CN113336523A - Environment-friendly high-temperature binder and preparation method thereof - Google Patents
Environment-friendly high-temperature binder and preparation method thereof Download PDFInfo
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- CN113336523A CN113336523A CN202110757804.6A CN202110757804A CN113336523A CN 113336523 A CN113336523 A CN 113336523A CN 202110757804 A CN202110757804 A CN 202110757804A CN 113336523 A CN113336523 A CN 113336523A
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- 239000011230 binding agent Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 62
- 239000000654 additive Substances 0.000 claims abstract description 36
- 230000000996 additive effect Effects 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 17
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000000853 adhesive Substances 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 239000011630 iodine Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 8
- 239000007818 Grignard reagent Substances 0.000 claims description 7
- 150000004795 grignard reagents Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011521 glass Substances 0.000 abstract description 15
- 238000002310 reflectometry Methods 0.000 abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005619 boric acid group Chemical group 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 3
- 238000005496 tempering Methods 0.000 abstract description 3
- 238000013082 photovoltaic technology Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000009965 odorless effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000003747 Grignard reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical group B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/342—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more reactive oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an environment-friendly high-temperature binder and a preparation method thereof, and relates to the field of binders, wherein the environment-friendly high-temperature binder is obtained by adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing; the adhesive is lead-free, cadmium-free and fluorine-free, is used in a high-reflection coating, is odorless during printing, does not generate pungent odor, is not harmful to tempering equipment, can improve the reflectivity of the reflection coating after a high-temperature resistant additive is added, can reduce the thermal expansion coefficient of the reflection coating, can be used at the temperature of 680-720 ℃, is matched with glass, meets the requirements of photovoltaic technology, has good high-temperature resistance under the synergistic action of a benzene ring, a boric acid group and a triazine ring, is added into the high-reflection coating, improves the matching degree of the high-reflection coating and the glass, and improves the heat resistance of the high-reflection coating.
Description
Technical Field
The invention relates to the field of adhesives, in particular to an environment-friendly high-temperature adhesive and a preparation method thereof.
Background
The types of the back plates on the market at present are two major types, namely a TPT (thermoplastic vulcanizate) structural back plate containing fluoropolymer and a full PET (polyethylene terephthalate) structural back plate, and the TPT and PET back plates have some hidden dangers, such as the problems of back plate weathering, aging and embrittlement, and the problems of delamination of an adhesive and interlayer adhesive force attenuation; the back plate needs to withstand more severe tests, and the failure of the back plate can directly expose the packaging material and the battery inside the component to severe outdoor environment, so that a series of problems such as packaging material hydrolysis, battery and welding strip corrosion and delamination are caused, the power output and the service life of the component are further reduced, and the back plate is directly related to the profitability and the service life of a photovoltaic power station;
in recent years, research and development of double-glass photovoltaic modules are started, namely a composite layer is formed by two pieces of glass (front plate glass and back plate glass) and a solar cell, and a lead wire is connected in series and in parallel between the cells to collect the photovoltaic cell module formed by leading wire ends, the double-glass module is developed rapidly, particularly in application occasions with harsh climatic environments, the glass back plate is mainly used in the double-glass module and is formed by edging, punching and toughening a common float glass sheet serving as a substrate, and compared with common TPT and PET back plates, the glass back plate has excellent durability, weather resistance, chemical corrosion resistance and the like;
in order to increase the sunlight utilization rate among the battery pieces, a layer of white high-reflection coating needs to be printed among the battery pieces, the reflectivity is more than 80%, but the existing white high-reflection coating has the defects that the smell is strong during printing, pungent odor is generated during baking, even the coating is unfavorable for tempering equipment, and the coating contains fluorine, lead and the like;
the photovoltaic glass back plate needs to be tempered at the temperature of 680-720 ℃, and the high-reflection ink is baked on the back plate glass while being tempered, so that a high-temperature binder with an expansion coefficient matched with that of the glass is urgently needed, the photovoltaic technical requirements are met, the requirements are lead-free, cadmium-free and fluorine-free, the requirements are high in reflectivity, and the photovoltaic glass back plate is colorless and pure white;
in view of the above technical drawbacks, a solution is proposed.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide an environment-friendly high-temperature adhesive and a preparation method thereof, wherein the environment-friendly high-temperature adhesive comprises the following steps: the environment-friendly high-temperature binder is obtained by adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water and stirring and dispersing, and the problems that the expansion coefficient of the existing white high-reflection coating is not matched with that of glass, and the existing white high-reflection coating contains lead, cadmium and fluorine elements and is poor in environmental protection performance are solved.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly high-temperature binder comprises the following components in parts by weight:
15-25 parts of titanium dioxide, 15-35 parts of phosphoric acid, 5-25 parts of high-temperature resistant additive, 0.5-3 parts of zirconium oxide, 0.5-3 parts of yttrium oxide, 0.1-0.9 part of lanthanum oxide, 10-25 parts of silica sol and 10-50 parts of water;
the environment-friendly high-temperature binder is prepared by the following steps:
adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 2-5h under the conditions that the temperature is 80-100 ℃ and the stirring speed is 8000-;
the high-temperature resistant additive is prepared by the following steps:
a1: adding magnesium powder and iodine particles into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, dropwise adding 1/4 tribromophenol solution while stirring under the condition that the stirring speed is 100-300r/min, controlling the dropwise adding speed to be 1-2mL/min, after finishing dropwise adding, continuously stirring until format reaction is initiated, heating to 50-55 ℃, controlling the heating speed to be 1-5 ℃/min, then dropwise adding the rest tribromophenol solution, after finishing dropwise adding, continuously reacting for 1-2h, finishing the reaction, and cooling to room temperature to obtain a format reagent;
a2: adding trimethyl borate and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, introducing nitrogen, cooling to below-25 ℃, dropwise adding a format reagent while stirring under the condition that the stirring speed is 300-one-year sand 500r/min, controlling the dropwise adding speed to be 1 drop/s, after the dropwise adding is finished, carrying out heat preservation reaction for 2-3h, then heating to 0-5 ℃, adding a hydrochloric acid solution, continuously stirring for 30-50min, then adding ethyl acetate, standing for layering, washing an organic phase with distilled water for 3-5 times, then drying with anhydrous sodium sulfate, then carrying out rotary evaporation to remove the solvent, and recrystallizing an evaporation product with 1, 2-dichloroethane to obtain an intermediate product;
the reaction principle is as follows:
a3: under the protection of nitrogen, adding the intermediate product, sodium hydroxide and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, stirring and dispersing for 2-3h at room temperature and at a stirring speed of 500-600r/min, then dropwise adding a cyanuric chloride solution, heating to reflux after dropwise adding is finished, stirring and reacting for 15-20h, cooling the reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, hydrolyzing the filter cake for 2-3h by using a hydrochloric acid solution, then carrying out vacuum filtration again, and carrying out silica gel column chromatography separation on the filter cake by using a mixed solvent as a eluent to obtain the high-temperature resistant additive.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the magnesium powder, the iodine granules and the tribromophenol solution in the step A1 is 1.2 g: 0.3 g: 80mL, wherein the tribromophenol solution is tribromophenol according to a ratio of 135 mmol: 150mL of the solution was dissolved in tetrahydrofuran.
As a further scheme of the invention: in the step A2, the dosage ratio of trimethyl borate, tetrahydrofuran, the Grignard reagent, the hydrochloric acid solution and ethyl acetate is 5.6 g: 40mL of: 150mL of: 40mL of: 50mL, and the molar concentration of the hydrochloric acid solution is 2 mol/L.
As a further scheme of the invention: the dosage ratio of the intermediate product, the sodium hydroxide, the tetrahydrofuran and the cyanuric chloride solution in the step A3 is 31 mmol: 64 mmol: 50mL of: 40mL, wherein the cyanuric chloride solution is cyanuric chloride according to the molar ratio of 10 mmol: 10mL of solution formed by dissolving in tetrahydrofuran, wherein the molar concentration of the hydrochloric acid solution is 2mol/L, and the mixed solvent is dichloromethane and absolute ethyl alcohol according to a volume ratio of 7: 3 in a mixture of two or more.
As a further scheme of the invention: the preparation method of the environment-friendly high-temperature adhesive comprises the following steps:
the method comprises the following steps: weighing 15-25 parts of titanium dioxide, 15-35 parts of phosphoric acid, 5-25 parts of high-temperature resistant additive, 0.5-3 parts of zirconium oxide, 0.5-3 parts of yttrium oxide, 0.1-0.9 part of lanthanum oxide, 10-25 parts of silica sol and 10-50 parts of water according to parts by weight for later use;
step two: adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 2-5h under the conditions that the temperature is 80-100 ℃ and the stirring speed is 8000-.
The invention has the beneficial effects that:
according to the environment-friendly high-temperature binder and the preparation method thereof, the environment-friendly high-temperature binder is obtained by adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, stirring and dispersing; the adhesive is lead-free, cadmium-free and fluorine-free, is used in a high-reflection coating, has no odor during printing, does not generate pungent odor, is not harmful to tempering equipment, can improve the reflectivity of the reflection coating and reduce the thermal expansion coefficient after being added with a high-temperature resistant additive, can be used at the temperature of 680-720 ℃, is matched with glass, and meets the requirements of photovoltaic technology;
the environment-friendly high-temperature binder is prepared by preparing a high-temperature resistant additive, magnesium and tribromophenol are subjected to Grignard reaction to form an organic magnesium reagent, namely Grignard reagent, then the Grignard reagent is subjected to hydrolysis with trimethyl borate to generate an intermediate product, the intermediate product is subjected to reaction with cyanuric chloride to generate the high-temperature resistant additive, the molecule of the high-temperature resistant additive has a large amount of benzene rings and boric acid groups, and simultaneously contains triazine rings, the benzene rings are high in stability and difficult to damage, the boric acid groups are heated and dehydrated to form a boroxine structure, the boroxine structure is further heated to form a B-O-C carbon layer to cover the surface, so that the heat insulation and oxygen isolation effects are achieved, the formation of initial residual carbon is promoted, the triazine rings are decomposed to form a large amount of non-combustible gas, so that the carbon layer is expanded, and the expanded carbon layer can be used as a protective layer covering the surface of the, the high-temperature resistant additive has good high-temperature resistance under the synergistic action of a benzene ring, a boric acid group and a triazine ring, and is added into a high-reflection coating to improve the matching degree of the high-reflection coating and glass and improve the heat resistance of the high-reflection coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this example is a high temperature resistant additive, which is prepared by the following steps:
a1: adding magnesium powder and iodine granules into a three-neck flask provided with a gas guide pipe, a stirrer and a constant-pressure dropping funnel, dropwise adding 1/4 tribromophenol solution while stirring under the condition of stirring speed of 100r/min, controlling the dropwise adding speed to be 1mL/min, after dropwise adding, continuously stirring until Grignard reaction is initiated, heating to 50 ℃, controlling the heating speed to be 1 ℃/min, then dropwise adding the rest tribromophenol solution, after dropwise adding, continuously reacting for 1-2h, after reaction, cooling to room temperature, and obtaining Grignard reagent; controlling the dosage ratio of the magnesium powder, the iodine granules and the tribromophenol solution to be 1.2 g: 0.3 g: 80mL of tribromophenol solution is tribromophenol according to a molar ratio of 135 mmol: 150mL of solution formed by dissolving in tetrahydrofuran;
a2: adding trimethyl borate and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, introducing nitrogen, cooling to below-25 ℃, dropwise adding a format reagent while stirring under the condition that the stirring speed is 300r/min, controlling the dropwise adding speed to be 1 drop/s, carrying out heat preservation reaction for 2 hours after dropwise adding is finished, then heating to 0 ℃, adding a hydrochloric acid solution, continuously stirring for 30 minutes, then adding ethyl acetate, standing for layering, washing an organic phase for 3 times by using distilled water, then drying by using anhydrous sodium sulfate, then carrying out rotary evaporation to remove a solvent, and recrystallizing an evaporation product by using 1, 2-dichloroethane to obtain an intermediate product; controlling the dosage ratio of trimethyl borate to tetrahydrofuran to the format reagent to the hydrochloric acid solution to be 5.6 g: 40mL of: 150mL of: 40mL of: 50mL, wherein the molar concentration of the hydrochloric acid solution is 2 mol/L;
a3: under the protection of nitrogen, adding an intermediate product, sodium hydroxide and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, stirring and dispersing for 2 hours at room temperature under the condition that the stirring speed is 500r/min, then dropwise adding a cyanuric chloride solution, heating to reflux after dropwise adding, stirring and reacting for 15 hours, cooling a reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, hydrolyzing a filter cake for 2 hours by using a hydrochloric acid solution, then carrying out vacuum filtration again, and carrying out silica gel column chromatography separation on the filter cake to obtain the high-temperature resistant additive; controlling the dosage ratio of the intermediate product, sodium hydroxide, tetrahydrofuran and cyanuric chloride solution to be 31 mmol: 64 mmol: 50mL of: 40mL, cyanuric chloride solution is cyanuric chloride according to the ratio of 10 mmol: 10mL of solution formed by dissolving in tetrahydrofuran, wherein the molar concentration of the hydrochloric acid solution is 2mol/L, and the mixed solvent is dichloromethane and absolute ethyl alcohol according to a volume ratio of 7: 3 in a mixture of two or more.
Example 2:
this example is a high temperature resistant additive, which is prepared by the following steps:
a1: adding magnesium powder and iodine granules into a three-neck flask provided with a gas guide pipe, a stirrer and a constant-pressure dropping funnel, dropwise adding 1/4 tribromophenol solution while stirring under the condition of stirring speed of 200r/min, controlling the dropwise adding speed to be 1mL/min, after dropwise adding, continuously stirring until Grignard reaction is initiated, heating to 52 ℃, controlling the heating speed to be 3 ℃/min, then dropwise adding the rest tribromophenol solution, after dropwise adding, continuously reacting for 1.5h, after reaction, cooling to room temperature, and obtaining Grignard reagent; controlling the dosage ratio of the magnesium powder, the iodine granules and the tribromophenol solution to be 1.2 g: 0.3 g: 80mL of tribromophenol solution is tribromophenol according to a molar ratio of 135 mmol: 150mL of solution formed by dissolving in tetrahydrofuran;
a2: adding trimethyl borate and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, introducing nitrogen, cooling to below-25 ℃, dropwise adding a format reagent while stirring under the condition that the stirring speed is 400r/min, controlling the dropwise adding speed to be 1 drop/s, after the dropwise adding is finished, carrying out heat preservation reaction for 2.5 hours, then heating to 3 ℃, adding a hydrochloric acid solution, continuously stirring for 40 minutes, then adding ethyl acetate, standing for layering, washing an organic phase for 4 times by using distilled water, then drying by using anhydrous sodium sulfate, then carrying out rotary evaporation to remove a solvent, and recrystallizing an evaporation product by using 1, 2-dichloroethane to obtain an intermediate product; controlling the dosage ratio of trimethyl borate to tetrahydrofuran to the format reagent to the hydrochloric acid solution to be 5.6 g: 40mL of: 150mL of: 40mL of: 50mL, wherein the molar concentration of the hydrochloric acid solution is 2 mol/L;
a3: under the protection of nitrogen, adding an intermediate product, sodium hydroxide and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, stirring and dispersing for 2.5h at room temperature and at a stirring speed of 550r/min, then dropwise adding a cyanuric chloride solution, heating to reflux after dropwise adding, stirring and reacting for 17h, cooling a reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, hydrolyzing a filter cake for 2.5h by using a hydrochloric acid solution, then carrying out vacuum filtration again, and carrying out silica gel column chromatographic separation on the filter cake to obtain the high-temperature resistant additive; controlling the dosage ratio of the intermediate product, sodium hydroxide, tetrahydrofuran and cyanuric chloride solution to be 31 mmol: 64 mmol: 50mL of: 40mL, cyanuric chloride solution is cyanuric chloride according to the ratio of 10 mmol: 10mL of solution formed by dissolving in tetrahydrofuran, wherein the molar concentration of the hydrochloric acid solution is 2mol/L, and the mixed solvent is dichloromethane and absolute ethyl alcohol according to a volume ratio of 7: 3 in a mixture of two or more.
Example 3:
this example is a high temperature resistant additive, which is prepared by the following steps:
a1: adding magnesium powder and iodine granules into a three-neck flask provided with a gas guide pipe, a stirrer and a constant-pressure dropping funnel, dropwise adding 1/4 tribromophenol solution while stirring under the condition that the stirring speed is 300r/min, controlling the dropwise adding speed to be 2mL/min, after dropwise adding, continuously stirring until the Grignard reaction is initiated, heating to 55 ℃, controlling the heating speed to be 5 ℃/min, then dropwise adding the rest tribromophenol solution, after dropwise adding, continuously reacting for 2h, after the reaction is finished, cooling to room temperature, and obtaining a Grignard reagent; controlling the dosage ratio of the magnesium powder, the iodine granules and the tribromophenol solution to be 1.2 g: 0.3 g: 80mL of tribromophenol solution is tribromophenol according to a molar ratio of 135 mmol: 150mL of solution formed by dissolving in tetrahydrofuran;
a2: adding trimethyl borate and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, introducing nitrogen, cooling to below-25 ℃, dropwise adding a format reagent while stirring under the condition that the stirring speed is 500r/min, controlling the dropwise adding speed to be 1 drop/s, carrying out heat preservation reaction for 3 hours after dropwise adding, then heating to 5 ℃, adding a hydrochloric acid solution, continuously stirring for 50 minutes, then adding ethyl acetate, standing for layering, washing an organic phase for 5 times by using distilled water, then drying by using anhydrous sodium sulfate, then carrying out rotary evaporation to remove a solvent, and recrystallizing an evaporation product by using 1, 2-dichloroethane to obtain an intermediate product; controlling the dosage ratio of trimethyl borate to tetrahydrofuran to the format reagent to the hydrochloric acid solution to be 5.6 g: 40mL of: 150mL of: 40mL of: 50mL, wherein the molar concentration of the hydrochloric acid solution is 2 mol/L;
a3: under the protection of nitrogen, adding an intermediate product, sodium hydroxide and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, stirring and dispersing for 3 hours at room temperature under the condition that the stirring speed is 600r/min, then dropwise adding a cyanuric chloride solution, heating to reflux after dropwise adding, stirring and reacting for 20 hours, cooling a reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, hydrolyzing a filter cake for 3 hours by using a hydrochloric acid solution, then carrying out vacuum filtration again, and carrying out silica gel column chromatography separation on the filter cake to obtain the high-temperature resistant additive; controlling the dosage ratio of the intermediate product, sodium hydroxide, tetrahydrofuran and cyanuric chloride solution to be 31 mmol: 64 mmol: 50mL of: 40mL, cyanuric chloride solution is cyanuric chloride according to the ratio of 10 mmol: 10mL of solution formed by dissolving in tetrahydrofuran, wherein the molar concentration of the hydrochloric acid solution is 2mol/L, and the mixed solvent is dichloromethane and absolute ethyl alcohol according to a volume ratio of 7: 3 in a mixture of two or more.
Example 4:
the embodiment is a preparation method of an environment-friendly high-temperature binder, which comprises the following steps:
the method comprises the following steps: weighing 15 parts of titanium dioxide, 15 parts of phosphoric acid, 5 parts of high-temperature resistant additive from example 1, 0.5 part of zirconium oxide, 0.5 part of yttrium oxide, 0.1 part of lanthanum oxide, 10 parts of silica sol and 10 parts of water according to parts by weight for later use;
step two: adding titanium dioxide, phosphoric acid, a high-temperature-resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 2 hours at the temperature of 80 ℃ and the stirring speed of 8000r/min to obtain the environment-friendly high-temperature binder.
Example 5:
the embodiment is a preparation method of an environment-friendly high-temperature binder, which comprises the following steps:
the method comprises the following steps: weighing 20 parts of titanium dioxide, 25 parts of phosphoric acid, 15 parts of high-temperature resistant additive from example 2, 1.8 parts of zirconium oxide, 1.8 parts of yttrium oxide, 0.5 part of lanthanum oxide, 18 parts of silica sol and 30 parts of water according to parts by weight for later use;
step two: adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 3.5 hours under the conditions that the temperature is 90 ℃ and the stirring speed is 10000r/min to obtain the environment-friendly high-temperature binder.
Example 6:
the embodiment is a preparation method of an environment-friendly high-temperature binder, which comprises the following steps:
the method comprises the following steps: weighing 25 parts of titanium dioxide, 35 parts of phosphoric acid, 25 parts of high-temperature resistant additive from example 3, 3 parts of zirconium oxide, 3 parts of yttrium oxide, 0.9 part of lanthanum oxide, 25 parts of silica sol and 50 parts of water according to parts by weight for later use;
step two: adding titanium dioxide, phosphoric acid, a high-temperature-resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 5 hours at the temperature of 100 ℃ and the stirring speed of 12000r/min to obtain the environment-friendly high-temperature binder.
Comparative example 1:
comparative example 1 differs from example 6 in that no high temperature resistant additive is added.
Comparative example 2:
comparative example 2 is different from example 6 in that the high temperature resistant inorganic composite binder of application No. 200780010654.0 is used instead of the environment-friendly high temperature binder.
The thermal expansion coefficients of the adhesives of the examples 4-6 and the comparative examples 1-2 are detected by using a DIL 402Expedis Select & Superme thermal expansion measuring instrument, the visible light reflectivity of the adhesives of the examples 4-6 and the comparative examples 1-2 is detected by using an SMN-R full intelligent reflectivity instrument, and the detection results are as follows:
referring to the data in the table, according to the comparison between the example and the comparative example 1, it can be known that the thermal expansion coefficient of the adhesive is obviously reduced by adding the high temperature resistant additive, and the thermal expansion coefficient can reach a thermal expansion coefficient similar to that of glass, and according to the comparison between the example and the comparative example 2, the adhesive with the high temperature resistant additive has better high temperature resistance than the high temperature resistant inorganic composite adhesive in the prior art.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The environment-friendly high-temperature binder is characterized by comprising the following components in parts by weight:
15-25 parts of titanium dioxide, 15-35 parts of phosphoric acid, 5-25 parts of high-temperature resistant additive, 0.5-3 parts of zirconium oxide, 0.5-3 parts of yttrium oxide, 0.1-0.9 part of lanthanum oxide, 10-25 parts of silica sol and 10-50 parts of water;
the environment-friendly high-temperature binder is prepared by the following steps:
adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 2-5h under the conditions that the temperature is 80-100 ℃ and the stirring speed is 8000-;
the high-temperature resistant additive is prepared by the following steps:
a1: adding magnesium powder and iodine particles into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, dropwise adding 1/4 tribromophenol solution while stirring under the condition that the stirring speed is 100-300r/min, controlling the dropwise adding speed to be 1-2mL/min, after finishing dropwise adding, continuously stirring until format reaction is initiated, heating to 50-55 ℃, controlling the heating speed to be 1-5 ℃/min, then dropwise adding the rest tribromophenol solution, after finishing dropwise adding, continuously reacting for 1-2h, finishing the reaction, and cooling to room temperature to obtain a format reagent;
a2: adding trimethyl borate and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, introducing nitrogen, cooling to below-25 ℃, dropwise adding a format reagent while stirring under the condition that the stirring speed is 300-one-year sand 500r/min, controlling the dropwise adding speed to be 1 drop/s, after the dropwise adding is finished, carrying out heat preservation reaction for 2-3h, then heating to 0-5 ℃, adding a hydrochloric acid solution, continuously stirring for 30-50min, then adding ethyl acetate, standing for layering, washing an organic phase with distilled water for 3-5 times, then drying with anhydrous sodium sulfate, then carrying out rotary evaporation to remove the solvent, and recrystallizing an evaporation product with 1, 2-dichloroethane to obtain an intermediate product;
a3: under the protection of nitrogen, adding the intermediate product, sodium hydroxide and tetrahydrofuran into a three-neck flask provided with a gas guide tube, a stirrer and a constant-pressure dropping funnel, stirring and dispersing for 2-3h at room temperature and at a stirring speed of 500-600r/min, then dropwise adding a cyanuric chloride solution, heating to reflux after dropwise adding is finished, stirring and reacting for 15-20h, cooling the reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, hydrolyzing the filter cake for 2-3h by using a hydrochloric acid solution, then carrying out vacuum filtration again, and carrying out silica gel column chromatography separation on the filter cake to obtain the high-temperature resistant additive.
2. The environment-friendly high-temperature binder as claimed in claim 1, wherein the ratio of the magnesium powder, the iodine granules and the tribromophenol solution in step A1 is 1.2 g: 0.3 g: 80mL, wherein the tribromophenol solution is tribromophenol according to a ratio of 135 mmol: 150mL of the solution was dissolved in tetrahydrofuran.
3. The environment-friendly high-temperature binder as claimed in claim 1, wherein the trimethyl borate, tetrahydrofuran, the Grignard reagent, the hydrochloric acid solution and ethyl acetate are used in a ratio of 5.6 g: 40mL of: 150mL of: 40mL of: 50mL, and the molar concentration of the hydrochloric acid solution is 2 mol/L.
4. The environment-friendly high-temperature adhesive as claimed in claim 1, wherein the intermediate product, the sodium hydroxide, the tetrahydrofuran and the cyanuric chloride solution in the step A3 are used in a ratio of 31 mmol: 64 mmol: 50mL of: 40mL, wherein the cyanuric chloride solution is cyanuric chloride according to the molar ratio of 10 mmol: 10mL of solution formed by dissolving in tetrahydrofuran, wherein the molar concentration of the hydrochloric acid solution is 2mol/L, and the mixed solvent is dichloromethane and absolute ethyl alcohol according to a volume ratio of 7: 3 in a mixture of two or more.
5. The method for preparing the environment-friendly high-temperature adhesive according to claim 1, comprising the following steps:
the method comprises the following steps: weighing 15-25 parts of titanium dioxide, 15-35 parts of phosphoric acid, 5-25 parts of high-temperature resistant additive, 0.5-3 parts of zirconium oxide, 0.5-3 parts of yttrium oxide, 0.1-0.9 part of lanthanum oxide, 10-25 parts of silica sol and 10-50 parts of water according to parts by weight for later use;
step two: adding titanium dioxide, phosphoric acid, a high-temperature resistant additive, zirconium oxide, yttrium oxide, lanthanum oxide and silica sol into water, and stirring and dispersing for 2-5h under the conditions that the temperature is 80-100 ℃ and the stirring speed is 8000-.
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| CN101426872A (en) * | 2007-02-15 | 2009-05-06 | 中国科学院过程工程研究所 | High temperature resistant inorganic composite adhesive |
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| CN101426872A (en) * | 2007-02-15 | 2009-05-06 | 中国科学院过程工程研究所 | High temperature resistant inorganic composite adhesive |
| CN106220665B (en) * | 2016-07-22 | 2018-06-19 | 华南理工大学 | Expansion type flame retardant of star-like pyrrolotriazine derivatives and preparation method thereof |
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