CN115717000A - Preparation method of rubber compatible nano calcium carbonate - Google Patents
Preparation method of rubber compatible nano calcium carbonate Download PDFInfo
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- CN115717000A CN115717000A CN202211448790.0A CN202211448790A CN115717000A CN 115717000 A CN115717000 A CN 115717000A CN 202211448790 A CN202211448790 A CN 202211448790A CN 115717000 A CN115717000 A CN 115717000A
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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 200
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 100
- 229920001971 elastomer Polymers 0.000 title claims abstract description 31
- 239000005060 rubber Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000000843 powder Substances 0.000 claims abstract description 132
- 238000003756 stirring Methods 0.000 claims abstract description 132
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000007788 liquid Substances 0.000 claims abstract description 92
- 239000000725 suspension Substances 0.000 claims abstract description 57
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000007790 solid phase Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 28
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 139
- 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
- 239000000292 calcium oxide Substances 0.000 claims description 69
- 235000012255 calcium oxide Nutrition 0.000 claims description 69
- 239000007864 aqueous solution Substances 0.000 claims description 67
- 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
- 239000003607 modifier Substances 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 35
- 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 30
- 239000000600 sorbitol Substances 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 29
- 229930006000 Sucrose Natural products 0.000 claims description 27
- 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 27
- 229960002989 glutamic acid Drugs 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 239000005720 sucrose Substances 0.000 claims description 27
- 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 26
- 230000032683 aging Effects 0.000 claims description 22
- 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 10
- 230000004913 activation Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012071 phase Substances 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
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 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 15
- 239000000945 filler Substances 0.000 description 9
- 238000012216 screening Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 6
- 238000005273 aeration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 230000008859 change 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
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009423 ventilation 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
Landscapes
- 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) carrying out secondary modification to obtain secondary modified powder; (4) Dispersing the secondary modified powder in absolute ethyl alcohol, 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 of 30 +/-2 ℃ on the mixed solution in the stirring state after the addition is finished, stirring for more than 5 hours at constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate. The method improves the compatibility and bonding strength of the nano calcium carbonate and a 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
Because of its high quality and low cost, calcium carbonate is widely used as filler in plastics, rubber, paint, paper making industry, etc. With the development of science and technology, the demand of various industries on rubber products is continuously expanded, but the quality requirement is more severe. At present, carbon black and white carbon black are generally adopted as main reinforcing agents of rubber products, and heavy calcium carbonate and common light calcium carbonate are matched as fillers.
In recent years, the nano calcium carbonate industry in China develops rapidly, and great progress is made in the setting of production process and matched production equipment. The synthesis and surface treatment technology of the nano calcium carbonate is taken as a core technology related to the use performance of the nano calcium carbonate in various industries, and different crystal forms and different coating layers can be designed according to the difference of application fields, so that the special design and production are realized. The chain-like nano calcium carbonate is acknowledged to have good reinforcing effect in rubber, but the use effect is influenced because the dispersibility is poor and the chain-like nano calcium carbonate cannot be well compatible with rubber sizing materials.
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, sieving the lime milk by using a screen with more than 300 meshes, collecting the sieved lime milk, standing and aging for more than 20h, respectively adding sorbitol and sucrose into the lime milk after aging is finished, stirring the lime milk after adding the materials, keeping the temperature to 30 +/-5 ℃, introducing kiln gas into the lime milk under the stirring state for reaction after keeping the temperature constant, stopping ventilation until the pH value of the lime milk is less than or equal to 7, then adding a TM-200S water-soluble titanate coupling agent aqueous solution into the lime milk, stirring for more than 1h for activation, carrying out solid-liquid separation 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 on the slurry at constant temperature of 80 +/-5 ℃, preserving heat, and carrying out condensation reflux; 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 is finished, then carrying out solid-liquid separation, washing a solid phase by hot water at the temperature of 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, continuously stirring the suspension for 2-3 hours after the addition is finished, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, 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 of the mixed solution to 30 +/-2 ℃ in the stirring state, stirring at the constant temperature for more than 5 hours, carrying out solid-liquid separation, washing the solid phase with absolute ethyl alcohol for 2 times, washing with deionized water for 2 times, and drying to obtain the rubber compatible nano calcium carbonate.
Further, the mass ratio of the quicklime added into the water is quicklime: water =1.
Further, the mass ratio of the added mass of the sorbitol and the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime =0.8 to 1.3 to 1.2.
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 addition mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime =10 to 20.
Further, in the step (2), the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1 to 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.
Further, in the step (3), the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1 to 15, and the modifier is bis- (γ -triethoxysilylpropyl) tetrasulfide in a weight ratio of bis- (γ -triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of = 4-5 g/100mL, wherein the ethanol aqueous solution is a solution with an ethanol volume fraction of 75%, and the volume ratio of the modifier added to the suspension is 1.
Further, in the step (4), the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethyl alcohol is solid/liquid =1 to 10-15, and the ratio of the added mass of toluene to the amount of the secondary modified powder is toluene: secondary modified powder =5 to 8mL:10g of a mixture; the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder =1 to 2.
The invention has the beneficial effects that: the method improves the compatibility and bonding strength of the nano calcium carbonate and a rubber matrix by improving the surface state of the nano calcium carbonate, and 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 the high and low temperature resistance of the rubber can be remarkably improved, and the application field of rubber materials is widened.
Detailed Description
The present invention will be further described with reference to the following 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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.8; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction) to react, stopping introducing gas until the pH value of lime milk is less than or equal to 7, adding the aqueous solution of the TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, wherein the TM-200S water-soluble titanate coupleThe mass percentage of solute in the aqueous solution of the coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 10; solid-liquid separation is carried out to remove a soluble phase, and the solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water of 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, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol water solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of =4g/100mL, stirring the suspension, and adding the modifier to the suspension under stirring, wherein the volume ratio of the modifier to the suspension is 1; continuously stirring the suspension for 2h 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 ethanol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethanol is solid/liquid =1: secondary modified powder =5mL:10g of the total weight of the mixture; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1; and after the addition is finished, keeping the water bath constant temperature of the mixed solution to 30 +/-2 ℃ in a stirring state, stirring for 5 hours at the constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.9; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction) to react, stopping aeration until the pH value of 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 1h for activation, wherein the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2 percent, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 14; solid-liquid separation is carried out to remove a soluble phase, and the solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water at the temperature of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio of: adding an ethanol aqueous solution with a ratio of =4g/100mL into an ethanol aqueous solution, stirring the suspension, adding the modifier into the suspension under stirring, wherein the volume ratio of the modifier added into the suspension is 1; after the addition is finished, continuously stirring the suspension for 2 hours, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethanol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethanol is solid/liquid =1: secondary modified powder =6mL:10g of a mixture; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1; and after the addition is finished, keeping the water bath constant temperature of the mixed solution to 30 +/-2 ℃ in a stirring state, stirring for 5 hours at the constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
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 stoneLime milk, the mass ratio of the quick lime added into the water is quicklime: water =1. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.9; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent by mass) of the calcium carbonate, stopping introducing gas until the pH value of lime milk is less than or equal to 7, then adding an 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 the TM-200S water-soluble titanate coupling agent is 3 percent, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 16; solid-liquid separation is carried out to remove a soluble phase, and a solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio of: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of =5g/100mL, stirring the suspension, and adding the modifier to the suspension under stirring, wherein the volume ratio of the modifier to the suspension is 1; after the addition is finished, continuously stirring the suspension for 2 hours, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethanol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethanol is solid/liquid =1: secondary modified powder =7mL:10g of a mixture; stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 2; and after the addition is finished, keeping the water bath constant temperature of the mixed solution to 30 +/-2 ℃ in a stirring state, stirring for 5 hours at the constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 1.2; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction), stopping aeration until the pH value of lime milk is less than or equal to 7, adding aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk, stirring for 1h for activation, and adding the aqueous solution of TM-200S water-soluble titanate coupling agent into the lime milk for activationThe mass percentage of the medium solute is 3%, the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 20; solid-liquid separation is carried out to remove a soluble phase, and a solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio of: adding an ethanol aqueous solution with the ratio of =5g/100mL into an ethanol aqueous solution, stirring the suspension, adding the modifier into the suspension under the stirring state, wherein the volume ratio of the modifier added into the suspension is 1; continuously stirring the suspension for 2h 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, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethyl alcohol is solid/liquid =1: secondary modified powder =8mL:10g of the total weight of the mixture; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 2; and after the addition is finished, keeping the water bath constant temperature of the mixed solution to 30 +/-2 ℃ in a stirring state, stirring for 5 hours at the constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
Comparative example 1
A preparation method of nano calcium carbonate used as a contrast 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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.9; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent by mass) of the calcium carbonate, stopping introducing gas until the pH value of lime milk is less than or equal to 7, then adding an 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 the TM-200S water-soluble titanate coupling agent is 2 percent, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 14; solid-liquid separation is carried out to remove a soluble phase, and the solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the absolute ethanol to form the suspension is solid/liquid =1, adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol water solution to prepare a modifier, wherein the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into a bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of =4g/100mL, stirring the suspension, and adding the modifier to the suspension under stirring, wherein the volume ratio of the modifier to the suspension is 1; continuously stirring the suspension for 2h after the addition is finished, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain primary modified powder of the comparative example;
(3) Dispersing the primary modified powder in the absolute ethyl alcohol according to the comparative example, wherein the solid-liquid mass ratio of the primary modified powder dispersed in the absolute ethyl alcohol is solid/liquid =1: primary modified powder =6mL:10g of a mixture; stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the primary modified powder is triethyl (trifluoromethyl) silane: primary modified powder = 1; after the addition is finished, the mixed solution is subjected to water bath constant temperature to 30 +/-2 ℃ in a stirring state, is stirred for 5 hours at constant temperature, is subjected to solid-liquid separation, and is washed by absolute ethyl alcohol for 2 times and deionized water for 2 times and is dried to obtain the nano calcium carbonate of the comparative example.
Comparative example 2
A preparation method of nano calcium carbonate used as a contrast 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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.9; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction) to react until the pH value of the lime milk is less than or equal to 7Introducing gas, then adding an aqueous solution of a TM-200S water-soluble titanate coupling agent into lime milk, stirring for 1h for activation, wherein the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2%, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 14; solid-liquid separation is carried out to remove a soluble phase, and the solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water at the temperature of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol, wherein the solid-liquid mass ratio of the primary modified powder dispersed in the absolute ethanol is solid/liquid =1: primary modified powder =6mL:10g of a mixture; stirring the mixed solution, and adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the primary modified powder is triethyl (trifluoromethyl) silane: primary modified powder = 1; after the addition is finished, the mixed solution is subjected to water bath constant temperature to 30 +/-2 ℃ in a stirring state, stirred for 5 hours at constant temperature, then solid-liquid separation is carried out, the solid phase is washed for 2 times by using absolute ethyl alcohol, washed for 2 times by using deionized water and dried, and the nano calcium carbonate of the comparative example is obtained.
Comparative example 3
A preparation method of nano calcium carbonate used as a contrast comprises the following steps:
(1) Adding calx into water, mixing and stirring for 20min to form lime milkAnd the mass ratio of the quicklime added into the water is quicklime: water =1. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, and respectively adding sorbitol and sucrose into the lime milk after aging is completed, wherein the mass ratio of the added mass of the sorbitol to the added mass of the sucrose to the mass of the quicklime is sorbitol: sucrose: quicklime = 0.9; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction) to react, stopping aeration until the pH value of 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 1h for activation, wherein the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2 percent, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 14; solid-liquid separation is carried out to remove a soluble phase, and a solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid = 1; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio of: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of =4g/100mL, stirring the suspension, and adding the modifier to the suspension under stirring, wherein the volume ratio of the modifier to the suspension is 1; and after the addition is finished, continuously stirring the suspension for 2 hours, 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 preparation method of nano calcium carbonate used as a contrast 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. And (2) screening the lime milk by using a 300-mesh screen, collecting the screened lime milk, standing and aging for 20h, adding sorbitol into the lime milk after aging is completed, wherein the mass ratio of the added sorbitol to the quick lime is sorbitol: quicklime = 1.5; stirring lime milk after feeding, keeping the temperature to 30 +/-5 ℃, and introducing kiln gas (CO) into the lime milk in a stirring state after keeping the temperature constant 2 25 percent of mass fraction) to react, stopping aeration until the pH value of 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 1h for activation, wherein the mass percentage of solute in the aqueous solution of the TM-200S water-soluble titanate coupling agent is 2 percent, and the mass ratio of the added mass of the aqueous solution of the TM-200S water-soluble titanate coupling agent to the mass of quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime = 14; solid-liquid separation is carried out to remove a soluble phase, and the solid phase is washed by deionized water and dried to obtain calcium carbonate powder;
(2) Dispersing the calcium carbonate powder in deionized water to form slurry, wherein the solid-liquid mass ratio of the calcium carbonate powder dispersed in the deionized water is solid/liquid =1, carrying out water bath constant temperature on the slurry to 80 +/-5 ℃, carrying out heat preservation, and carrying out condensation reflux; stirring the slurry, and adding L-glutamic acid into the slurry under 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; stirring and preserving heat for 50min after feeding, then carrying out solid-liquid separation, washing a solid phase with hot water of 80 ℃, and drying to obtain primary modified powder;
(3) Dispersing the primary modified powder in absolute ethanol to form a suspension, wherein the solid-liquid mass ratio of the suspension formed by dispersing the primary modified powder in absolute ethanol is solid/liquid =1, adding bis- (gamma-triethoxysilylpropyl) tetrasulfide into an ethanol aqueous solution to prepare a modifier, and the modifier is prepared by adding the bis- (gamma-triethoxysilylpropyl) tetrasulfide into bis- (gamma-triethoxysilylpropyl) tetrasulfide according to the weight ratio of: adding an ethanol aqueous solution with a ratio of =4g/100mL into an ethanol aqueous solution, stirring the suspension, adding the modifier into the suspension under stirring, wherein the volume ratio of the modifier added into the suspension is 1; after the addition is finished, continuously stirring the suspension for 2 hours, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethanol, wherein the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethanol is solid/liquid =1: secondary modified powder =6mL:10g of a mixture; stirring the mixed solution, adding triethyl (trifluoromethyl) silane into the mixed solution during stirring, wherein the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder = 1; and after the addition is finished, keeping the water bath constant temperature of the mixed solution to 30 +/-2 ℃ in a stirring state, stirring for 5 hours at the constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
Example 5
The calcium carbonate prepared in each of the above 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 mixed in a two-roll mill, the front roll temperature was set to 40. + -.5 ℃ and the rear roll temperature was set to 45. + -.5 ℃, and the normal vulcanization time was measured using a vulcanizer, and the rubber compound was vulcanized in a flat plate vulcanizer at a vulcanization temperature of 150 ℃ and a vulcanization time as the measured normal vulcanization time.
TABLE 1
| Components | Number of copies |
| Nitrile rubber | 100 |
| Zinc oxide | 5 |
| Stearic acid | 2 |
| Sulfur | 2 |
| Accelerant CZ | 1.5 |
| N-phenyl-2-naphthylamine | 2 |
| Nano calcium carbonate | 45 |
The rubber tensile properties of the nano calcium carbonate filler prepared by the methods of the above examples and comparative examples are tested according to the requirements of the national standard GB/T528-2009; the low-temperature brittleness of the alloy is tested according to the requirements of the national standard GB/T1682-1994, and the hot air aging performance of the alloy is tested 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) | Brittleness temperature (. Degree.C.) | The change rate of tensile strength after aging at 100 ℃ for 24 hours 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 |
It can be seen from table 2 that the nano calcium carbonate prepared by the method of the present invention is added into rubber as a filler, which can significantly improve the strength and high and low temperature resistance of the rubber, and this is probably because the modified nano calcium carbonate has good dispersibility in the rubber matrix and the compatibility between the filler and the matrix is improved, so that the optimization of the filler on the mechanical properties of the rubber is more obvious, and microcracks are not easily generated at the interface between the matrix and the filler during the stretching process, which is expressed as the improvement of the tensile strength.
The technical solutions provided by the present invention are described in detail above, and for those skilled in the art, the ideas according to the embodiments of the present invention may be changed in the specific implementation manners and the application ranges, and in summary, the content of the present description should not be construed as limiting the present invention.
Claims (7)
1. A preparation method of rubber compatible nano calcium carbonate is characterized by comprising the following steps:
(1) Adding quicklime into water, mixing and stirring to form lime milk, sieving the lime milk by using a screen mesh with the mesh size of more than 300, collecting the sieved lime milk, standing and aging for more than 20h, respectively adding sorbitol and sucrose into the lime milk after aging is finished, stirring the lime milk after the addition is finished, keeping the temperature to be 30 +/-5 ℃, introducing kiln gas into the lime milk under the stirring state for reaction after the constant temperature is kept, stopping introducing gas until the pH value of the lime milk is less than or equal to 7, then adding a TM-200S water-soluble titanate coupling agent aqueous solution into the lime milk, stirring for more than 1h for activation, performing solid-liquid separation to remove a soluble phase, washing a solid phase by using 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 on the slurry at constant temperature of 80 +/-5 ℃, preserving heat, and carrying out condensation reflux; 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 is finished, then carrying out solid-liquid separation, washing a solid phase by hot water at the temperature of 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, continuously stirring the suspension for 2-3 hours after the addition is finished, then carrying out solid-liquid separation, washing a solid phase by using absolute ethyl alcohol, and drying to obtain secondary modified powder;
(4) Dispersing the secondary modified powder in absolute ethyl alcohol, 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 of 30 +/-2 ℃ on the mixed solution in the stirring state after the addition is finished, stirring for more than 5 hours at constant temperature, then carrying out solid-liquid separation, washing the solid phase for 2 times by using absolute ethyl alcohol, washing for 2 times by using deionized water, and drying to obtain the rubber-compatible nano calcium carbonate.
2. The preparation method of the rubber compatible nano calcium carbonate according to claim 1, wherein the mass ratio of the quicklime added into the water is quicklime: water =1.
3. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein the mass ratio of the added mass of sorbitol and sucrose to the mass of quicklime is sorbitol: sucrose: quicklime =0.8 to 1.3 to 1.2.
4. The preparation method of 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 of the quicklime is the aqueous solution of the TM-200S water-soluble titanate coupling agent: quicklime =10 to 20.
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 the deionized water is solid/liquid =1 to 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.
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 to 10-15, and the modifier is bis- (γ -triethoxysilylpropyl) tetrasulfide: adding an ethanol aqueous solution to an ethanol aqueous solution with a ratio of = 4-5 g/100mL, wherein the ethanol aqueous solution is a solution with an ethanol volume fraction of 75%, and the volume ratio of the modifier added to the suspension is 1.
7. The method for preparing rubber-compatible nano calcium carbonate according to claim 1, wherein in the step (4), the solid-liquid mass ratio of the secondary modified powder dispersed in the absolute ethyl alcohol is solid/liquid =1 to 10-15, and the ratio of the mass of the added toluene to the amount of the secondary modified powder is toluene: secondary modified powder =5 to 8mL:10g of a mixture; the mass ratio of the added triethyl (trifluoromethyl) silane to the secondary modified powder is triethyl (trifluoromethyl) silane: secondary modified powder =1 to 2.
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| CN116426034A (en) * | 2023-03-21 | 2023-07-14 | 江西华明纳米碳酸钙有限公司 | A nano-calcium carbonate modification method and its application in PE blown film |
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