comparative example product
The surface modified nano calcium carbonate product of each embodiment and comparative example is applied to silicone sealant according to a conventional method fill, compares and verify surface modification effect.
Product application is specifically filled a prescription in silicone sealant, in table 2.
Table 2: silicone sealant formula table
In upper table, linking agent used is methyl tributanoximo silane (D-30); Coupling agent is γ-aminopropyl triethoxysilane (KH-550); Catalyzer is dibutyl tin laurate (D-80).
Each embodiment and comparative example gained silicone sealant performance, in table 3.
Table 3: each embodiment and comparative example gained silicone sealant performance table
In upper table, silicone sealant performance test adopts GB 16776-2005 (structural silicone sealant for building) standard.
As can be seen from above Experimental comparison, the tensile bond intensity of silicone sealant of filling after using phosphate ester salt to carry out surface treatment to nano-calcium carbonate and aging after tensile bond intensity all will far above the simple silicone sealant using the nano-calcium carbonate of lipid acid or phosphate ester salt process fill.Namely product of the present invention can give the good adhesiveproperties of silicone sealant and weather resistance.
Claims (4)
1. a surface treatment method for nano-calcium carbonate, is characterized in that: its technological operation is:
The preparation of A, nano-calcium carbonate:
(1) diluted by the milk of lime after refining, ageing 72h, proportion is adjusted to 1.050-1.065, and control temperature is 20-25 DEG C, is then transported to the bubbling carbonizing tower with stirring;
(2) pass into purification, cooled kiln gas carries out carbonation reaction, kiln gas flow is 6-10m3/h, carbonic acid gas volume content is 25-35%, when reaction solution pH drops to below 7.0, continue to pass into kiln gas and cross carbonization 10min, carbonation reaction completes, and nano-calcium carbonate slurries specific surface area controls as 23-30m
2/ g;
The modification of B, nano-calcium carbonate:
Be delivered in surface processing trough by gained nano-calcium carbonate slurries after carbonization, control temperature 80 ~ 90 DEG C, stirs; And then add in the surface treatment agent of calcium carbonate butt mass parts 2 ~ 4%, Keep agitation 60 ~ 90min completes the modification of nano-calcium carbonate.
2. the surface treatment method of a kind of nano-calcium carbonate according to claim 1, it is characterized in that: described surface treatment agent is the mixture of saturated fatty acid and the phosphate ester salt containing silicone hydroxyl, saturated fatty acid with the quality proportioning of the phosphate ester salt containing silicone hydroxyl is: 1: 0.5 ~ 3, and the dosage of surface treatment agent is account for 2 ~ 4% of nano-calcium carbonate total amount by quality proportioning.
3. the surface treatment method of a kind of nano-calcium carbonate according to claim 1, it is characterized in that: described saturated fatty acid to be carbon atom number be 18 ~ 22 saturated fatty acid, be preferably the saturated fatty acid of a kind of or wherein several arbitrarily any proportioning in stearic acid, eicosanoic acid, behenic acid.
4. the surface treatment method of a kind of nano-calcium carbonate according to claim 1, it is characterized in that: the preparation method of described surface treatment agent, sodium hydroxide or potassium hydroxide is added in the hot water of 90 ~ 97 DEG C, add-on is 8 ~ 14% of saturated fatty acid consumption, add lipid acid after abundant dissolving and carry out saponification reaction, stir 30min, it is silica-based then to add 3-(trihydroxy-) the third methyl phosphorodithioate, obtain required surface treatment agent after stirring 20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410685319.2A CN104497633B (en) | 2014-11-25 | 2014-11-25 | Nano calcium carbonate surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410685319.2A CN104497633B (en) | 2014-11-25 | 2014-11-25 | Nano calcium carbonate surface treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104497633A true CN104497633A (en) | 2015-04-08 |
| CN104497633B CN104497633B (en) | 2017-04-19 |
Family
ID=52939095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410685319.2A Active CN104497633B (en) | 2014-11-25 | 2014-11-25 | Nano calcium carbonate surface treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104497633B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN105384968A (en) * | 2015-12-11 | 2016-03-09 | 广西华纳新材料科技有限公司 | Surface treatment method of nanometer calcium carbonate for rubber filling |
| CN105400238A (en) * | 2015-12-17 | 2016-03-16 | 广西华纳新材料科技有限公司 | Surface treatment method for nanometer calcium carbonate filled with PVC plastic paste |
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN105504881A (en) * | 2015-12-17 | 2016-04-20 | 广西华纳新材料科技有限公司 | Modification method of nano calcium carbonate special for PVC injection molding material |
| CN105820601A (en) * | 2016-04-18 | 2016-08-03 | 安徽省宣城市华纳新材料科技有限公司 | Preparation of special nano calcium carbonate for high-grade ink |
| CN106366287A (en) * | 2016-08-22 | 2017-02-01 | 连州市万仕达新材料有限公司 | Polyurethane modifier, preparation method thereof, and preparation method of nanometer calcium carbonate |
| CN107325587A (en) * | 2017-07-13 | 2017-11-07 | 广西田东民泰实业有限责任公司 | The Nano calcium carbonate dedicated preparation method of silicone structure sealant |
| CN109879303A (en) * | 2019-03-29 | 2019-06-14 | 桂林理工大学 | A kind of preparation method of the nanometer calcium carbonate of the dispersion of stable suspersion in aqueous solution |
| CN113416430A (en) * | 2021-06-29 | 2021-09-21 | 常州碳酸钙有限公司 | Preparation method and application of special nano calcium carbonate for polyurethane sealant |
| CN114410129A (en) * | 2022-02-16 | 2022-04-29 | 安徽省宣城市华纳新材料科技有限公司 | Nano calcium carbonate for double-component MS sealant and surface treatment method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286704B (en) * | 2017-07-13 | 2019-05-03 | 广西田东民泰实业有限责任公司 | The preparation method of mildew resistance silicone adhesive nanometer calcium carbonate |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848915A (en) * | 1994-08-03 | 1996-02-20 | Nippon Fine Chem Co Ltd | Calcium carbonate dispersion and its preparation |
| CN1330039A (en) * | 2001-08-03 | 2002-01-09 | 上海卓越纳米新材料股份有限公司 | Industrial process for preparing nm-class active calcium carbonate |
| CN101108741A (en) * | 2006-07-21 | 2008-01-23 | 北京市化工建材厂 | Industrial process for preparing nm-class active calcium carbonate |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| CN101863503A (en) * | 2010-06-22 | 2010-10-20 | 恩平市燕华化工实业有限公司 | Preparation method of nanometer calcium carbonate applied to top-grade silicone adhesive |
| CN102702795A (en) * | 2012-05-02 | 2012-10-03 | 石家庄市三兴钙业有限公司 | Preparation method of special nano calcium carbonate for polyurethane adhesives |
| CN102898838A (en) * | 2012-10-22 | 2013-01-30 | 广东普赛特电子科技股份有限公司 | Nanometer modified electronic silicone adhesive and preparation method of nanometer modified electronic silicone adhesive |
| CN103232732A (en) * | 2013-05-02 | 2013-08-07 | 潍坊飞龙功能碳酸钙科技有限公司 | Preparation method of superfine modified ground limestone |
| CN103754914A (en) * | 2013-12-04 | 2014-04-30 | 芜湖卓越纳米新材料有限公司 | Preparation method for submicron active calcium carbonate special for PVC and with low oil absorption value |
| WO2014086048A1 (en) * | 2012-12-09 | 2014-06-12 | 李广 | High-concentration carbonation method for adjusting shape of lime mud (calcium carbonate) particles |
| CN104016391A (en) * | 2014-04-10 | 2014-09-03 | 连州市凯恩斯纳米材料有限公司 | Method for preparing nanometer calcium carbonate for organic silicone electronic sealant by adopting continuous carbonization device |
-
2014
- 2014-11-25 CN CN201410685319.2A patent/CN104497633B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848915A (en) * | 1994-08-03 | 1996-02-20 | Nippon Fine Chem Co Ltd | Calcium carbonate dispersion and its preparation |
| CN1330039A (en) * | 2001-08-03 | 2002-01-09 | 上海卓越纳米新材料股份有限公司 | Industrial process for preparing nm-class active calcium carbonate |
| CN101108741A (en) * | 2006-07-21 | 2008-01-23 | 北京市化工建材厂 | Industrial process for preparing nm-class active calcium carbonate |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| CN101863503A (en) * | 2010-06-22 | 2010-10-20 | 恩平市燕华化工实业有限公司 | Preparation method of nanometer calcium carbonate applied to top-grade silicone adhesive |
| CN102702795A (en) * | 2012-05-02 | 2012-10-03 | 石家庄市三兴钙业有限公司 | Preparation method of special nano calcium carbonate for polyurethane adhesives |
| CN102898838A (en) * | 2012-10-22 | 2013-01-30 | 广东普赛特电子科技股份有限公司 | Nanometer modified electronic silicone adhesive and preparation method of nanometer modified electronic silicone adhesive |
| WO2014086048A1 (en) * | 2012-12-09 | 2014-06-12 | 李广 | High-concentration carbonation method for adjusting shape of lime mud (calcium carbonate) particles |
| CN103232732A (en) * | 2013-05-02 | 2013-08-07 | 潍坊飞龙功能碳酸钙科技有限公司 | Preparation method of superfine modified ground limestone |
| CN103754914A (en) * | 2013-12-04 | 2014-04-30 | 芜湖卓越纳米新材料有限公司 | Preparation method for submicron active calcium carbonate special for PVC and with low oil absorption value |
| CN104016391A (en) * | 2014-04-10 | 2014-09-03 | 连州市凯恩斯纳米材料有限公司 | Method for preparing nanometer calcium carbonate for organic silicone electronic sealant by adopting continuous carbonization device |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105482500A (en) * | 2015-11-25 | 2016-04-13 | 广西华纳新材料科技有限公司 | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant |
| CN105482500B (en) * | 2015-11-25 | 2018-09-14 | 广西华纳新材料科技有限公司 | The surface modifying method of silicone sealant antioxidant nano-calcium carbonate |
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN105384968B (en) * | 2015-12-11 | 2018-03-02 | 广西华纳新材料科技有限公司 | The surface treatment method of rubber filling nano-calcium carbonate |
| CN105384968A (en) * | 2015-12-11 | 2016-03-09 | 广西华纳新材料科技有限公司 | Surface treatment method of nanometer calcium carbonate for rubber filling |
| CN105504881A (en) * | 2015-12-17 | 2016-04-20 | 广西华纳新材料科技有限公司 | Modification method of nano calcium carbonate special for PVC injection molding material |
| CN105400238B (en) * | 2015-12-17 | 2018-02-16 | 广西华纳新材料科技有限公司 | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste |
| CN105400238A (en) * | 2015-12-17 | 2016-03-16 | 广西华纳新材料科技有限公司 | Surface treatment method for nanometer calcium carbonate filled with PVC plastic paste |
| CN105820601A (en) * | 2016-04-18 | 2016-08-03 | 安徽省宣城市华纳新材料科技有限公司 | Preparation of special nano calcium carbonate for high-grade ink |
| CN106366287A (en) * | 2016-08-22 | 2017-02-01 | 连州市万仕达新材料有限公司 | Polyurethane modifier, preparation method thereof, and preparation method of nanometer calcium carbonate |
| CN107325587A (en) * | 2017-07-13 | 2017-11-07 | 广西田东民泰实业有限责任公司 | The Nano calcium carbonate dedicated preparation method of silicone structure sealant |
| CN109879303A (en) * | 2019-03-29 | 2019-06-14 | 桂林理工大学 | A kind of preparation method of the nanometer calcium carbonate of the dispersion of stable suspersion in aqueous solution |
| CN109879303B (en) * | 2019-03-29 | 2022-11-11 | 桂林理工大学 | Preparation method of nano calcium carbonate capable of stably suspending and dispersing in aqueous solution |
| CN113416430A (en) * | 2021-06-29 | 2021-09-21 | 常州碳酸钙有限公司 | Preparation method and application of special nano calcium carbonate for polyurethane sealant |
| CN114410129A (en) * | 2022-02-16 | 2022-04-29 | 安徽省宣城市华纳新材料科技有限公司 | Nano calcium carbonate for double-component MS sealant and surface treatment method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104497633B (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104497633A (en) | Nano calcium carbonate surface treatment method | |
| CN106700657B (en) | A kind of surface treatment method of thermostable silicone glue nano-calcium carbonate | |
| CN103897434B (en) | The preparation method that plastic master batch is Nano calcium carbonate dedicated | |
| CN104844269B (en) | Inorganic silicate waterproof agent with depth permeability and filling property and preparation method of waterproof agent | |
| CN113278118B (en) | Temperature-resistant and salt-resistant nano polymer emulsion and synthesis method and application thereof | |
| CN104231264A (en) | Preparation method and application of graphene oxide/silicon dioxide/polyaniline composite material | |
| CN104876528B (en) | A kind of method that utilization lithium aluminium houghite prepares the early injection pulp material of dual liquid type | |
| CN104876204A (en) | Method for modifying graphene oxide | |
| CN107488435A (en) | A kind of high resiliency one-component silicone sealant and preparation method thereof | |
| CN105400237A (en) | Surface treatment method for nanometer calcium carbonate applied to fill silicone sealant | |
| CN109651975B (en) | Preparation method of nano calcium carbonate for double-component silane modified polyether sealant | |
| CN105731862B (en) | Anti- mud agent of diminishing and preparation method thereof | |
| CN105482500A (en) | Surface modification method of anti-oxidation nanometer calcium carbonate used for silicone sealant | |
| CN105400238B (en) | A kind of surface treatment method of the nano-calcium carbonate of filled PVC plasticized paste | |
| CN105330334A (en) | Preparation method of silane modified concrete internal curing agent | |
| CN107903827A (en) | A kind of preparation method of high-adhesion high temperature resistant anchoring adhesive | |
| CN105217673B (en) | A kind of preparation method of high thixotropic silicone adhesive special-purpose nanometer activated Calcium carbonate | |
| CN107986657B (en) | Active stone powder for concrete and preparation method thereof | |
| CN105330783A (en) | Preparation method of silane modified concrete internal curing agent | |
| CN104974763A (en) | Compound earthen site reinforcement material and earthen site reinforcement method | |
| CN104831364A (en) | Method for surface modification of calcium sulfate whiskers | |
| CN107540998A (en) | A kind of recreation ground recreation facility foundation soil strengthening agent preparation method | |
| CN102775109A (en) | Preparation method of hydrophilic-group nano SiO2 composite quick-setting cement grout | |
| CN102634325A (en) | Water and leakage plugging material of retarded crosslinking gel wrapping high valence metal ions | |
| CN109718003A (en) | A kind of graphene fever composite material and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Surface treatment method of nano calcium carbonate Effective date of registration: 20190515 Granted publication date: 20170419 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: 2019450000021 |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 530103 No.29, Ganwei street, Ganwei Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region Patentee after: Guangxi Warner New Material Co.,Ltd. Address before: 530103 No.29, Ganwei street, Ganwei Town, Wuming County, Nanning City, Guangxi Zhuang Autonomous Region Patentee before: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20170419 Pledgee: Bank of Communications Ltd. the Guangxi Zhuang Autonomous Region branch Pledgor: GUANGXI HUANA NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: 2019450000021 |