CN115717000B - Preparation method of rubber-compatible nano calcium carbonate - Google Patents
Preparation method of rubber-compatible nano calcium carbonate Download PDFInfo
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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 196
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 192
- 239000000843 powder Substances 0.000 claims abstract description 139
- 238000003756 stirring Methods 0.000 claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007788 liquid Substances 0.000 claims abstract description 92
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000000725 suspension Substances 0.000 claims abstract description 64
- 239000007790 solid phase Substances 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 33
- ZHSKFONQCREGOG-UHFFFAOYSA-N triethyl(trifluoromethyl)silane Chemical compound CC[Si](CC)(CC)C(F)(F)F ZHSKFONQCREGOG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 140
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 80
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 80
- 239000004571 lime Substances 0.000 claims description 80
- 235000013336 milk Nutrition 0.000 claims description 80
- 239000008267 milk Substances 0.000 claims description 80
- 210000004080 milk Anatomy 0.000 claims description 80
- 239000007864 aqueous solution Substances 0.000 claims description 70
- 239000000292 calcium oxide Substances 0.000 claims description 70
- 235000012255 calcium oxide Nutrition 0.000 claims description 70
- 235000019441 ethanol Nutrition 0.000 claims description 46
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- 239000007822 coupling agent Substances 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 38
- 239000003607 modifier Substances 0.000 claims description 36
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 31
- 239000000600 sorbitol Substances 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 29
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 28
- 229960002989 glutamic acid Drugs 0.000 claims description 27
- 229930006000 Sucrose Natural products 0.000 claims description 26
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 26
- 239000005720 sucrose Substances 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 10
- 238000009423 ventilation Methods 0.000 claims description 10
- 125000003338 L-glutaminyl group Chemical group O=C([*])[C@](N([H])[H])([H])C([H])([H])C([H])([H])C(=O)N([H])[H] 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 125000003944 tolyl group Chemical group 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 18
- 239000005060 rubber Substances 0.000 abstract description 18
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000945 filler Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a preparation method of rubber-compatible nano calcium carbonate, which comprises the following steps: (1) preparing calcium carbonate powder; (2) carrying out primary modification to obtain primary modified powder; (3) performing secondary modification to obtain secondary modified powder; (4) Dispersing the secondary modified powder in absolute ethyl alcohol, then adding toluene into the suspension to form a mixed solution, stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, carrying out water bath constant temperature to 30+/-2 ℃ in a stirring state after the addition, carrying out constant temperature stirring for more than 5 hours, then carrying out solid-liquid separation, washing a solid phase with absolute ethyl alcohol for 2 times, washing deionized water for 2 times, and drying to obtain the rubber-compatible nano calcium carbonate. The method improves the compatibility and the bonding strength of the nano calcium carbonate and the rubber matrix by improving the surface state of the nano calcium carbonate.
Description
Technical Field
The invention relates to the technical field of rubber additive materials, in particular to a preparation method of rubber-compatible nano calcium carbonate.
Background
Calcium carbonate is widely used as a filler in industries such as plastics, rubber, paint, paper and the like because of its excellent quality and low cost. With the development of technology, the requirements of various industries on rubber products are continuously expanding, but the requirements on quality are more severe. At present, carbon black and white carbon black are commonly adopted as main reinforcing agents of rubber products, and heavy calcium carbonate and common light calcium carbonate are adopted as fillers.
In recent years, the development of the nano calcium carbonate industry in China is rapid, and no small progress is made in the setting of the production process and the matched production equipment. The nano calcium carbonate synthesis and surface treatment technology is used as a core technology related to the use performance of nano calcium carbonate in various industries, and can design different crystal forms and provide different coating layers according to the difference of application fields, so that the special design and production are realized. The accepted chain nano calcium carbonate has good reinforcing effect in rubber, but has poor dispersibility, and can not be well compatible with rubber sizing materials, so that the using effect is affected.
Disclosure of Invention
Therefore, the invention provides a preparation method of rubber-compatible nano calcium carbonate, which comprises the following steps:
(1) Adding quicklime into water, mixing and stirring to form lime milk, passing the lime milk through a screen with more than 300 meshes, collecting the screened lime milk, standing and ageing for more than 20 hours, respectively adding sorbitol and sucrose into the lime milk after ageing, stirring the lime milk after ageing, keeping the temperature to 30+/-5 ℃, introducing kiln gas into the lime milk under a stirring state for reaction after the feeding is finished, stopping ventilation until the pH value of the lime milk is less than or equal to 7, then adding an aqueous solution of a TM-200S water-soluble titanate coupling agent into the lime milk, stirring for more than 1 hour for activation, separating solid from liquid to remove a soluble phase, washing a solid phase with deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, carrying out water bath constant temperature on the slurry to 80+/-5 ℃, carrying out heat preservation, and condensing and refluxing; stirring the slurry, adding L-glutamic acid into the slurry in a stirring state, stirring and preserving heat for 50-60 min after the addition, then carrying out solid-liquid separation, washing a solid phase with hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, stirring the suspension, adding the modifier into the suspension in a stirring state, continuing stirring the suspension for 2-3 h after the addition is finished, then carrying out solid-liquid separation, washing a solid phase with absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, then adding toluene into the suspension to form a mixed solution, stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, carrying out water bath constant temperature to 30+/-2 ℃ in a stirring state after the addition, carrying out constant temperature stirring for more than 5 hours, then carrying out solid-liquid separation, washing a solid phase with absolute ethyl alcohol for 2 times, washing deionized water for 2 times, and drying to obtain the rubber-compatible nano calcium carbonate.
Further, the mass ratio of the quicklime to the water is quicklime: water=1:6-10.
Further, the mass ratio of the added mass of sorbitol and sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime=0.8-1:0.3-1.2:100.
Further, the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2-3%, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass ratio of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime=10 to 20:100.
Further, in the step (2), the solid-liquid mass ratio of the calcium carbonate powder dispersed in deionized water is solid/liquid=1:10-15, and the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=8 to 10:100.
Further, in the step (3), the solid-liquid mass ratio of the primary modified powder dispersed in absolute ethanol to form a suspension is solid/liquid=1:10-15, and the modifier is bis- (gamma-triethoxysilylpropyl) tetrasulfide, wherein the mass ratio of the bis- (gamma-triethoxysilylpropyl) tetrasulfide is that of the bis- (gamma-triethoxysilylpropyl) tetrasulfide: the aqueous ethanol solution=4-5 g/100mL is added into the aqueous ethanol solution, wherein the aqueous ethanol solution is a solution with the volume fraction of 75% of ethanol, and the volume ratio of the modifier added into the suspension is 1:1.
Further, in the step (4), the mass ratio of solid to liquid of the secondary modified powder dispersed in absolute ethanol is solid/liquid=1:10-15, and the ratio of the addition amount of toluene to the secondary modified powder is toluene: secondary modified powder = 5-8 mL:10g; the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is that the mass ratio of the added triethyl (trifluoromethyl) silane is that: secondary modified powder=1-2:10.
The invention has the beneficial effects that: according to the method, the surface state of the nano calcium carbonate is improved, so that the compatibility and the bonding strength of the nano calcium carbonate and a rubber matrix are improved, and the nano calcium carbonate has good dispersibility in rubber; the prepared nano calcium carbonate is used as a filler to be added into rubber, so that the strength and high and low temperature resistance of the rubber can be obviously improved, and the application field of rubber materials is widened.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
A preparation method of rubber-compatible nano calcium carbonate comprises the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the mass ratio of the sorbitol to the sucrose to the quicklime is sorbitol: sucrose: quicklime=0.8:0.3:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=10:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder = 8:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution=4 g/100mL ratio into an ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in absolute ethyl alcohol is solid/liquid=1:10, and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the secondary modified powder is toluene: secondary modified powder = 5mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondarily modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, the solid phase is washed for 2 times by deionized water, and the rubber-compatible nano calcium carbonate is obtained after drying.
Example 2
A preparation method of rubber-compatible nano calcium carbonate comprises the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with 300 mesh sieve, collecting the sieved lime milk, standing and aging for 20h, and respectively adding sorbitol and sorbitol into the lime milk after aging is completedSucrose, wherein the mass ratio of the added mass of sorbitol and sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime=0.9:0.6:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=14:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=9:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution=4 g/100mL ratio into an ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in absolute ethyl alcohol is solid/liquid=1:10, and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the secondary modified powder is toluene: secondary modified powder = 6mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondarily modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, the solid phase is washed for 2 times by deionized water, and the rubber-compatible nano calcium carbonate is obtained after drying.
Example 3
A preparation method of rubber-compatible nano calcium carbonate comprises the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the mass ratio of the sorbitol to the sucrose to the quicklime is sorbitol: sucrose: quicklime=0.9:0.8:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 3%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=16:100; solid-liquid separationRemoving soluble phase, washing solid phase with deionized water, and oven drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=9:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding ethanol aqueous solution=5 g/100mL into ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in absolute ethyl alcohol is solid/liquid=1:10, and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the secondary modified powder is toluene: secondary modified powder = 7mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondarily modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 2:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, the solid phase is washed for 2 times by deionized water, and the rubber-compatible nano calcium carbonate is obtained after drying.
Example 4
A preparation method of rubber-compatible nano calcium carbonate comprises the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the mass ratio of the sorbitol to the sucrose to the quicklime is sorbitol: sucrose: quicklime=1:1.2:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 3%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=20:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder = 10:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding ethanol aqueous solution=5 g/100mL into ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in absolute ethyl alcohol is solid/liquid=1:10, and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the secondary modified powder is toluene: secondary modified powder = 8mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondarily modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 2:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, the solid phase is washed for 2 times by deionized water, and the rubber-compatible nano calcium carbonate is obtained after drying.
Comparative example 1
A method for preparing nano calcium carbonate for comparison, comprising the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with 300 mesh sieve, collecting the sieved lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the sorbitol isThe mass ratio of the added mass of the alcohol and the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime=0.9:0.6:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=14:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the calcium carbonate powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide into the bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the mass ratio: adding an ethanol aqueous solution=4 g/100mL ratio into an ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain primary modified powder of the comparative example;
(3) Dispersing the primary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the primary modified powder dispersed in absolute ethyl alcohol is (solid/liquid=1:10), and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the primary modified powder is toluene: primary modified powder = 6mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the primary modified powder is triethyl (trifluoromethyl) silane: primary modified powder = 1:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, and is washed for 2 times by deionized water, and then the nano calcium carbonate in the comparative example is obtained after drying.
Comparative example 2
A method for preparing nano calcium carbonate for comparison, comprising the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the mass ratio of the sorbitol to the sucrose to the quicklime is sorbitol: sucrose: quicklime=0.9:0.6:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=14:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=9:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the primary modified powder dispersed in absolute ethyl alcohol is (solid/liquid=1:10), and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the primary modified powder is toluene: primary modified powder = 6mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the primary modified powder is triethyl (trifluoromethyl) silane: primary modified powder = 1:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, and is washed for 2 times by deionized water, and then the nano calcium carbonate in the comparative example is obtained after drying.
Comparative example 3
A method for preparing nano calcium carbonate for comparison, comprising the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and respectively adding sorbitol and sucrose into the lime milk after aging, wherein the mass ratio of the sorbitol to the sucrose to the quicklime is sorbitol: sucrose: quicklime=0.9:0.6:100; stirring lime milk after the addition is completed, keeping the temperature to 30+/-5 ℃, and introducing kiln gas (CO) into the lime milk under the stirring state after keeping the temperature constant 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=14:100; solid-liquid separation to remove solublesWashing the solid phase with deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=9:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution=4 g/100mL ratio into an ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; and (3) continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain the nano calcium carbonate of the comparative example.
Comparative example 4
A method for preparing nano calcium carbonate for comparison, comprising the following steps:
(1) Adding quicklime into water, mixing and stirring for 20min to form lime milk, wherein the mass ratio of the quicklime to the water is quicklime: water=1:8. Sieving the lime milk with a 300-mesh screen, collecting the sieved lime milk, standing and aging for 20 hours, and adding sorbitol into the lime milk after aging, wherein the mass ratio of the sorbitol to the quicklime is sorbitol: quicklime=1.5:100; stirring lime milk after the addition is completed and keeping the temperature constantIntroducing kiln gas (CO) into lime milk under stirring at 30+ -5deg.C 2 And (3) stopping ventilation until the pH value of lime milk is less than or equal to 7, then adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of TM-200S water-soluble titanate coupling agent to the mass ratio of quick lime is the aqueous solution of TM-200S water-soluble titanate coupling agent: quicklime=14:100; removing a soluble phase by solid-liquid separation, washing a solid phase by deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the mass ratio of solid to liquid of the calcium carbonate powder dispersed in the deionized water is (solid/liquid=1:10), and carrying out water bath constant temperature to 80+/-5 ℃ for heat preservation, condensing and refluxing; stirring the slurry, and adding L-glutamic acid into the slurry in a stirring state, wherein the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=9:100; stirring and preserving heat for 50min after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethyl alcohol is (solid/liquid=1:10), adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by mixing the bis- (gamma-triethoxysilylpropyl) tetrasulfide with the following weight ratio of bis- (gamma-triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution=4 g/100mL ratio into an ethanol aqueous solution, wherein the ethanol aqueous solution is a solution with ethanol volume fraction of 75%, stirring the suspension, adding the modifier into the suspension in a stirring state, and adding the modifier into the suspension in a volume ratio of 1:1; continuously stirring the suspension for 2 hours after the addition is completed, then carrying out solid-liquid separation, washing a solid phase by absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in absolute ethyl alcohol is solid/liquid=1:10, and then adding toluene into the suspension to form a mixed solution, wherein the ratio of the addition amount of toluene to the addition amount of the secondary modified powder is toluene: secondary modified powder = 6mL:10g; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondarily modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1:10; after the addition, the mixed solution is subjected to water bath constant temperature to 30+/-2 ℃ under the stirring state, constant temperature stirring is carried out for 5 hours, then solid-liquid separation is carried out, the solid phase is washed for 2 times by absolute ethyl alcohol, the solid phase is washed for 2 times by deionized water, and the rubber-compatible nano calcium carbonate is obtained after drying.
Example 5
The calcium carbonate prepared in each of the examples and comparative examples was added as a filler to a nitrile rubber formulation according to the formulation shown in table 1, and the raw materials were kneaded in a twin roll mill, the front roll temperature was set at 40±5 ℃, the rear roll temperature was set at 45±5 ℃, and the positive vulcanization time was measured by a vulcanizing machine, and the rubber compound was vulcanized on a press vulcanizer at 150 ℃ for the positive vulcanization time measured.
TABLE 1
| Component (A) | Parts by weight |
| Nitrile rubber | 100 |
| Zinc oxide | 5 |
| Stearic acid | 2 |
| Sulfur, sulfur and its preparation method | 2 |
| Promoter CZ | 1.5 |
| N-phenyl-2-naphthylamine | 2 |
| Nanometer calcium carbonate | 45 |
Rubber tensile properties of the nano calcium carbonate filler prepared by the method of each example and comparative example are tested according to the requirements of national standard GB/T528-2009; the low temperature brittleness was measured according to the requirements of the national standard GB/T1682-1994, and the hot air aging performance was measured according to the requirements of the national standard GB/T3512-2001, and the results are shown in Table 2.
TABLE 2
| Test group | Tensile Strength (MPa) | Brittle temperature (. Degree. C.) | After aging at 100 ℃ for 24 hours, the change rate of tensile strength is% |
| Example 1 | 7.2 | -53 | -1.8 |
| Example 2 | 7.6 | -54 | -1.3 |
| Example 3 | 7.9 | -54 | -1.4 |
| Example 4 | 7.7 | -51 | -1.6 |
| Comparative example 1 | 5.2 | -47 | -3.7 |
| Comparative example 2 | 4.9 | -48 | -4.1 |
| Comparative example 3 | 4.4 | -44 | -3.9 |
| Comparative example 4 | 7.1 | -52 | -2.2 |
As can be seen from Table 2, the nano calcium carbonate prepared by the method of the invention is added into rubber as filler, and can obviously improve the strength and high and low temperature resistance of the rubber, probably because the modified nano calcium carbonate has good dispersibility in a rubber matrix and the compatibility of the filler and the matrix is improved, so that the filler has more obvious optimization on the mechanical properties of the rubber, microcracks are not easy to generate at the interface of the matrix and the filler in the stretching process, and the tensile strength is improved.
The foregoing detailed description of the embodiments of the present invention will be provided to those skilled in the art, and the detailed description and the examples should not be construed as limiting the invention.
Claims (7)
1. The preparation method of the rubber-compatible nano calcium carbonate is characterized by comprising the following steps of:
(1) Adding quicklime into water, mixing and stirring to form lime milk, passing the lime milk through a screen with more than 300 meshes, collecting the screened lime milk, standing and ageing for more than 20 hours, respectively adding sorbitol and sucrose into the lime milk after ageing, stirring the lime milk after ageing, keeping the temperature to 30+/-5 ℃, introducing kiln gas into the lime milk under a stirring state for reaction after the feeding is finished, stopping ventilation until the pH value of the lime milk is less than or equal to 7, then adding an aqueous solution of a TM-200S water-soluble titanate coupling agent into the lime milk, stirring for more than 1 hour for activation, separating solid from liquid to remove a soluble phase, washing a solid phase with deionized water, and drying to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, carrying out water bath constant temperature on the slurry to 80+/-5 ℃, carrying out heat preservation, and condensing and refluxing; stirring the slurry, adding L-glutamic acid into the slurry in a stirring state, stirring and preserving heat for 50-60 min after the addition, then carrying out solid-liquid separation, washing a solid phase with hot water at 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethyl alcohol to form a suspension, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, stirring the suspension, adding the modifier into the suspension in a stirring state, continuing stirring the suspension for 2-3 h after the addition is finished, then carrying out solid-liquid separation, washing a solid phase with absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, then adding toluene into the suspension to form a mixed solution, stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution in the stirring process, carrying out water bath constant temperature to 30+/-2 ℃ in a stirring state after the addition, carrying out constant temperature stirring for more than 5 hours, then carrying out solid-liquid separation, washing a solid phase with absolute ethyl alcohol for 2 times, washing deionized water for 2 times, and drying to obtain the rubber-compatible nano calcium carbonate.
2. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein the mass ratio of the quicklime to the water is quicklime: water=1:6-10.
3. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein the mass ratio of sorbitol and sucrose added to the quicklime is sorbitol: sucrose: quicklime=0.8-1:0.3-1.2:100.
4. The preparation method of the rubber-compatible nano calcium carbonate according to claim 1, wherein the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2% -3%, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass ratio of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime=10 to 20:100.
5. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein in the step (2), the solid-liquid mass ratio of the calcium carbonate powder dispersed in deionized water is solid/liquid=1:10-15, and the mass ratio of the added L-glutamic acid to the calcium carbonate powder is L-glutamic acid: calcium carbonate powder=8 to 10:100.
6. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein in the step (3), the solid-liquid mass ratio of the primary modified powder dispersed in absolute ethanol to form a suspension is solid/liquid=1:10-15, and the modifier is bis- (gamma-triethoxysilylpropyl) tetrasulfide, wherein the mass ratio of the bis- (gamma-triethoxysilylpropyl) tetrasulfide is as follows: the aqueous ethanol solution=4-5 g/100mL is added into the aqueous ethanol solution, wherein the aqueous ethanol solution is a solution with the volume fraction of 75% of ethanol, and the volume ratio of the modifier added into the suspension is 1:1.
7. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein in the step (4), the mass ratio of solid to liquid of the secondary modified powder dispersed in absolute ethanol is solid/liquid=1:10-15, and the ratio of the addition amount of toluene to the amount of the secondary modified powder is toluene: secondary modified powder = 5-8 mL:10g; the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is that the mass ratio of the added triethyl (trifluoromethyl) silane is that: secondary modified powder=1-2:10.
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| CN111606343A (en) * | 2020-04-28 | 2020-09-01 | 广西夏阳环保科技有限公司 | Preparation method of modified nano calcium carbonate |
| CN111909424A (en) * | 2020-07-07 | 2020-11-10 | 广西夏阳环保科技有限公司 | Preparation method and application of modified nano calcium carbonate for rubber |
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| JPH03126616A (en) * | 1989-10-12 | 1991-05-29 | Agency Of Ind Science & Technol | Production of basic calcium carbonate |
| CN201172643Y (en) * | 2008-02-21 | 2008-12-31 | 王平 | Equipment for preparing multifunction superfine calcium carbonate |
| CN106830043A (en) * | 2017-04-07 | 2017-06-13 | 张剑星 | A kind of method of surface modified nano calcium carbonate |
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