CN114196023B - Surface modifier and application thereof in preparation of silicon-based composite functional coating material - Google Patents
Surface modifier and application thereof in preparation of silicon-based composite functional coating material Download PDFInfo
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- CN114196023B CN114196023B CN202111646809.8A CN202111646809A CN114196023B CN 114196023 B CN114196023 B CN 114196023B CN 202111646809 A CN202111646809 A CN 202111646809A CN 114196023 B CN114196023 B CN 114196023B
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- 239000002131 composite material Substances 0.000 title claims abstract description 93
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 92
- 239000010703 silicon Substances 0.000 title claims abstract description 92
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 239000011248 coating agent Substances 0.000 title claims abstract description 49
- 239000003607 modifier Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000006255 coating slurry Substances 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- -1 allyl compound Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 18
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- BSMILTTURCQDGJ-UHFFFAOYSA-N N-(3-Hydroxypropyl)phthalimide Chemical compound C1=CC=C2C(=O)N(CCCO)C(=O)C2=C1 BSMILTTURCQDGJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 12
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims description 51
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000945 filler Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005495 investment casting Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001804 emulsifying effect Effects 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 7
- 238000005058 metal casting Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000523 sample Substances 0.000 description 13
- 238000009736 wetting Methods 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 239000012744 reinforcing agent Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000012488 sample solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000011677 pyridoxine Substances 0.000 description 5
- 229940011671 vitamin b6 Drugs 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a surface modifier and application thereof in preparation of a silicon-based composite functional coating material, belongs to the technical field of metal casting, and particularly relates to a method for preparing hydrogen-containing siloxane from octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane, preparing allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide into an allyl compound, then obtaining the surface modifier from the hydrogen-containing siloxane and the allyl compound under the catalysis of a Castaned catalyst, and preparing silicon-based composite functional coating slurry from the surface modifier. The surface modifier obtained by the invention has good wettability; the surface modifier has good emulsifying property; the strength of the silicon-based composite functional coating slurry obtained by the invention is high after drying; the anti-dripping performance of the silicon-based composite functional coating slurry is good.
Description
Technical Field
The invention belongs to the technical field of metal casting, and particularly relates to a surface modifier and application thereof in preparation of a silicon-based composite functional coating material.
Background
The research on the coating is relatively laggard in China, and although relevant researchers respectively carry out certain research on different types of precision casting coating material systems, the defects of poor storage and transportation performance, poor service performance, poor stripping performance and the like exist in the use process; at present, relevant researchers respectively research different types of precision casting silicon-based composite functional coating material systems, but the requirements of precision casting silicon-based composite functional coating materials are really met, the domestic situation is blank, so that key materials of the precision casting silicon-based composite functional coating which are urgently needed have to be imported, the price is high, and the functional coating materials for precision casting of part of domestic military products are frequently out of stock due to military use. Although a great deal of research and exploration on the formula of the silicon-based composite functional coating, the preparation process of the organic uniformly-dispersed stable suspension slurry and the regulation and control of functional addition in the early period can obtain a basis for good results, the current composite functional coating material still has some defects.
Disclosure of Invention
The invention aims to provide a preparation method of a surface modifier which has good wetting property and emulsifying property and can be used for metal coating materials.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a method of preparing a surface modifying agent comprising:
preparing hydrogen-containing siloxane from octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane under the action of concentrated acid, wherein the concentrated acid is concentrated sulfuric acid;
preparing allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide under the action of alkali to obtain an allyl compound, wherein the alkali is sodium hydroxide or potassium hydroxide;
the surface modifier is prepared by hydrosiloxane and allyl compound in solvent under the action of catalyst. According to the invention, the allyl compound is connected to the hydrogen-containing siloxane molecular chain by the method to prepare the surfactant, the surfactant is mixed with water to obtain good wetting property, compared with the hydrogen-containing siloxane, the wetting property is greatly improved, the surfactant is mixed with liquid paraffin to form emulsion to obtain excellent emulsifying property, after the surfactant is used for preparing the silicon-based composite functional coating slurry, the anti-dripping property of the silicon-based composite functional coating slurry is good, and the strength of the silicon-based composite functional coating slurry after being cured is improved.
Preferably, the catalyst is a casytard catalyst.
Preferably, the solvent is isopropanol.
Preferably, the polymethylhydrosiloxane is used in an amount of 50 to 70wt% of the octamethylcyclotetrasiloxane.
Preferably, allyl glycidyl ether is used in an amount of 40 to 60wt% based on N- (3-hydroxypropyl) phthalimide.
Preferably, in the preparation of the hydrogen-containing siloxane, octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane are mixed, concentrated sulfuric acid is added at the temperature of 40-50 ℃ in the nitrogen atmosphere, stirring is carried out for 24-96h, after the reaction is finished, the pH value is adjusted to be neutral, treatment is carried out at the temperature of 80-90 ℃ for 3-9h, then cooling is carried out to the room temperature, and impurities are removed through suction filtration, so that the hydrogen-containing siloxane is obtained.
More preferably, the polymethylhydrosiloxane is used in an amount of 50 to 70wt% of octamethylcyclotetrasiloxane.
More preferably, hexamethyldisiloxane is added in an amount of 6-12wt% of octamethylcyclotetrasiloxane.
More preferably, the concentrated sulfuric acid is added in an amount of 1.5 to 3wt% of octamethylcyclotetrasiloxane.
Preferably, in the preparation of the allyl compound, the allyl glycidyl ether is mixed with N- (3-hydroxypropyl) phthalimide, sodium hydroxide is added under the protection of nitrogen, the mixture is stirred and reacted for 2 to 6 hours at the temperature of between 90 and 95 ℃, and after the reaction is finished, water and low-boiling-point substances are removed by vacuum distillation at room temperature to obtain the allyl compound.
More preferably, allyl glycidyl ether is used in an amount of 40 to 60wt% based on N- (3-hydroxypropyl) phthalimide.
More preferably, sodium hydroxide is used in an amount of 1.3 to 1.9wt% of the allyl glycidyl ether.
Preferably, the preparation of the surface modifier: adding a Castanea catalyst, hydrogen-containing siloxane and an allyl compound into isopropanol at the temperature of 80-90 ℃, reacting for 2-9h, and distilling to remove the isopropanol serving as a solvent after the reaction is finished to obtain the modified organosilane surfactant.
More preferably, the cassiterite catalyst is used in an amount of 0.006 to 0.03wt% based on the hydrosiloxane.
More preferably, the hydrogen-containing siloxane is used in an amount of 15 to 30wt% of the isopropyl alcohol.
More preferably, the allyl compound is used in an amount of 20-40wt% of the isopropyl alcohol.
The invention discloses a surface modifier prepared by the method.
The invention aims to provide silicon-based composite functional coating slurry with good strength and good anti-dripping performance after being dried.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a silicon-based composite functional coating slurry comprising: contains the above surface modifier.
Preferably, the slurry contains filler, binder and solvent.
Preferably, the silicon-based composite functional coating slurry comprises the following components: filler, adhesive, functional agent and solvent.
Preferably, the filler contains at least SiO 2 And may further contain Y 2 O 3 。
Preferably, the binder is at least one of zirconium acetate and water glass.
Preferably, the functional agent is at least one of KH602 and a surface modifier.
Preferably, the solvent is any one of water and ethanol or a mixture thereof.
Preferably, in the preparation of the silicon-based composite functional coating slurry, the filler and the binder are added into the solvent, stirred and mixed uniformly, then the activator is added, and stirred and mixed uniformly to obtain the silicon-based composite functional coating slurry.
More preferably, the solvent is an ethanol solution, and the content of ethanol in the solvent is 20-60wt%.
More preferably, the filler is SiO 2 And Y 2 O 3 In the filler of SiO 2 And Y 2 O 3 According to the mass ratio of 1: 0.1-0.4.
More preferably, the filler is used in an amount of 60 to 80wt% of the solvent.
More preferably, the binder is zirconium acetate.
More preferably, the binder is used in an amount of 20 to 40wt% of the solvent.
More preferably, the functional agent is a surface modifier.
More preferably, the functional agent is used in an amount of 0.6 to 4.2wt% of the solvent.
More preferably, a reinforcing agent can be further added into the silicon-based composite functional coating slurry, and the reinforcing agent is dipalmitoyl-3, 4-pyridoxine diester. When the silicon-based composite functional coating slurry is prepared and used according to the method, the reinforcing agent dipalmitic acid-3, 4-pyridoxine diester is added, so that the dripping resistance and the cured strength of the silicon-based composite functional coating slurry can be enhanced, and the silicon-based composite functional coating slurry has an excellent reinforcing effect.
Still more preferably, the reinforcing agent is used in an amount of 0.4 to 3.2wt% of the solvent.
A casting having a silicon-based composite functional coating, comprising: the base body and the silicon-based composite functional coating which is attached to the base body and is dried and/or sintered by the slurry are/is adopted, and the base body is made of metal and/or non-metal solid materials.
The invention discloses application of the surface modifier in preparation of precision casting and/or metal coatings.
The invention prepares hydrogen-containing siloxane by octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane, prepares allyl compound by allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide, then obtains surface modifier by catalyzing hydrogen-containing siloxane and allyl compound by a Karstard catalyst, and prepares silicon-based composite functional coating slurry by adopting the surface modifier, thus having the following beneficial effects: the surface modifier obtained by the invention has good wetting property; the surface modifier has good emulsifying property; the strength of the silicon-based composite functional coating slurry obtained by the invention is high after drying; the anti-dripping performance of the silicon-based composite functional coating slurry is good. Therefore, the invention is a surface modifier which has good wetting property and emulsifying property and can be used for metal coating materials and the application thereof in preparing silicon-based composite functional coating materials.
Drawings
FIG. 1 is a graph of the results of a wettability test of a surface modifier;
FIG. 2 is a graph showing the results of the emulsification properties test of the surface modifier;
FIG. 3 is a graph of the strength of the slurry of the silicon-based composite functional coating after drying;
FIG. 4 is a dripping quality diagram of the slurry of the silicon-based composite functional coating.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a preparation method of silicon-based composite functional coating slurry,
preparation of hydrogen-containing siloxane: mixing octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane, adding concentrated sulfuric acid at 50 ℃ in a nitrogen atmosphere, stirring for reaction for 72 hours, adjusting the pH to be neutral after the reaction is finished, treating for 6 hours at 90 ℃, cooling to room temperature, and filtering to remove impurities to obtain the hydrogen-containing siloxane. The usage amount of the polymethylhydrosiloxane is 60wt% of the octamethylcyclotetrasiloxane, the addition amount of the hexamethyldisiloxane is 10wt% of the octamethylcyclotetrasiloxane, and the addition amount of the concentrated sulfuric acid is 2.4wt% of the octamethylcyclotetrasiloxane.
Preparation of allyl Compound: mixing allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide, adding sodium hydroxide under the protection of nitrogen, stirring and reacting at the temperature of 95 ℃ for 4 hours, and after the reaction is finished, performing vacuum distillation at room temperature to remove water and low-boiling-point substances to obtain the allyl compound. The amount of allyl glycidyl ether used was 50% by weight of N- (3-hydroxypropyl) phthalimide, and the amount of sodium hydroxide used was 1.6% by weight of allyl glycidyl ether.
Preparation of surface modifier: adding a Castaned catalyst, hydrogen-containing siloxane and an allyl compound into isopropanol at the temperature of 90 ℃, reacting for 6 hours, and distilling to remove the isopropanol serving as a solvent after the reaction is finished to obtain the modified organosilane surfactant. The amount of the Cassied catalyst used was 0.02wt% of the hydrogen-containing siloxane, 20wt% of the isopropyl alcohol, and 30wt% of the allyl compound.
Preparing silicon-based composite functional coating slurry: adding the filler and the binder into the solvent, stirring and mixing uniformly, then adding the active agent, and stirring and mixing uniformly to obtain the silicon-based composite functional coating slurry. The solvent is ethanol solution, the content of ethanol in the solvent is 50wt%, and the filler is SiO 2 The using amount of the filler is 70wt% of the solvent, the binder is zirconium acetate, the using amount of the binder is 30wt% of the solvent, the functional agent is a surface modifier, and the using amount of the functional agent is 1.2wt% of the solvent.
Example 2:
a preparation method of silicon-based composite functional coating slurry,
this example differs from example 1 only in the formulation of the silicon-based composite functional coating slurry.
Preparing silicon-based composite functional coating slurry: adding the filler and the binder into the solvent, stirring and mixing uniformly, then adding the active agent, and stirring and mixing uniformly to obtain the silicon-based composite functional coating slurry. The solvent is ethanol solution, the content of ethanol in the solvent is 50wt%, and the filler is SiO 2 And Y 2 O 3 In the filler of SiO 2 And Y 2 O 3 According to the mass ratio of 1:0.2, the using amount of the filler is 70wt% of the solvent, the binder is water glass, the using amount of the binder is 30wt% of the solvent, the functional agent is a surface modifier, and the using amount of the functional agent is 1.8wt% of the solvent.
Example 3:
a preparation method of silicon-based composite functional coating slurry,
this example differs from example 1 only in the formulation of the silicon-based composite functional coating slurry.
Preparing silicon-based composite functional coating slurry: adding the filler and the binder into the solvent, stirring and mixing uniformly, then adding the active agent, and stirring and mixing uniformly to obtain the silicon-based composite functional coating slurry. The solvent is ethanol solution, the content of ethanol in the solvent is 50wt%, and the filler is SiO 2 And Y 2 O 3 In the filler of SiO 2 And Y 2 O 3 According to the mass ratio of 1:0.2, the filler is used in an amount of 70wt% of the solvent, the binder is water glass, the binder is used in an amount of 30wt% of the solvent, the functional agent is KH602, and the functional agent is used in an amount of 2.4wt% of the solvent.
Example 4:
a preparation method of silicon-based composite functional coating slurry,
this example differs from example 1 only in the formulation of the silicon-based composite functional coating slurry.
Preparing silicon-based composite functional coating slurry: adding the filler and the binder into the solvent, stirring and mixing uniformly, then adding the active agent, and stirring and mixing uniformly to obtain the silicon-based composite functional coating slurry. The solvent is ethanol solution, the content of ethanol in the solvent is 50wt%, and the filler is SiO 2 And Y 2 O 3 In the filler of SiO 2 And Y 2 O 3 According to the mass ratio of 1:0.2, the using amount of the filler is 70wt% of the solvent, the binder is zirconium acetate, the using amount of the binder is 30wt% of the solvent, the functional agent is a surface modifier, and the using amount of the functional agent is 1.2wt% of the solvent.
Example 5:
a preparation method of silicon-based composite functional coating slurry,
this example is different from example 4 only in that the amount of the functional agent used in the preparation of the silicon-based composite functional coating slurry is 3.6wt% of the solvent.
Example 6:
a preparation method of silicon-based composite functional coating slurry,
preparation of hydrogen-containing siloxane: mixing octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane, adding concentrated sulfuric acid at 50 ℃ in a nitrogen atmosphere, stirring for reaction for 72 hours, adjusting the pH to be neutral after the reaction is finished, treating for 6 hours at 90 ℃, cooling to room temperature, and filtering to remove impurities to obtain the hydrogen-containing siloxane. The usage amount of the polymethylhydrosiloxane is 60wt% of the octamethylcyclotetrasiloxane, the addition amount of the hexamethyldisiloxane is 10wt% of the octamethylcyclotetrasiloxane, and the addition amount of the concentrated sulfuric acid is 2.4wt% of the octamethylcyclotetrasiloxane.
Preparation of allyl Compound: mixing allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide, adding sodium hydroxide under the protection of nitrogen, stirring and reacting at the temperature of 95 ℃ for 4 hours, and after the reaction is finished, carrying out vacuum distillation at room temperature to remove water and low-boiling-point substances to obtain the allyl compound. The amount of allyl glycidyl ether used was 50% by weight of N- (3-hydroxypropyl) phthalimide, and the amount of sodium hydroxide used was 1.6% by weight of allyl glycidyl ether.
Preparation of surface modifier: adding a Castaned catalyst, hydrogen-containing siloxane and an allyl compound into isopropanol at the temperature of 90 ℃, reacting for 6 hours, and distilling to remove the isopropanol serving as a solvent after the reaction is finished to obtain the modified organosilane surfactant. The amount of the Cassied catalyst used was 0.02wt% of the hydrogen-containing siloxane, 20wt% of the isopropyl alcohol, and 30wt% of the allyl compound.
Preparing silicon-based composite functional coating slurry: adding the filler and the binder into the solvent, stirring and mixing uniformly, then adding the activator and the reinforcing agent, and stirring and mixing uniformly to obtain the silicon-based composite functional coating slurry. The solvent is ethanol solution, the content of ethanol in the solvent is 50wt%, and the filler is SiO 2 And Y 2 O 3 In the filler of SiO 2 And Y 2 O 3 According to the mass ratio of 1:0.2, the using amount of the filler is 70wt% of the solvent, the binder is zirconium acetate, the using amount of the binder is 30wt% of the solvent, the functional agent is a surface modifier, the using amount of the functional agent is 3.6wt% of the solvent, the reinforcing agent is dipalmitic acid-3, 4-pyridoxine diester, and the using amount of the reinforcing agent is 0.9wt% of the solvent.
Example 7:
a preparation method of silicon-based composite functional coating slurry,
this example is different from example 6 only in that the reinforcing agent is used in an amount of 2.6wt% of the solvent in the formulation of the silicon-based composite functional coating slurry.
Example 8:
a method for preparing a casting with a silicon-based composite functional coating,
and brushing the silicon-based composite functional coating slurry on the surface of the metal solid, and drying. The silicon-based composite functional coating slurry was derived from example 5. The metal is iron.
Example 9:
a method for preparing a casting with a silicon-based composite functional coating,
and brushing the silicon-based composite functional coating slurry on the surface of the metal solid, drying and sintering. The silicon-based composite functional coating slurry was derived from example 5. The metal is copper.
Example 10:
a method for preparing a casting with a silicon-based composite functional coating,
and brushing the silicon-based composite functional coating slurry on the surface of the non-metal solid, drying and sintering. The silicon-based composite functional coating slurry was derived from example 5. The nonmetal is ceramic.
Comparative example 1:
this comparative example is different from example 5 only in that no functional agent is used in the formulation of the silicon-based composite functional coating slurry.
Test example:
1. wetting Performance test
Test samples: the surface modifier obtained in example 4.
The samples were tested for their wetting properties according to the method of the national standard GB/T11983-2008. The samples are prepared into sample solutions with the concentrations of 100, 200, 300, 400 and 500mg/L respectively for testing.
As shown in FIG. 1, it is understood that the wettability of the surface modifier prepared by the present invention is increased with the increase of the content of the surface modifier in the solution, and the wetting time is decreased, and the wetting time is longest and is 4944s at a surface modifier concentration of 100mg/L, and the wetting time is shortest and is 1096s at a surface modifier concentration of 500 mg/L.
The comparative group was set, and the hydrosiloxane prepared according to the present invention was used as a comparative sample. The invention prepares the hydrogen-containing siloxane into the concentration of 500mg/L, carries out the wetting performance test and takes 1832s.
2. Testing of emulsifying Properties
Test samples: the surface modifier obtained in example 4.
The samples are prepared into sample solutions with the concentrations of 100mg/L, 200 mg/L, 300 mg/L, 400 mg/L and 500mg/L respectively, 40mL of the sample solutions and 40mL of liquid paraffin are added into a 100mL measuring cylinder, the sample solutions and the liquid paraffin are greatly and violently oscillated for 5 times at an angle of 90 degrees, and standing is repeated for 3 times. Recording was started at the moment the last oscillation was stopped until 10mL of water separated from the aqueous phase. The average value was obtained by repeating the above steps several times. The longer the water-separating time of the surfactant, the stronger the emulsifying ability thereof is indicated.
As shown in FIG. 2, the emulsifying properties of the surface modifier prepared according to the present invention are shown, and it is understood that the wetting properties of the surface modifier show an increasing tendency with increasing content in the solution, which means that the water-separating time is longer, the water-separating time is shortest and the required time is 17s when the concentration of the surface modifier is 100mg/L, and the wetting time is longest and the required time is 528s when the concentration of the surface modifier is 500 mg/L.
The comparative group was set up with the hydrosiloxane prepared according to the invention as a comparative sample. The invention prepares the hydrogen-containing siloxane into the concentration of 500mg/L, and carries out the emulsification performance test, and the required time is 319s.
3. Stability to acid, base and salt
Test samples: the surface modifier obtained in example 4.
Preparing the sample into a sample solution with the mass fraction of 1%, taking 50mL of the solution, adjusting the pH value to 5, testing the stability of the sample at the temperature of 25 ℃, and observing whether the phenomena of layering, oil slick and wall sticking exist. Test time 72h.
Preparing the sample into a sample solution with the mass fraction of 1%, taking 50mL of the solution, adjusting the pH value to 9, testing the stability of the sample at the temperature of 25 ℃, and observing whether the phenomena of layering, oil slick and wall sticking exist. Test time 72h.
Preparing the sample into a sample solution with the mass fraction of 1%, adding potassium chloride in the solution until the content reaches 2wt%, taking 50mL of the solution, adjusting the pH value to 5, testing the stability of the sample at the temperature of 25 ℃, and observing whether the phenomena of layering, oil slick and wall sticking exist. Test time 72h.
The surface modifier prepared by the method has emulsifying property, excellent acid resistance, alkali resistance and salt resistance, and good stability, and no phenomena of layering, oil floating and wall sticking are observed after 72 hours of testing by the method.
4. Strength test
Test samples: the silicon-based composite functional coating slurry prepared in each example and comparative example is prepared by coating a silicon-based composite functional coating material on a glass sheet and drying.
The 4-coat viscosity cup was placed 1000mm from the above sample and the test sample was placed at an angle of 45 degrees to the horizontal. The coating 4 viscosity cup is filled with sand. During measurement, the viscosity cup falls sand on the test sample until a round hole of about 2-4mm appears on the test sample. Collecting the sand under the surface, and weighing the total mass as a performance index for judging the strength of the coating.
The strength test result of the silicon-based composite functional coating slurry prepared by the invention is shown in fig. 3, wherein the strength of the silicon-based composite functional coating material prepared in the embodiment 4 after being coated on a glass sheet and dried is 98g, the strength of the silicon-based composite functional coating material prepared in the embodiment 5 after being coated on the glass sheet and dried is 104g, the strength of the silicon-based composite functional coating material prepared in the comparative example 1 after being coated on the glass sheet and dried is 87g, and compared with the comparative example 1, the embodiment 5 shows that the silicon-based composite functional coating material has better effect after the surface modifier is used in the prepared silicon-based composite functional coating material, the strength of the silicon-based composite functional coating material after being coated on the glass sheet and dried is improved by 19.54 percent; the strength of the silicon-based composite functional coating material prepared in example 6 after being coated on a glass sheet and dried is 113g, the strength of the silicon-based composite functional coating material prepared in example 7 after being coated on the glass sheet and dried is 119g, and compared with example 5, the strength of the silicon-based composite functional coating material prepared in example 7 after being coated on the glass sheet and dried is improved by 14.42%, which shows that the strength of the silicon-based composite functional coating material after being coated on the glass sheet is improved by using the reinforcing agent dipalmitoyl-3, 4-pyridoxine diester.
5. Drip resistance test
Test samples: the silicon-based composite functional coating slurry prepared in each example and comparative example.
A glass slide of 80X 30mm in area of 40X 30mm was immersed in the sample and removed vertically by holding the upper end of the slide so that the surface coating dropped freely onto the prepared glass slide. And finally weighing the mass of the dripping paint, namely the dripping property of the paint. The lower the mass, the better the drip resistance.
The anti-dripping test result of the silicon-based composite functional coating slurry prepared by the invention is shown in fig. 4, wherein the dripping mass of the silicon-based composite functional coating material prepared in the example 4 on a glass slide is 0.39g, the dripping mass of the silicon-based composite functional coating material prepared in the example 5 on the glass slide is 0.36, the dripping mass of the silicon-based composite functional coating material prepared in the comparative example 1 on the glass slide is 0.46g, and compared with the comparative example 1, the example 5 shows that the prepared silicon-based composite functional coating material has a better effect after the surface modifier is used, which is represented by the reduction of the dripping mass of the prepared silicon-based composite functional coating material on the glass slide, compared with the comparative example 1, the dripping mass of the silicon-based composite functional coating material prepared in the example 5 on the glass slide is reduced by 15.21%, namely the anti-dripping performance is improved by 15.21%; the dripping mass of the silicon-based composite functional coating material prepared in example 6 on a glass slide is 0.32g, the dripping mass of the silicon-based composite functional coating material prepared in example 7 on the glass slide is 0.28g, and compared with example 5, in example 7, the dripping mass of the silicon-based composite functional coating material prepared in example 7 on the glass slide is reduced by 28.21%, namely the dripping resistance is improved by 28.21%, which indicates that the use of the reinforcing agent dipalmitic acid-3, 4-pyridoxine diester improves the dripping resistance of the silicon-based composite functional coating material.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A method of preparing a surface modifying agent comprising:
preparing hydrogen-containing siloxane from octamethylcyclotetrasiloxane, polymethylhydrosiloxane and hexamethyldisiloxane under the action of concentrated acid, wherein the concentrated acid is concentrated sulfuric acid;
preparing allyl glycidyl ether and N- (3-hydroxypropyl) phthalimide under the action of alkali to obtain an allyl compound, wherein the alkali is sodium hydroxide or potassium hydroxide;
the surface modifier is prepared by hydrosiloxane and allyl compound in solvent under the action of catalyst.
2. The method for preparing a surface modifier according to claim 1, wherein: the catalyst is a casytard catalyst.
3. The method for preparing a surface modifier according to claim 1, wherein: the solvent is isopropanol.
4. The method for preparing a surface modifier according to claim 1, wherein: the usage amount of the polymethylhydrosiloxane is 50-70wt% of the octamethylcyclotetrasiloxane.
5. The method for preparing a surface modifier according to claim 1, wherein: the using amount of the allyl glycidyl ether is 40-60wt% of N- (3-hydroxypropyl) phthalimide.
6. A surface-modifying agent prepared by the process of any one of claims 1 to 5.
7. A silicon-based composite functional coating slurry comprising: comprising the surface modifier of claim 6.
8. The silicon-based composite functional coating slurry according to claim 7, wherein: the slurry contains filler, binder and solvent.
9. A casting having a silicon-based composite functional coating, comprising: a substrate and a silicon-based composite functional coating which is attached on the substrate and dried and/or sintered by the slurry of claim 7, wherein the substrate is a metal and/or non-metal solid material.
10. Use of the surface-modifying agent according to claim 6 for the production of precision casting and/or metal coatings.
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| WO1999007767A1 (en) * | 1997-08-07 | 1999-02-18 | Wacker-Chemie Gmbh | SILICONIMIDES CONTAINING Si-H GROUPS |
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Effective date of registration: 20240229 Address after: No. 26 Qilin Avenue, West District, Donghai County Development Zone, Lianyungang City, Jiangsu Province, 222300 Patentee after: SINOMA JIANGSU SOLAR ENERGY NEW MATERIAL CO.,LTD. Country or region after: China Address before: 222000 east of Weixing River and south of Shunda Road, West Zone, Donghai County Development Zone, Lianyungang City, Jiangsu Province Patentee before: SINOMA ADVANCED JIANGSU SILICON MATERIALS Co.,Ltd. Country or region before: China Patentee before: SINOMA JIANGSU SOLAR ENERGY NEW MATERIAL CO.,LTD. |