CN114262527A - Special nano calcium carbonate for silane modified polyether sealant and preparation method thereof - Google Patents
Special nano calcium carbonate for silane modified polyether sealant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a special nano calcium carbonate for silane modified polyether sealant and a preparation method thereof. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant comprises the following steps: 1) preparing calcium hydroxide coarse pulp; 2) preparing calcium hydroxide fine slurry; 3) preparing nano calcium carbonate slurry; 4) preparing a modifier; 5) modifying the nano calcium carbonate by using a modifier. The nano calcium carbonate special for the silane modified polyether sealant has good compatibility and dispersibility in the MS sealant, can effectively improve the basic performances of the MS sealant such as thixotropic property, reinforcing property, bonding property and the like, and can also effectively improve the pollution resistance of the MS sealant in the outdoor use process.
Description
Technical Field
The invention relates to the technical field of nano calcium carbonate, in particular to nano calcium carbonate special for silane modified polyether sealant and a preparation method thereof.
Background
The silane modified polyether sealant (MS sealant for short) is a high-performance environment-friendly sealant prepared by taking silyl-terminated polyether (polyether is taken as a main chain, and both ends of the silyl-terminated polyether are terminated by siloxane) as a basic polymer. Because of their low surface energy and high permeability, the silane-terminated polyethers provide MS sealants having good wetting properties on many inorganic, metallic and plastic substrates, and thus provide good adhesion to such substrates. Meanwhile, the MS sealant has very low content of volatile organic compounds (TVOC) in the moisture curing process, and is more environment-friendly than the traditional polyurethane sealant.
However, when the MS sealant is applied to the outer wall of a building, its surface is easily adhered to dust or solid waste in the environment with the lapse of time, resulting in a great problem in its appearance. The nano calcium carbonate is the most commonly used filler in the MS sealant, and can effectively improve the thixotropic property, the reinforcing property and the heat resistance of a sealant system. However, since the nano calcium carbonate product is usually surface-modified by fatty acid or its salt, the oily substance on the surface of the nano calcium carbonate product will gradually separate out when the nano calcium carbonate product is used in an MS sealant in outdoor use, which will further aggravate the problem of appearance pollution of the MS sealant.
CN 109082245A discloses a method for preparing nano calcium carbonate for single-component MS glue, which adopts two modifiers to modify the nano calcium carbonate, one modifier is a mixture of polypropylene glycol, ammonium bicarbonate and oleic acid, and the other modifier is C12～C18The nano calcium carbonate product prepared by the method can solve the problem that the indexes such as moisture, oil absorption, whiteness, dispersion, reinforcement and the like cannot be considered when the traditional nano calcium carbonate is used for single-component MS glue, but the problem that the glue body is polluted by the environment in the use process of the MS glue cannot be solved because the modifier is mainly fatty acid.
CN 109628045A discloses a nano calcium carbonate for silane modified polyether sealant, which is prepared by firstly carrying out primary modification on nano calcium carbonate by using a sodium abietate solution and then carrying out secondary modification by using a mixed modifier consisting of a coupling agent KH602 and tung oil, and finally obtaining a nano calcium carbonate product for silane modified polyether sealant.
In conclusion, the nano calcium carbonate capable of effectively improving the outdoor stain resistance of the MS glue does not exist at present, so that the development of the nano calcium carbonate product has very important significance.
The foregoing merely provides background information related to the present invention and does not necessarily constitute prior art.
Disclosure of Invention
The invention aims to provide nano calcium carbonate special for silane modified polyether sealant and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the special nano calcium carbonate for the silane modified polyether sealant comprises the following steps:
1) calcining limestone to prepare calcium oxide, and adding water for reaction to obtain calcium hydroxide coarse slurry;
2) sieving the calcium hydroxide coarse pulp and then aging to obtain calcium hydroxide fine pulp;
3) introducing lime kiln gas into the calcium hydroxide fine slurry, and performing carbonization reaction until the pH value of the reaction system is reduced to below 7.0 to obtain nano calcium carbonate slurry I;
4) adding strong acid with 0.3-0.8% of the dry basis weight of the nano calcium carbonate into the nano calcium carbonate slurry I for reaction to obtain nano calcium carbonate slurry II;
5) c is to be14～C20Heating the mixture of the linear alkyl diacid and the terephthalic acid to a molten state, introducing ammonia gas, performing ammoniation reaction, adding ethanol solution of metallic nickel and KOH, and performing esterification reaction to obtain a modifier;
6) adding a modifier accounting for 3.0-6.0 percent of the dry basis weight of the nano calcium carbonate into the nano calcium carbonate slurry II for modification, and then dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
Preferably, the limestone in the step 1) is limestone with calcium carbonate content more than or equal to 97 percent.
Preferably, the calcination in step 1) is carried out at a temperature of 1000 ℃ to 1200 ℃.
Preferably, the calcination of step 1) is carried out in a shaft kiln.
Preferably, the mass ratio of the calcium oxide to the water in the step 1) is 1: 4-6.
Preferably, the sieving in step 2) is sequentially through 100 meshes, 200 meshes and 325 meshes of vibrating sieves.
Preferably, the aging time of the step 2) is 48-96 h.
Preferably, the specific gravity of the calcium hydroxide fine slurry in the step 2) is 1.050-1.060.
Preferably, the volume concentration of the carbon dioxide in the lime kiln gas in the step 3) is more than or equal to 25%.
Preferably, the lime kiln gas in the step 3) is obtained by purifying tail gas generated in the process of calcining limestone in a vertical kiln.
Preferably, the carbonization reaction in step 3) is carried out at 18 to 23 ℃.
Preferably, the specific surface area of the nano calcium carbonate in the nano calcium carbonate slurry I in the step 3) is 20m2/g～25m2/g。
Preferably, the strong acid in step 4) is at least one of phosphoric acid, hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the mass fraction of the strong acid in the step 4) is less than or equal to 10 percent.
Preferably, the nano calcium carbonate in the nano calcium carbonate slurry II in the step 4) has a porosity (measured by mercury intrusion) of 70-85%. The low porosity of the nano calcium carbonate can lead to the weakening of the adsorbability of the nano calcium carbonate, and the high porosity can lead to the difficulty in processing the nano calcium carbonate in an MS sealant system.
Preferably, the ammoniation reaction in the step 5) is carried out at the temperature of 100-120 ℃ and the pressure of 1.4-1.6 MPa, and the reaction time is 2-4 h.
Preferably, the addition amount of the metallic nickel in the step 5) is 0.008% -0.012% of the mass of the ammoniation reaction product.
Preferably, the addition amount of the ethanol solution of KOH in the step 5) is 25 to 35 percent of the mass of the ammoniation reaction product.
Preferably, the mass fraction of the ethanol solution of KOH in the step 5) is 15-25%.
Preferably, the esterification reaction in the step 5) is carried out at the temperature of 140-160 ℃ and under the pressure of 2.0-3.0 MPa, and the reaction time is 0.5-1 h.
Preferably, step 5) said C14～C20The mass ratio of the linear alkyl diacid to the terephthalic acid is 1: 0.4-0.8. C14～C20The linear alkyl diacid has too high proportion, is separated out too obviously in the later application of the MS sealant, and cannot reach the expected anti-fouling effect, while the terephthalic acid has too high proportion, and the processability and thixotropic property of the MS sealant cannot be ensured.
Preferably, step 5) said C14～C20The linear alkyl diacid of (a) is at least one of tetradecyl diacid, hexadecyl diacid, octadecyl diacid and eicosyl diacid. C14～C20The number of the C atoms of the alkyl chain in the linear alkyl diacid can not be lower than 14, otherwise the linear alkyl diacid is easy to precipitate in the outdoor use process, and the number of the C atoms can not exceed 20, otherwise the processability of the nano calcium carbonate product in the MS sealant production process is too poor.
Preferably, in the modifying agent in the step 5), the mass of carboxyl is 5-10%, the content of amino is 55-70%, and the content of ester group is 25-35% (by C)14～C20The amount of the total material of the terminal carboxyl groups in the linear alkyl diacid and the terephthalic acid of (a) is 100%). The low carboxyl content can lead to insufficient chemical anchoring amount of the modifier on the surface of the nano calcium carbonate and easy precipitation, and the high carboxyl content can lead to the content of hydrophilic functional groups such as amino, ester and the likeAnd the MS sealant is not beneficial to achieving the anti-pollution effect. The amino content is too low to achieve effective adhesion and anti-pollution effects, and the amino content is too high to cause poor compatibility of the calcium carbonate and the MS sealant, which is not beneficial to improving the mechanical property of the MS sealant. Too low ester group content is not beneficial to the compatibility and the anti-fouling effect of the nano calcium carbonate and the MS sealant, and too high ester group content can cause the adhesion of the MS sealant to be influenced.
Preferably, the modification in the step 6) is carried out at the temperature of 80-95 ℃, and the modification time is 60-120 min.
The invention has the beneficial effects that: the nano calcium carbonate special for the silane modified polyether sealant has good compatibility and dispersibility in the MS sealant, can effectively improve the basic performances of the MS sealant such as thixotropic property, reinforcing property, bonding property and the like, and can also effectively improve the pollution resistance of the MS sealant in the outdoor use process.
Drawings
FIG. 1 is an SEM image of nano calcium carbonate specially used for silane modified polyether sealant in example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
the preparation method of the nano calcium carbonate special for the silane modified polyether sealant comprises the following steps:
1) adding limestone with calcium carbonate content of 97.6% into a vertical kiln, calcining at 1200 ℃ to prepare calcium oxide, and adding water according to the mass ratio of the calcium oxide to the water of 1:5 to carry out digestion reaction to obtain calcium hydroxide coarse slurry;
2) sequentially passing the calcium hydroxide coarse slurry through vibrating screens of 100 meshes, 200 meshes and 325 meshes, and aging for 72h to obtain calcium hydroxide fine slurry (the specific gravity is 1.050);
3) transferring the calcium hydroxide fine slurry into a stirring kettle, introducing lime kiln gas (obtained by purifying tail gas formed in the process of calcining limestone in a vertical kiln) with the volume concentration of carbon dioxide of 32%, and carrying out carbonization reaction at 18 ℃ until the pH value of a reaction system is reduced to below 7.0 to obtain nano calcium carbonate slurryI (surface area of nano calcium carbonate is 24.8 m)2/g)；
4) Adding a phosphoric acid solution (the mass fraction is 8%) accounting for 0.8% of the dry basis mass of the nano calcium carbonate into the nano calcium carbonate slurry I, and stirring for 15min to obtain nano calcium carbonate slurry II (the porosity of the nano calcium carbonate is 78.5%);
5) adding hexadecyl diacid and terephthalic acid with the mass ratio of 1:0.4 into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammonification reaction for 2 hours under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammonification reaction to be about 70%, transferring the product of the ammonification reaction into a high-pressure reaction kettle, adding metallic nickel with the mass of 0.01% of that of the ammonification reaction product and an ethanol solution (the mass fraction is 20%) of KOH with the mass of 30% of that of the ammonification reaction product, carrying out esterification reaction for 0.8 hour under the conditions of 150 ℃ and 2.5MPa, and obtaining a modifier (the content of carboxyl is 8.3%, the content of amino is 60.8%, the content of ester group is 30.9%, and the total amount of terminal carboxyl groups in the hexadecyl diacid and the terephthalic acid is 100%);
6) and transferring the nano calcium carbonate slurry II into an activation kettle, adding a modifier accounting for 6.0 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
Example 2:
the preparation method of the nano calcium carbonate special for the silane modified polyether sealant comprises the following steps:
1) adding limestone with calcium carbonate content of 97.3% into a vertical kiln, calcining at 1200 ℃ to prepare calcium oxide, and adding water according to the mass ratio of the calcium oxide to the water of 1:5 to carry out digestion reaction to obtain calcium hydroxide coarse slurry;
2) sequentially passing the calcium hydroxide coarse pulp through vibrating screens of 100 meshes, 200 meshes and 325 meshes, and aging for 72h to obtain calcium hydroxide fine pulp (the specific gravity is 1.055);
3) transferring the calcium hydroxide fine slurry into a stirring kettle, introducing lime kiln gas (obtained by purifying tail gas formed in the process of calcining limestone in a vertical kiln) with the volume concentration of carbon dioxide of 30%, and performing carbonization reaction at 20 ℃ until the calcium hydroxide fine slurry is stirredUntil the pH value of the reaction system is reduced to below 7.0, and nano calcium carbonate slurry I is obtained (the surface area of the nano calcium carbonate is 22.3 m)2/g)；
4) Adding a sulfuric acid solution (the mass fraction is 8%) accounting for 0.5% of the dry basis mass of the nano calcium carbonate into the nano calcium carbonate slurry I, and stirring for 15min to obtain nano calcium carbonate slurry II (the porosity of the nano calcium carbonate is 71.3%);
5) adding octadecyl diacid and terephthalic acid in a mass ratio of 1:0.6 into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammonification reaction for 3h under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammonification reaction to be about 75%, transferring the product of the ammonification reaction into a high-pressure reaction kettle, adding metallic nickel accounting for 0.01% of the mass of the product of the ammonification reaction and an ethanol solution (the mass fraction is 20%) of KOH accounting for 30% of the mass of the product of the ammonification reaction, and carrying out esterification reaction for 0.5h under the conditions of 150 ℃ and 2.5MPa to obtain a modifier (the content of carboxyl is 5.2%, the content of amino is 68.9%, the content of ester group is 25.9%, and the total amount of terminal carboxyl groups in the octadecyl diacid and the terephthalic acid is 100%);
6) and transferring the nano calcium carbonate slurry II into an activation kettle, adding a modifier accounting for 4.5 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
Example 3:
the preparation method of the nano calcium carbonate special for the silane modified polyether sealant comprises the following steps:
1) adding limestone with calcium carbonate content of 97.8% into a vertical kiln, calcining at 1200 ℃ to prepare calcium oxide, and adding water according to the mass ratio of the calcium oxide to the water of 1:5 to carry out digestion reaction to obtain calcium hydroxide coarse slurry;
2) sequentially passing the calcium hydroxide coarse pulp through vibrating screens of 100 meshes, 200 meshes and 325 meshes, and aging for 72h to obtain calcium hydroxide fine pulp (the specific gravity is 1.060);
3) transferring the calcium hydroxide fine slurry into a stirring kettle, and introducing lime kiln gas (formed in the process of calcining limestone in a vertical kiln) with the carbon dioxide volume concentration of 25 percentPurifying the resultant tail gas), performing carbonization reaction at 20 deg.C until the pH of the reaction system is reduced to below 7.0 to obtain nano calcium carbonate slurry I (the surface area of nano calcium carbonate is 20.5 m)2/g)；
4) Adding a sulfuric acid solution (the mass fraction is 8%) accounting for 0.7% of the dry basis mass of the nano calcium carbonate into the nano calcium carbonate slurry I, and stirring for 15min to obtain nano calcium carbonate slurry II (the porosity of the nano calcium carbonate is 83.2%);
5) adding eicosyl diacid, octadecyl diacid and terephthalic acid with the mass ratio of 0.2:0.8:0.6 into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out 2h ammonification reaction under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammonification reaction to be about 60%, transferring the ammonification reaction product into a high-pressure reaction kettle, adding metallic nickel with the mass of 0.01% of the ammonification reaction product and ethanol solution (the mass fraction is 20%) of KOH with the mass of 30% of the ammonification reaction product, carrying out 0.5h esterification reaction under the conditions of 150 ℃ and 2.5MPa, and obtaining a modifier (the content of carboxyl is 9.4%, the content of amino is 57.4%, the content of ester group is 33.2%, and the total amount of terminal carboxyl in the eicosyl diacid, the octadecyl diacid and the terephthalic acid is 100%);
6) and transferring the nano calcium carbonate slurry II into an activation kettle, adding a modifier accounting for 3.0 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
Example 4:
the preparation method of the nano calcium carbonate special for the silane modified polyether sealant comprises the following steps:
1) adding limestone with calcium carbonate content of 97.8% into a vertical kiln, calcining at 1200 ℃ to prepare calcium oxide, and adding water according to the mass ratio of the calcium oxide to the water of 1:5 to carry out digestion reaction to obtain calcium hydroxide coarse slurry;
2) sequentially passing the calcium hydroxide coarse pulp through vibrating screens of 100 meshes, 200 meshes and 325 meshes, and aging for 72h to obtain calcium hydroxide fine pulp (the specific gravity is 1.058);
3) refining calcium hydroxideTransferring the slurry into a stirring kettle, introducing lime kiln gas (obtained by purifying tail gas formed in the process of calcining limestone in a vertical kiln) with the carbon dioxide volume concentration of 29%, and performing carbonization reaction at 20 ℃ until the pH value of a reaction system is reduced to below 7.0 to obtain nano calcium carbonate slurry I (the surface area of nano calcium carbonate is 21.3 m)2/g)；
4) Adding a nitric acid solution (the mass fraction is 8%) accounting for 0.3% of the dry basis mass of the nano calcium carbonate into the nano calcium carbonate slurry I, and stirring for 15min to obtain nano calcium carbonate slurry II (the porosity of the nano calcium carbonate is 70.6%);
5) adding eicosyl diacid, tetradecyl diacid and terephthalic acid with the mass ratio of 0.3:0.7:0.5 into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammonification reaction for 2.2h under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammonification reaction to be about 65%, transferring the ammonification reaction product into a high-pressure reaction kettle, adding metallic nickel with the mass of 0.01% of the ammonification reaction product and ethanol solution (the mass fraction is 20%) of KOH with the mass of 30% of the ammonification reaction product, carrying out esterification reaction for 0.8h under the conditions of 150 ℃ and 2.5MPa, and obtaining a modifier (the content of carboxyl is 7.8%, the content of amino is 59.6%, the content of ester group is 32.6%, and the total amount of terminal carboxyl groups in the eicosyl diacid, the tetradecyl diacid and the terephthalic acid is 100%);
6) and transferring the nano calcium carbonate slurry II into an activation kettle, adding a modifier accounting for 3.8 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
Comparative example 1:
the preparation method of the modified nano calcium carbonate comprises the following steps:
the nano calcium carbonate slurry (nano calcium carbonate slurry I in example 4, the surface area of nano calcium carbonate is 21.3m2And/g) adding the mixture into an activation kettle, adding sodium stearate accounting for 3.8 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
Comparative example 2:
the preparation method of the modified nano calcium carbonate comprises the following steps:
adding the nano calcium carbonate slurry (nano calcium carbonate slurry I in the embodiment 4) into an activation kettle, adding a modifier (the modifier in the embodiment 4) accounting for 3.8 percent of the dry mass of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
Comparative example 3:
the preparation method of the modified nano calcium carbonate comprises the following steps:
1) adding eicosyl diacid, tetradecyl diacid and terephthalic acid with the mass ratio of 0.3:0.7:0.5 into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammonification reaction for 1.0 hour under the conditions of 110 ℃ and 0.8MPa, controlling the conversion rate of the ammonification reaction to be about 25 percent, transferring the ammonification reaction product into a high-pressure reaction kettle, adding metallic nickel with the mass of 0.01 percent of the ammonification reaction product and ethanol solution (the mass fraction is 20 percent) of KOH with the mass of 30 percent of the ammonification reaction product, and carrying out esterification reaction for 0.8 hour under the conditions of 150 ℃ and 2.5MPa to obtain a modifier (the content of carboxyl is 42.4 percent, the content of amino is 19.5 percent, the content of ester group is 38.1 percent, and the total amount of terminal carboxyl groups in the eicosyl diacid, the tetradecyl diacid and the terephthalic acid is 100 percent);
2) adding the nano calcium carbonate slurry (the nano calcium carbonate slurry I in the embodiment 4) into an activation kettle, adding a modifier accounting for 3.8 percent of the dry mass of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
Comparative example 4:
the preparation method of the modified nano calcium carbonate comprises the following steps:
1) adding dodecyl diacid into an ammonification reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammonification reaction for 2.2h under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammonification reaction to be about 65%, transferring the product of the ammonification reaction into a high-pressure reaction kettle, adding metal nickel accounting for 0.01% of the mass of the product of the ammonification reaction and KOH ethanol solution accounting for 30% of the mass of the product of the ammonification reaction (the mass fraction is 20%), carrying out esterification reaction for 0.8h under the conditions of 150 ℃ and 2.5MPa, and obtaining a modifier (the content of carboxyl is 8.2%, the content of amino is 63.3%, the content of ester group is 28.5%, and the amount of carboxyl-terminated substances in the dodecyl diacid is 100%);
2) adding the nano calcium carbonate slurry (the nano calcium carbonate slurry I in the embodiment 4) into an activation kettle, adding a modifier accounting for 3.8 percent of the dry mass of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
Comparative example 5:
the preparation method of the modified nano calcium carbonate comprises the following steps:
1) adding terephthalic acid into an ammoniation reaction device, heating and melting, introducing excessive ammonia gas, carrying out ammoniation reaction for 2.2h under the conditions of 110 ℃ and 1.5MPa, controlling the conversion rate of the ammoniation reaction to be about 65%, transferring the product of the ammoniation reaction into a high-pressure reaction kettle, adding metal nickel accounting for 0.01% of the mass of the ammoniation reaction product and KOH ethanol solution accounting for 30% of the mass of the ammoniation reaction product (the mass fraction is 20%), carrying out esterification reaction for 0.8h under the conditions of 150 ℃ and 2.5MPa, and obtaining a modifier (the content of carboxyl is 5.3%, the content of amino is 61.4%, the content of ester group is 33.3%, and the amount of the carboxyl-terminated substance in the terephthalic acid is 100%);
2) adding the nano calcium carbonate slurry (the nano calcium carbonate slurry I in the embodiment 4) into an activation kettle, adding a modifier accounting for 3.8 percent of the dry mass of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
Comparative example 6:
the preparation method of the modified nano calcium carbonate comprises the following steps:
1) adding a nitric acid solution (with a mass fraction of 8%) with a dry basis mass of 0.3% of the nano calcium carbonate into the nano calcium carbonate slurry (nano calcium carbonate slurry I in example 4), and stirring for 15min to obtain nano calcium carbonate slurry II (with a porosity of 70.6% of nano calcium carbonate);
2) and transferring the nano calcium carbonate slurry II into an activation kettle, adding sodium stearate accounting for 3.0 percent of the dry basis weight of the nano calcium carbonate, stirring for 80min at 85 ℃, and then dehydrating, drying and crushing to obtain the modified nano calcium carbonate.
And (3) performance testing:
1) the Scanning Electron Microscope (SEM) image of the nano calcium carbonate specially used for the silane modified polyether sealant in example 1 is shown in fig. 1.
As can be seen from fig. 1: the nano calcium carbonate special for the silane modified polyether sealant in the embodiment 1 has uniform particle size, and the particle size is mainly concentrated to about 100 nm.
In addition, SEM tests show that the morphology of the nano calcium carbonate special for the silane modified polyether sealant in the embodiments 2-4 is highly similar to that of the nano calcium carbonate special for the silane modified polyether sealant in the embodiment 4, and the particle size of the nano calcium carbonate is very close to that of the nano calcium carbonate.
2) The silane modified polyether sealant is prepared by respectively using the nano calcium carbonate special for the silane modified polyether sealant in the embodiments 1 to 4 and the modified nano calcium carbonate in the comparative examples 1 to 6 according to the formula in the table 1, and then the silane modified polyether sealant is sequentially prepared into sample strips 1 to 4 and comparative sample strips 1 to 6 for performance test, wherein the test results are shown in the table 2:
TABLE 1 formulation of silane modified polyether sealant
Note:
silyl-terminated polyether (S303H): japanese Kochia Co;
dehydrating agent A-171: jie chemical technology, Inc. in Guangzhou City;
catalyst chelated organotin: japan Bell chemical company.
TABLE 2 Performance test results for splines 1-4 and comparative splines 1-6
Note:
melt index, tensile strength and elongation at break: the test is carried out according to the determination of the tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber, and an I-shaped part with the sample specification of 12mm multiplied by 50mm is cured for 28 days at 23 ℃ and 55% RH environment;
surface fouling property: injecting the silane modified polyether sealant into a curing mold with the specification of 50mm multiplied by 2mm, then placing the curing mold in an outdoor condition for natural curing for 30d, observing the anti-pollution effect, and evaluating the pollution property: :: not less than 0 dust particles and not more than 10 dust particles; :: 10 particles of dust are less than or equal to 20 particles; :: 20 particles of dust are less than or equal to 35 particles; :: 35 particles of dust are less than or equal to 55 particles; : (i): (ii): dust particles > 55.
As can be seen from Table 2: the silane modified polyether sealant added with the special nano calcium carbonate for the silane modified polyether sealant of the embodiment 1-4 can effectively solve the problem of surface pollution of the silane modified polyether sealant while keeping the conventional performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant is characterized by comprising the following steps:
1) calcining limestone to prepare calcium oxide, and adding water for reaction to obtain calcium hydroxide coarse slurry;
2) sieving the calcium hydroxide coarse pulp and then aging to obtain calcium hydroxide fine pulp;
3) introducing lime kiln gas into the calcium hydroxide fine slurry, and performing carbonization reaction until the pH value of the reaction system is reduced to below 7.0 to obtain nano calcium carbonate slurry I;
4) adding strong acid with 0.3-0.8% of the dry basis weight of the nano calcium carbonate into the nano calcium carbonate slurry I for reaction to obtain nano calcium carbonate slurry II;
5) c is to be14～C20Heating the mixture of the linear alkyl diacid and the terephthalic acid to a molten state, introducing ammonia gas, performing ammoniation reaction, adding ethanol solution of metallic nickel and KOH, and performing esterification reaction to obtain a modifier;
6) adding a modifier accounting for 3.0-6.0 percent of the dry basis weight of the nano calcium carbonate into the nano calcium carbonate slurry II for modification, and then dehydrating, drying and crushing to obtain the special nano calcium carbonate for the silane modified polyether sealant.
2. The preparation method of the nano calcium carbonate special for the silane modified polyether sealant as claimed in claim 1, which is characterized in that: the specific surface area of the nano calcium carbonate in the nano calcium carbonate slurry I in the step 3) is 20m2/g～25m2/g。
3. The preparation method of the nano calcium carbonate special for the silane modified polyether sealant as claimed in claim 1, which is characterized in that: and 4) the strong acid is at least one of phosphoric acid, hydrochloric acid, sulfuric acid and nitric acid.
4. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant according to any one of claims 1 to 3, which is characterized by comprising the following steps: the porosity of the nano calcium carbonate in the nano calcium carbonate slurry II in the step 4) is 70-85%.
5. The preparation method of the nano calcium carbonate special for the silane modified polyether sealant as claimed in claim 1, which is characterized in that: the ammoniation reaction in the step 5) is carried out at the temperature of 100-120 ℃ and the pressure of 1.4-1.6 MPa, and the reaction time is 2-4 h.
6. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant according to any one of claims 1 to 3 and 5, which is characterized by comprising the following steps: the esterification reaction in the step 5) is carried out at the temperature of 140-160 ℃ and the pressure of 2.0-3.0 MPa, and the reaction time is 0.5-1 h.
7. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant according to any one of claims 1 to 3 and 5, which is characterized by comprising the following steps: step 5) said C14～C20The mass ratio of the linear alkyl diacid to the terephthalic acid is 1: 0.4-0.8.
8. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant according to any one of claims 1 to 3 and 5, which is characterized by comprising the following steps: in the step 5), the content of carboxyl in the modifier is 5-10%, the content of amino is 55-70%, and the content of ester group is 25-35%.
9. The preparation method of the special nano calcium carbonate for the silane modified polyether sealant according to any one of claims 1 to 3 and 5, which is characterized by comprising the following steps: the modification of the step 6) is carried out at the temperature of 80-95 ℃, and the modification time is 60-120 min.
10. The special nano calcium carbonate for the silane modified polyether sealant is characterized by being prepared by the method of any one of claims 1 to 9.
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