CN116812940A - Preparation method of silicate solution with high modulus and high stability and silicate solution - Google Patents
Preparation method of silicate solution with high modulus and high stability and silicate solution Download PDFInfo
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- CN116812940A CN116812940A CN202310756420.1A CN202310756420A CN116812940A CN 116812940 A CN116812940 A CN 116812940A CN 202310756420 A CN202310756420 A CN 202310756420A CN 116812940 A CN116812940 A CN 116812940A
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- silicate solution
- modulus
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 162
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 33
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 36
- 238000001879 gelation Methods 0.000 abstract description 13
- 150000004760 silicates Chemical class 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 125000003827 glycol group Chemical group 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 21
- 239000004111 Potassium silicate Substances 0.000 description 20
- 235000019353 potassium silicate Nutrition 0.000 description 20
- 229910052913 potassium silicate Inorganic materials 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 239000004110 Zinc silicate Substances 0.000 description 6
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 235000019352 zinc silicate Nutrition 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
- C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a preparation method of a silicate solution with high modulus and high stability and the silicate solution, which comprises the following steps: step S1: preparing a high-modulus silicate prefabricated solution by adopting a two-step method; step S2: adding a modifier into the silicate prefabricated solution obtained in the step S1; obtaining silicate solution with high modulus and high stability; wherein the modifier is polyethylene glycol and/or silicone-acrylate emulsion. According to the invention, polyethylene glycol and silicone-acrylic emulsion are used as a modifier to prepare silicate solution, and hydroxyl groups of polyethylene glycol chain segments can form hydrogen bonds with hydroxyl groups on the surfaces of silicate colloidal particles, so that silicate gelation is prevented, and the storage stability of the silicate solution is enhanced; the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of silicate shop primer, the storage stability of silicate solution can be improved by adding the silicone-acrylic emulsion, the gelation process of the modified silicate solution is slowed down, and the modified silicate solution has high modulus and high storage stability.
Description
Technical Field
The invention relates to the technical field of chemical materials, in particular to a preparation method of a silicate solution with high modulus and high stability and the silicate solution.
Background
In the construction process of marine equipment such as large ships, ocean platforms and the like, the surface of steel is usually required to be temporarily protected by coating workshop primer, so that the steel is prevented from being corroded in a large amount. Because the traditional solvent type shop primer has the problems of low volume solid content and exceeding VOC (volatile organic compounds, volatile organic compound) content, the marine engineering equipment mainly uses the inorganic zinc silicate shop primer, and the inorganic zinc silicate shop primer has the excellent properties of low VOC content, high solid content, good workability, quick drying property and the like, so the traditional solvent type shop primer is widely applied.
The component A of the inorganic zinc silicate shop primer mainly consists of silicate solution, and the higher the modulus of silicate is, the better the film forming performance of the shop primer is; however, the higher the modulus of the silicate, the poorer the storage stability of the silicate solution. Therefore, the inorganic zinc silicate shop primer with high modulus and storage stability has considerable application prospect and market potential.
Chinese patent CN114180590a discloses a preparation method of silicate aqueous solution, in which an active silicic acid-containing solution obtained by reacting fluosilicic acid with calcium carbonate is used as a silicon source, sodium hydroxide, potassium hydroxide, or aqueous solution of lithium hydroxide is used as an alkali source, the two are reacted at room temperature and normal pressure to obtain a corresponding silicate dilute solution product, and then the dilute solution is concentrated by membrane filtration to obtain the product meeting the market demand. The silicate preparation method provided by the invention has low energy consumption, heating and pressurizing are not needed, and the prepared silicate product has high modulus, and the modulus can be controlled between 1 and 12 according to the needs. However, this method does not ensure the storage stability of the high modulus silicate solution.
Chinese patent CN1261335a discloses a suspension with high storage stability containing silicate aqueous solution and filler, which is improved by adding inert particles such as zeolite, graphite and carbon black to the silicate solution. However, the method has good effect on silicate solutions with modulus ranging from 2.8 to 4.2, and can not ensure the storage stability of silicate solutions with higher modulus.
Disclosure of Invention
The problem to be solved by the invention is that in the prior art, silicate solution with high modulus is easy to gel and has poor storage stability.
The invention discloses a preparation method of a silicate solution with high modulus and high stability, which comprises the following steps:
step S1: preparing a high-modulus silicate prefabricated solution by adopting a two-step method;
step S2: adding a modifier into the silicate prefabricated solution obtained in the step S1; obtaining silicate solution with high modulus and high stability;
wherein the modifier is polyethylene glycol and/or silicone-acrylate emulsion.
The particle size of silicate colloidal particles in the silicate solution can be effectively controlled by a two-step method, so that the high-modulus silicate solution with uniform particle size of silicate colloidal particles is prepared, the reduction of the storage stability of the silicate solution due to the large particle size of silicate colloidal particles is avoided, in addition, the hydroxyl groups of polyethylene glycol chain segments can form hydrogen bonds with the hydroxyl groups on the surface of silicate colloidal particles, the occurrence of silicate gelation is prevented, and the storage stability of the silicate solution is enhanced; the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of silicate shop primer and can also improve the storage stability of silicate solution.
Further, the silicate solution comprises the following raw material components:
the weight components are as follows: 100-300 parts of silica sol, 10-30 parts of alkali metal hydroxide aqueous solution, 1-35 parts of polyvinyl alcohol and 1-35 parts of silicone-acrylic emulsion;
wherein the mass fraction of the silica sol is 10% -35%.
Through the arrangement, when the silicate solution is prepared, the high-modulus silicate solution is modified through the addition of the polyvinyl alcohol and/or the silicone-acrylic emulsion, the gelation speed of the silicate solution is obviously slowed down, and the storage stability of the silicate solution is improved.
Further, the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
Further, the two-step method of step S1 includes:
step S11: weighing SiO 2 Heating silica sol with a mass of a; weighing alkali metal hydroxide with the mass of b, dissolving the alkali metal hydroxide in deionized water with the mass of c to form an alkali metal hydroxide aqueous solution with the mass of d, weighing the alkali metal hydroxide aqueous solution with the mass of e, slowly and uniformly dripping the alkali metal hydroxide aqueous solution into silica sol, and continuously stirring to obtain silica sol prefabricated liquid;
step S12: re-weighing SiO 2 The silica sol with the mass f is added into the silica sol prefabricated solution obtained in the step S1 at a constant speed with the rest alkali metal hydroxide solution in the step S11, and the silica sol is continuously stirred to obtain a high-modulus silicate prefabricated solution;
wherein e < d.
Through the arrangement, the low-modulus silica sol prefabricated liquid with a lower modulus is prepared in the step S11, the low-modulus silica sol prefabricated liquid prepared in the step S11 is used as seeds, and the high-modulus silicate solution is prepared in a gradual dropwise adding mode, so that the particle size of silicate colloidal particles in the obtained silicate solution is more uniform, and the generation of large-particle-size silicate colloidal particles is effectively prevented, so that the storage stability of the silicate solution is reduced.
Further, in step S11, the ratio of e/d is in the range of 0.75 to 0.85.
Through the arrangement, the low-modulus silica sol prefabricated liquid with proper modulus is formed in the step S11, so that the high-modulus silicate solution with uniform granularity is gradually formed in the second dripping process, and the excessive granularity of silicate colloidal particles is avoided.
Further, in step S11, the dropping speed of the alkali metal hydroxide aqueous solution is lower than 15ml/h; in step S12, the silica sol has a drop velocity of less than 15ml/h, and the alkali metal hydroxide solution has a drop velocity of less than 5ml/h.
Through the arrangement, the slow reaction in the preparation process of the high-modulus silicate solution can be ensured, so that the uniform and fine silicate colloidal particle size is formed, and the condition of overlarge silicate colloidal particle size is avoided.
Further, in the silicate solution, the modulus of silicate is:
and n is more than or equal to 5.
The silicate solution prepared by the preparation method has high modulus, and meanwhile, has relatively uniform and fine silicate colloidal particle size, and can effectively improve the storage stability. And the modulus of the finished silicate solution can be adjusted by controlling a, b and f so as to prepare according to the requirements.
Further, step S2 includes:
step S21: adding polyethylene glycol according to the mass components, and stirring for a first preset time; and/or dropwise adding the silicon-acrylic solution at a constant speed according to the mass components, and stirring for a second preset time.
For the high-modulus silicate solution, the initial particle size is smaller, polyethylene glycol is added to improve the dispersibility of silicate particles, and collision contact among silicate colloid particles is delayed, so that silicate gelation is delayed, and the effect of enhancing the storage stability of the silicate solution is achieved; the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of silicate shop primer and can also improve the storage stability of silicate solution.
Further, the silicone-acrylate emulsion is a silicone-acrylate emulsion containing an organosiloxane component and an acrylic component.
The invention also discloses a silicate solution, which is prepared by adopting the preparation method of the silicate solution with high modulus and high stability.
Compared with the original silicate solution, the modified silicate solution has the advantages that the gelation process of the modified silicate solution is slowed down under the combined action of the polyvinyl alcohol and the silicone-acrylic emulsion, the silicate solution has high modulus and high storage stability, and meanwhile, the silicate shop primer is endowed with high temperature resistance, and the silicate shop primer is suitable for preparation and application of inorganic silicate shop primer.
Compared with the prior art, the preparation method of the silicate solution with high modulus and high stability and the silicate solution have the following advantages:
according to the invention, polyethylene glycol and silicone-acrylic emulsion are used as a modifier to prepare silicate solution, and hydroxyl groups of polyethylene glycol chain segments can form hydrogen bonds with hydroxyl groups on the surfaces of silicate colloidal particles, so that silicate gelation is prevented, and the storage stability of the silicate solution is enhanced; in addition, the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of the silicate shop primer, the storage stability of the silicate solution can be improved by adding the silicone-acrylic emulsion, the gelation process of the modified silicate solution is slowed down, the high modulus and the high storage stability can be achieved, and meanwhile, the high temperature resistance characteristic required by the silicate shop primer is provided. The preparation method provided by the invention is simple to operate, and the storage stability of the high-modulus silicate solution is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a potassium silicate solution of example 2 of the present invention and a modified potassium silicate solution of polyethylene glycol and silicone-acrylic emulsion prepared according to the preparation method of example 1;
FIG. 2 is a graph showing the particle size analysis of a potassium silicate solution according to example 2 of the present invention after standing for 1 month;
FIG. 3 is a graph showing the analysis of particle size of a potassium silicate solution prepared by the preparation method of example 2 of the present invention after standing for 1 month.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the described embodiments are some, but not all, embodiments of the invention. The specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The following describes a preparation method of a silicate solution with high modulus and high stability and a silicate solution according to an embodiment of the present invention in detail with reference to the accompanying drawings.
The invention provides a preparation method of a silicate solution with high modulus and high stability, which comprises the following steps:
step S1: preparing a high-modulus silicate prefabricated solution by adopting a two-step method;
step S2: adding a modifier into the silicate prefabricated solution obtained in the step S1; obtaining silicate solution with high modulus and high stability;
wherein the modifier is polyethylene glycol and/or silicone-acrylate emulsion.
In the prior art, colloidal particles with larger particle sizes are easy to appear in a silicate solution with high modulus, so that the gelation speed of the solution is increased, and the storage stability of the solution is seriously influenced; the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of silicate shop primer and can also improve the storage stability of silicate solution. The silicate solution obtained by the method has high modulus, good storage stability and high temperature resistance, and the inorganic zinc silicate shop primer prepared by the silicate solution has good film forming property and high temperature resistance protective property, and can give the inorganic zinc silicate shop primer a longer quality guarantee period.
In this example, the raw material components of the silicate solution include:
the weight components are as follows: 100-300 parts of silica sol, 10-30 parts of alkali metal hydroxide aqueous solution, 1-35 parts of polyvinyl alcohol and 1-35 parts of silicone-acrylic emulsion;
wherein the mass fraction of the silica sol is 10% -35%.
When silicate solutions with the corresponding mass fraction ranges are prepared, the silica sol with the same mass fraction is adopted. The alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide. Through the arrangement, when the silicate solution is prepared, the high-modulus silicate solution is modified through the addition of the polyvinyl alcohol and/or the silicone-acrylic emulsion, the gelation speed of the silicate solution is obviously slowed down, and the storage stability of the silicate solution is improved.
As an example of the present invention, the two-step method of step S1 includes:
step S11: weighing SiO 2 Heating silica sol with a mass of a; weighing alkali metal hydroxide with the mass of b, dissolving the alkali metal hydroxide in deionized water with the mass of c to form an alkali metal hydroxide aqueous solution with the mass of d, weighing the alkali metal hydroxide aqueous solution with the mass of e, slowly and uniformly dripping the alkali metal hydroxide aqueous solution into silica sol, and continuously stirring to obtain silica sol prefabricated liquid;
step S12: re-weighing SiO 2 The silica sol with the mass f is added into the silica sol prefabricated solution obtained in the step S1 at a constant speed with the rest alkali metal hydroxide solution in the step S11, and the silica sol is continuously stirred to obtain a high-modulus silicate prefabricated solution;
wherein e < d.
Through the arrangement, the low-modulus silica sol prefabricated liquid with a lower modulus is prepared in the step S11, the low-modulus silica sol prefabricated liquid prepared in the step S11 is used as seeds, and the high-modulus silicate solution is prepared in a gradual dropwise adding mode, so that the particle size of silicate colloidal particles in the obtained silicate solution is more uniform, and the generation of large-particle-size silicate colloidal particles is effectively prevented, so that the storage stability of the silicate solution is reduced. It should be noted that a and f may be equal or unequal. Wherein the first step of the two-step method is the method of step S11, and the second step is the method of step S12
As an alternative example, the ratio of e/d in step S11 ranges from 0.75 to 0.85.
Through the arrangement, the low-modulus silica sol prefabricated liquid with proper modulus is formed in the step S11, so that the high-modulus silicate solution with uniform granularity is gradually formed in the second dripping process, and the excessive granularity of silicate colloidal particles is avoided.
In this example, in step S11, the dropping speed of the aqueous alkali metal hydroxide solution is lower than 15ml/h; in step S12, the silica sol has a drop velocity of less than 15ml/h, and the alkali metal hydroxide solution has a drop velocity of less than 5ml/h.
Through the arrangement, the slow reaction in the preparation process of the high-modulus silicate solution can be ensured, so that the uniform and fine silicate colloidal particle size is formed, and the condition of overlarge silicate colloidal particle size is avoided.
Specifically, in this example, in the silicate solution, the modulus of silicate is:
and n is more than or equal to 5.
The silicate solution prepared by the preparation method has high modulus, and meanwhile, has relatively uniform and fine silicate colloidal particle size, and can effectively improve the storage stability. And the modulus of the finished silicate solution can be adjusted by controlling a, b and f so as to prepare according to the requirements.
As an example of the present invention, step S2 includes:
step S21: adding polyethylene glycol according to the mass components, and stirring for a first preset time; and/or dropwise adding the silicon-acrylic solution at a constant speed according to the mass components, and stirring for a second preset time.
It should be noted that, when the modifier includes polyethylene glycol and silicone-acrylic solution, the order of addition of the two is not limited, but after one of them is added, the other is added after the corresponding preset time is needed to be stirred and the corresponding preset time is continued to be stirred, if polyethylene glycol is added first, the silicone-acrylic solution is added after the first preset time is needed to be stirred and the second preset time is continued to be stirred; if the silicone-acrylic solution is added first, the polyethylene glycol is added after the second preset time is required to be stirred, and the first preset time is required to be continuously stirred, so that the silicate solution with high modulus and high stability required by the invention is obtained. Wherein the value range of the first preset time is 0.4-1h, preferably 0.5h, and the value range of the second preset time is 0.4-1h, preferably 0.5-1h. For the high-modulus silicate solution, the initial particle size is smaller, polyethylene glycol is added to improve the dispersibility of silicate particles, and collision contact among silicate colloid particles is delayed, so that silicate gelation is delayed, and the effect of enhancing the storage stability of the silicate solution is achieved; the silicone-acrylic emulsion can improve the high temperature resistance and weather resistance of silicate shop primer and can also improve the storage stability of silicate solution.
As one example thereof, the silicone-acrylic emulsion is a silicone-acrylic emulsion containing an organosiloxane component and an acrylic component. The silicone-acrylic emulsion is a commercially available common material and is not described and limited herein.
After the preparation of the high modulus and high stability silicate is completed, the potassium silicate modulus can be determined by adopting a titration method: 1g of potassium silicate solution was sucked up in a glass with a plastic tube. Adding deionized water 10ml for dissolution, adding methyl red-bromocresol3 drops of green mixed indicator are titrated by 0.5mol/L hydrochloric acid standard solution until the solution changes from blue-green to orange, and the reading V of the consumed hydrochloric acid standard solution is recorded 1 As shown in formula (1). Then, an excess of 48g/L sodium fluoride solution was added to the solution, so that the solution turned green again as in formula (2). Then titrating the hydrochloric acid standard solution with the concentration of 0.5mol/L to the end point of the redness of the wine, and recording the reading V of the hydrochloric acid standard solution consumed for the second time 2 As shown in formula (3).
K 2 O·mSiO 2 +2HCl+(m-2)H 2 O＝2KCl+mH 2 SiO 3 (1)
H 2 SiO 3 +6NaF+H 2 O＝Na 2 SiF 6 +4NaOH (2)
NaOH+HCl＝NaCl+H 2 O (3)
The modulus calculation formula is: n=0.5v 2/ V 1 . The modulus of the silicate solution after completion of the preparation can be examined in the above manner.
Example 1
The embodiment provides a preparation method of a potassium silicate solution with the mass fraction of 30% and the modulus of 6, which comprises the following steps:
(1) Firstly, 120g of 30% silica sol (0.6 mol) is weighed and heated; weighing 5.61g (0.1 mol) of potassium hydroxide, dissolving in 13.09g of deionized water, slowly and uniformly dripping 15g of potassium hydroxide solution into silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 120g of silica sol (0.6 mol) with the mass fraction of 30%, and simultaneously dripping 3.7g of potassium hydroxide solution remained in the first step into the silica sol at a constant speed, and continuously stirring in the process;
(3) Thirdly, adding polyethylene glycol into the potassium silicate solution according to the mass ratio, and continuously stirring for 0.5h;
(4) Fourthly, dropwise adding the silicone-acrylic emulsion at a constant speed according to the mass ratio, and continuously stirring for 0.5h;
finally, the high-modulus potassium silicate solution with the mass fraction of 30%, the modulus of 6 and high storage stability is obtained.
Example 2
The embodiment provides a preparation method of a potassium silicate solution with the mass fraction of 25% and the modulus of 5, which comprises the following steps:
(1) Firstly, weighing 120g of silica sol (0.5 mol) with the mass fraction of 25%, and heating; weighing 5.61g (0.1 mol) of potassium hydroxide, dissolving in 16.83g of deionized water, slowly and uniformly dripping 18g of potassium hydroxide solution into the silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 120g of silica sol (0.5 mol) with the mass fraction of 25%, and simultaneously dropwise adding 5.61g of potassium hydroxide solution into the silica sol at a constant speed with the rest 4.44g of potassium hydroxide solution in the first step, wherein the silica sol is continuously stirred in the process;
(3) Thirdly, adding 1.6g of polyethylene glycol into the potassium silicate solution, and continuously stirring for 0.5h;
(4) Fourth, adding 4.8g silicone-acrylic emulsion dropwise at a constant speed, and continuously stirring for 0.5h; finally, a potassium silicate solution with a modulus of 5 and high storage stability is obtained.
As shown in fig. 1 to 3, the left side of fig. 1 represents 0% of the potassium silicate solution without the modifier prepared in example 1, the right side represents 3% of the potassium silicate solution with high modulus and high storage stability prepared finally in example 1, and fig. 2 and 3 represent particle size analysis curves of the two potassium silicate solutions after standing for one month in fig. 1, wherein it can be seen that the silicate colloidal particle ratio of the unmodified silicate solution with the particle size exceeding 100 μm is greatly increased, the silicate solution modified by polyvinyl alcohol and silicone-acrylic emulsion does not have the silicate particle size greater than 100 μm after standing for one month, and the inorganic silicate resin gelation is significantly slowed down and the storage stability is greatly improved.
Example 3
The embodiment provides a preparation method of a potassium silicate solution with the mass fraction of 20% and the modulus of 7, which comprises the following steps:
(1) Firstly, weighing 210g of 20% silica sol (0.7 mol) by mass fraction, and heating; weighing 5.61g (0.1 mol) of potassium hydroxide, dissolving in 22.44g of deionized water, slowly and uniformly dripping 22g of potassium hydroxide solution into silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 210g of silica sol (0.7 mol) with the mass fraction of 20%, and simultaneously dripping the silica sol and the rest 6.05g of potassium hydroxide solution in the first step into the silica sol at a constant speed, and continuously stirring in the process;
(3) Thirdly, adding 4.0g of polyethylene glycol into the potassium silicate solution, and continuously stirring for 0.5h;
(4) Fourthly, adding 8.0g of silicone-acrylic emulsion dropwise at a constant speed, and continuously stirring for 1h; finally, a potassium silicate solution with a modulus of 7 and high storage stability is obtained.
Example 4
The embodiment provides a preparation method of a sodium silicate solution with the mass fraction of 30% and the modulus of 5, which comprises the following steps:
(1) Firstly, weighing 100g of 30% silica sol (0.5 mol) by mass fraction, and heating; weighing 4.0g (0.1 mol) of sodium hydroxide, dissolving in 9.33g of deionized water, slowly and uniformly dripping 11g of sodium hydroxide solution into silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 100g of silica sol (0.5 mol) with the mass fraction of 30%, and simultaneously dropwise adding 2.33g of sodium hydroxide solution 4 remained in the first step into the silica sol at a constant speed, and continuously stirring in the process;
(3) Thirdly, adding 2.0g of polyethylene glycol into the potassium silicate solution, and continuously stirring for 0.5h;
(4) Fourthly, adding 3.0g of silicone-acrylic emulsion dropwise at a constant speed, and continuously stirring for 1h; finally, a sodium silicate solution with a modulus of 5 and high storage stability is obtained.
Example 5
The embodiment provides a preparation method of a sodium silicate solution with the mass fraction of 25% and the modulus of 6, which comprises the following steps:
(1) Firstly, weighing 144g of silica sol (0.6 mol) with the mass fraction of 25%, and heating; weighing 4.0g (0.1 mol) of sodium hydroxide, dissolving in 12.0g of deionized water, slowly and uniformly dripping 13.0g of sodium hydroxide solution into silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 144g of silica sol (0.6 mol) with the mass fraction of 25%, and simultaneously dripping the silica sol and 3.0g of sodium hydroxide solution remained in the first step into the silica sol at a constant speed, and continuously stirring in the process;
(3) Thirdly, adding 3.0g of polyethylene glycol into the potassium silicate solution, and continuously stirring for 0.5h;
(4) Fourthly, adding 8.0g of silicone-acrylic emulsion dropwise at a constant speed, and continuously stirring for 1h; a sodium silicate solution with a modulus of 6 and high storage stability is finally obtained.
Example 6
The embodiment provides a preparation method of a sodium silicate solution with the mass fraction of 20% and the modulus of 7, which comprises the following steps:
(1) Firstly, weighing 210g of 20% silica sol (0.7 mol) by mass fraction, and heating; weighing 4.0g (0.1 mol) of sodium hydroxide, dissolving in 16.0g of deionized water, slowly and uniformly dripping 15.0g of sodium hydroxide solution into silica sol, and continuously stirring in the process;
(2) Secondly, continuously weighing 210g of silica sol (0.7 mol) with the mass fraction of 20%, and simultaneously dropwise adding the silica sol and the rest 5.0g of sodium hydroxide solution in the first step at a constant speed, and continuously stirring in the process;
(3) Thirdly, adding 5.0g of polyethylene glycol into the potassium silicate solution, and continuously stirring for 0.5h;
(4) Fourthly, dropwise adding 10.0g of silicone-acrylic emulsion at a constant speed, and continuously stirring for 1h; a sodium silicate solution having a modulus of 7 and a high storage stability is finally obtained.
In embodiments 1 to 6, the configuration method of a=f is simple and easy to calculate, and actually, the configuration may be performed in a manner that a and f are not equal, and the modulus of the final silicate solution may be controlled by a corresponding calculation method, which is not limited herein.
Example 7
This example provides a silicate solution of high modulus and high stability prepared using the preparation method described in the examples above.
Compared with the original silicate solution, under the combined action of the polyvinyl alcohol and the silicone-acrylic emulsion, the modified silicate solution has the advantages of slow gelation process, high modulus and high storage stability, and simultaneously endows the silicate shop primer with high temperature resistance, and is suitable for preparing and applying inorganic silicate shop primer.
It is to be noted that all terms used for directional and positional indication in the present invention, such as: the terms "upper", "lower", "left", "right", "front", "rear", "vertical", "horizontal", "inner", "outer", "top", "low", "tail", "head", "center", etc. are merely used to explain the relative positional relationship, connection, etc. between the components in a particular state, and are merely for convenience of description of the present invention, and do not require that the present invention must be constructed and operated in a particular orientation, and thus are not to be construed as limiting the present invention. Furthermore, the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention, and the scope of the invention should be assessed accordingly to that of the appended claims.
Claims (10)
1. The preparation method of the silicate solution with high modulus and high stability is characterized by comprising the following steps:
step S1: preparing a high-modulus silicate prefabricated solution by adopting a two-step method;
step S2: adding a modifier into the silicate prefabricated solution obtained in the step S1; obtaining silicate solution with high modulus and high stability;
wherein the modifier is polyethylene glycol and/or silicone-acrylate emulsion.
2. The method for preparing a high modulus, high stability silicate solution according to claim 1, wherein the silicate solution comprises the following raw material components:
the weight components are as follows: 100-300 parts of silica sol, 10-30 parts of alkali metal hydroxide aqueous solution, 1-35 parts of polyvinyl alcohol and 1-35 parts of silicone-acrylic emulsion;
wherein the mass fraction of the silica sol is 10% -35%.
3. The method for preparing a high modulus, high stability silicate solution according to claim 2, wherein the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
4. The method for preparing a high modulus, high stability silicate solution according to claim 2, wherein the two-step process of step S1 comprises:
step S11: weighing SiO 2 Heating silica sol with a mass of a; weighing alkali metal hydroxide with the mass of b, dissolving the alkali metal hydroxide in deionized water with the mass of c to form an alkali metal hydroxide aqueous solution with the mass of d, weighing the alkali metal hydroxide aqueous solution with the mass of e, slowly and uniformly dripping the alkali metal hydroxide aqueous solution into silica sol, and continuously stirring to obtain silica sol prefabricated liquid;
step S12: re-weighing SiO 2 The amount of the substance being fSilica sol, and dripping the re-weighed silica sol and the rest alkali metal hydroxide solution in the step S11 into the silica sol prefabricated solution obtained in the step S1 at a constant speed, and continuously stirring to obtain a high-modulus silicate prefabricated solution;
wherein e < d.
5. The method for preparing a silicate solution with high modulus and high stability according to claim 4, wherein the ratio of e/d in the step S11 is in the range of 0.75 to 0.85.
6. The method for producing a silicate solution with high modulus and high stability according to claim 4, wherein the dropping speed of the aqueous alkali metal hydroxide solution in step S11 is lower than 15ml/h; in step S12, the silica sol has a drop velocity of less than 15ml/h, and the alkali metal hydroxide solution has a drop velocity of less than 5ml/h.
7. The method for preparing a silicate solution with high modulus and high stability according to claim 4, wherein the silicate solution has a modulus of:
and n is more than or equal to 5.
8. The method for preparing a high modulus, high stability silicate solution according to claim 1, wherein step S2 comprises:
step S21: adding polyethylene glycol according to the mass components, and stirring for a first preset time; and/or dropwise adding the silicon-acrylic solution at a constant speed according to the mass components, and stirring for a second preset time.
9. The method for preparing a high modulus, high stability silicate solution according to any of claims 1 to 8, wherein the silicone-acrylic emulsion is a silicone-acrylic emulsion containing an organosiloxane component and an acrylic component.
10. A high modulus, high stability silicate solution prepared by the method of any one of claims 1-9.
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