CN117924708A - Preparation method of silane oligomer aqueous solution for metal protection - Google Patents
Preparation method of silane oligomer aqueous solution for metal protection Download PDFInfo
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- CN117924708A CN117924708A CN202410144259.7A CN202410144259A CN117924708A CN 117924708 A CN117924708 A CN 117924708A CN 202410144259 A CN202410144259 A CN 202410144259A CN 117924708 A CN117924708 A CN 117924708A
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- coupling agent
- silane coupling
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 61
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 85
- 239000000413 hydrolysate Substances 0.000 claims abstract description 84
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 79
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000004593 Epoxy Substances 0.000 claims abstract description 60
- 239000007822 coupling agent Substances 0.000 claims abstract description 58
- 238000002161 passivation Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 13
- 238000004383 yellowing Methods 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 42
- 239000000376 reactant Substances 0.000 claims description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 16
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 14
- 239000008397 galvanized steel Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 5
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 4
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 4
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- XCOASYLMDUQBHW-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)butan-1-amine Chemical compound CCCCNCCC[Si](OC)(OC)OC XCOASYLMDUQBHW-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- 230000007062 hydrolysis Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000012224 working solution Substances 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of metal surface treatment and protection, and particularly discloses a preparation method of a silane oligomer aqueous solution for metal protection. The preparation method of the silane oligomer aqueous solution comprises the following steps: (1) Mixing water and acid, dropwise adding an epoxy silane coupling agent, and fully hydrolyzing to obtain an epoxy silane coupling agent hydrolysate solution; (2) Mixing water and acid, dropwise adding an aminosilane coupling agent, and fully hydrolyzing to obtain an aminosilane coupling agent hydrolysate solution; (3) Mixing the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent, and preserving the temperature at 50-90 ℃ for 0.5-2 h to carry out ring-opening polymerization reaction to obtain the aqueous solution of the silane oligomer. After the silane oligomer aqueous solution is coated on the metal surface, the passivation film obtained after drying has good corrosion resistance and high-temperature yellowing resistance.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment and protection, and particularly relates to a preparation method of a silane oligomer aqueous solution for metal protection.
Background
The silane coupling agent contains silicon functional groups and carbon functional groups in molecules, is an excellent chemical modifier and treating agent for inorganic and composite materials, and is widely applied to the fields of paint, building, automobile, electronics, aviation and the like. The silane oligomer refers to a small molecular polymer with higher functionality obtained by hydrolysis and condensation reaction of one or more than two silane coupling agents. The silane oligomer has the advantages of low VOC, high boiling point, high temperature resistance, high functional group equivalent, and the like, and has wide application prospect in different industries such as the bonding sealing field, the paint coating industry, the plastic resin modification field, the powder surface treatment field, and the like.
At present, the silane oligomer is mainly reported by adopting an organic solvent method, reacting a silane coupling agent with water under the action of a catalyst, and separating the solvent from the catalyst to obtain the silane oligomer. For example, US6391999 reports that a silane hydrolysis oligomer is obtained by hydrolysis and condensation reaction of an epoxy silane coupling agent and water in an alcohol solvent using a cation exchange resin as a catalyst. For example, US7893183 reports the use of epoxysilanes and other copolymerizable silanes in a non-alcoholic chemical solvent in the presence of a catalyst to react with water to give epoxysilane oligomers as one of the components of aqueous coatings. For example, CN111205464a adopts a solvent method to synthesize the application of the coupling agent oligomer solution as semiconductor photoresist tackifier. The advantage of using a solvent process is that the degree of condensation of the oligomer can be controlled by varying the ratio of water to silane in the reaction mixture, with the disadvantage of requiring additional steps to remove solvent and catalyst.
It has also been reported that a silane coupling agent and water are directly mixed to carry out hydrolysis reaction to obtain a coupling agent hydrolysis solution. For example, CN115110318a reports that an epoxy silane coupling agent is mixed with water to perform hydrolysis reaction to obtain a pre-hydrolyzed solution, and then an acid is added to adjust pH, and the obtained hydrolyzed solution of the epoxy silane coupling agent is applied to glass fiber cloth to enhance the mechanical strength of glass fibers. For another example, CN113980577a reports that pre-hydrolyzed organosilicon precursors suitable for stone protection are obtained by first mixing and heating water, polyol and organic base, and then adding aminosilane and titanate coupling agent thereto for heat refluxing.
At present, the use of an aqueous solution of oligomers copolymerized by different silane coupling agents as a metal surface treatment agent for metal corrosion prevention is not reported.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a method for preparing an aqueous solution of a silane oligomer for metal protection. The invention adopts different silane coupling agents (containing organic functional groups) to obtain a silane oligomer aqueous solution with good storage stability, and then the obtained silane oligomer aqueous solution is applied to metal surface treatment and protection. The silane oligomer has the advantages of high temperature resistance and high functional group equivalent, so that the silane oligomer is very suitable for being applied to a metal surface passivation film, and the passivation film has good corrosion resistance and high temperature yellowing resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing an aqueous solution of a silane oligomer for metal protection, comprising the steps of:
(1) Mixing water and acid, dropwise adding an epoxy silane coupling agent, and fully hydrolyzing and reacting a silicon oxygen group on the epoxy silane coupling agent at the pH of between 0 and 2 and between 0 and 100 ℃ in a system to obtain an epoxy silane coupling agent hydrolysate solution;
(2) Mixing water and acid, dropwise adding an aminosilane coupling agent, and fully hydrolyzing silicon oxygen groups on the aminosilane coupling agent at the pH of between 0 and 2 and between 0 and 100 ℃ to obtain an aminosilane coupling agent hydrolysate solution;
(3) Mixing the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent, preserving heat for 0.5-2 h at 50-90 ℃, and carrying out ring-opening polymerization reaction on epoxy groups on the hydrolysate of the epoxy silane coupling agent and amino groups on the hydrolysate of the amino silane coupling agent to obtain the aqueous solution of the silane oligomer.
Preferably, the pH in the step (1) system is=1.0±0.5, and the pH in the step (2) system is=1.0±0.5.
Preferably, the epoxysilane coupling agent in step (1) comprises one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- [ (2, 3) -epoxypropoxy ] propylmethyldiethoxysilane, more preferably 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- [ (2, 3) -epoxypropoxy ] propylmethyldiethoxysilane.
Further, the acid in the step (1) is one of phosphoric acid or organic phosphonic acid, wherein the organic phosphonic acid comprises phytic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid and diethylenetriamine penta-methylene phosphonic acid; preferably, the acid is 85wt% phosphoric acid, hydroxyethylidene diphosphonic acid. The hydrolysis reaction of the epoxy silane coupling agent can be carried out under either acidic or alkaline conditions, and phosphoric acid or organic phosphonic acid is selected as a hydrolysis accelerator in the invention because the epoxy silane coupling agent has the highest hydrolysis rate under strong acidic conditions, and further large-scale condensation between silicon hydroxyl groups obtained after the hydrolysis does not substantially occur, so that more silicon hydroxyl groups on the hydrolysate of the epoxy silane coupling agent are retained to the greatest extent, and the phosphoric acid or organic phosphonic acid can provide the required strong acidic (ph=0 to 2, preferably ph=1.0±0.5) hydrolysis conditions. Of course, strong acids such as sulfuric acid, hydrochloric acid and nitric acid can also provide strong acid conditions, but the inventor proves that phosphoric acid or organic phosphonic acid can be used as one of passivation solution components for zinc or aluminum corrosion prevention treatment, so that the corrosion resistance of a passivation film can be improved, the sulfuric acid, the hydrochloric acid and the nitric acid cannot be replaced, and the phosphoric acid or the organic phosphonic acid is a relatively warm and safe acid, so that the passivation film is safer in industrial use.
Further, the acid amount in the step (1) is 0.5 to 5%, preferably 1 to 2%, more preferably 1% of the total mass of the hydrolysate solution of the epoxy silane coupling agent in the step (1); the dosage of the epoxy silane coupling agent in the step (1) is 5-50% of the total mass of the hydrolysate solution of the epoxy silane coupling agent in the step (1), preferably 20-30%, and more preferably 25%; in addition, the epoxy silane coupling agent can be subjected to hydrolysis reaction at any temperature of 0-100 ℃ under the catalysis of phosphoric acid or organic phosphonic acid, preferably, any environment temperature of 0-40 ℃ is selected, no special heating or cooling is needed, the epoxy silane coupling agent is dropwise added, the dropwise adding time of the epoxy silane coupling agent is 0.5-2 h, the reactant is refluxed for 1h at 90 ℃ after the epoxy silane coupling agent is dropwise added, so that the silicon oxygen groups on the epoxy silane coupling agent are fully hydrolyzed, and the reactant is cooled to below 40 ℃ after the reflux is completed, so that a clear and transparent hydrolysate solution of the epoxy silane coupling agent is obtained; more preferably, the epoxy silane coupling agent is dropwise added at 30 ℃ for 1h, after the dropwise addition is completed, the reactant is refluxed at 90 ℃ for 1h, and after the reflux is completed, the reactant is cooled to below 40 ℃ to obtain a clear and transparent hydrolysate solution of the epoxy silane coupling agent.
Preferably, the aminosilane coupling agent in step (2) comprises one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N- (N-butyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-aminopropyl methyldimethoxysilane, more preferably 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyldimethoxysilane.
Further, the acid in the step (2) is one of phosphoric acid or organic phosphonic acid, wherein the organic phosphonic acid comprises phytic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid and diethylenetriamine penta-methylene phosphonic acid; preferably, the acid is 85wt% phosphoric acid, hydroxyethylidene diphosphonic acid. The hydrolysis reaction of the aminosilane coupling agent can be carried out under either acidic or alkaline conditions, and phosphoric acid or organic phosphonic acid is selected as a hydrolysis accelerator in the invention because the silicon hydroxyl groups obtained after the hydrolysis of the aminosilane coupling agent under the strong acidic condition are not condensed further on a large scale, more silicon hydroxyl groups on the hydrolysate of the aminosilane coupling agent are retained to the maximum extent, the hydrolysate solution of the aminosilane coupling agent is also the most stable, and the phosphoric acid or organic phosphonic acid can provide the required strong acidic (pH=0 to 2, preferably pH=1.0.+ -. 0.5) hydrolysis conditions. Of course, strong acids such as sulfuric acid, hydrochloric acid and nitric acid can also provide strong acid conditions, but the inventor proves that phosphoric acid or organic phosphonic acid can be used as one of passivation solution components for zinc or aluminum corrosion prevention treatment, so that the corrosion resistance of a passivation film can be improved, the sulfuric acid, the hydrochloric acid and the nitric acid cannot be replaced, and the phosphoric acid or the organic phosphonic acid is a relatively warm and safe acid, so that the passivation film is safer in industrial use.
Further, the acid amount in the step (2) is 5% -30%, preferably 20% -30%, more preferably 25% of the total mass of the aminosilane coupling agent hydrolysate solution of the step (2); the dosage of the aminosilane coupling agent in the step (2) is 5-30% of the total mass of the hydrolysate solution of the aminosilane coupling agent in the step (2), preferably 20-30%, and more preferably 25%; and the mass ratio of the acid in the step (2) to the aminosilane coupling agent is 1:1, the aminosilane hydrolysate solution thus obtained is most stable, because: the acid (phosphoric acid or organic phosphonic acid) with equal mass ratio is mixed with the amino silane coupling agent, the mole number of the phosphorus hydroxyl (P-OH) is far more than 2 times of that of the amino group, the amino silane coupling agent still can provide strong acid (pH=0-2) hydrolysis conditions, and the silicon hydroxyl groups obtained after the amino silane coupling agent is hydrolyzed under the strong acid conditions can not be condensed in a large scale. The aminosilane coupling agent can be subjected to hydrolysis reaction at any temperature of 0-100 ℃ under the catalysis of phosphoric acid or organic phosphonic acid, preferably, any environment temperature of 0-40 ℃ is selected, no special heating or cooling is needed, the aminosilane coupling agent is dropwise added, the dropwise adding time of the aminosilane coupling agent is 0.5-2 h, the reactants are refluxed for 1h at 90 ℃ after the aminosilane coupling agent is dropwise added, so that the silica groups on the aminosilane coupling agent are fully hydrolyzed, and the reactants are cooled to below 40 ℃ after the reflux is completed, so that a clear and transparent aminosilane coupling agent hydrolysate solution is obtained; more preferably, the aminosilane coupling agent is dropwise added at 30 ℃ for 1h, after the dropwise addition is completed, the reactant is refluxed at 90 ℃ for 1h, and after the reflux is completed, the reactant is cooled to below 40 ℃ to obtain a clear and transparent aminosilane coupling agent hydrolysate solution.
Still further, step (3) is to mix the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the aminosilane coupling agent, heat up to a temperature of 50-70 ℃, heat up to a temperature of 1-2 hours, more preferably to a temperature of 60 ℃ and heat up to a temperature of 1 hour, thereby obtaining a clear and transparent aqueous solution of the silane oligomer. Under the condition, the epoxy group on the hydrolysate of the epoxy silane coupling agent and the amino group on the hydrolysate of the amino silane coupling agent are subjected to ring-opening polymerization reaction to generate the silane oligomer aqueous solution.
Further, in the step (3), the epoxy silane coupling agent hydrolysate solution and the aminosilane coupling agent hydrolysate solution are mixed according to a mass ratio of 1:1-2:1.
Preferably, the epoxy silane coupling agent in the step (1) is 3- (2, 3-glycidoxy) propyl trimethoxy silane or 3- (2, 3-glycidoxy) propyl triethoxy silane, the amino silane coupling agent in the step (2) is 3-aminopropyl trimethoxy silane or 3-aminopropyl triethoxy silane, and the epoxy silane coupling agent hydrolysate solution and the amino silane coupling agent hydrolysate solution are mixed according to a mass ratio of 2:1 in the step (3).
In addition, the invention also aims at applying the silane oligomer aqueous solution prepared by the method to metal protection, coating the silane oligomer aqueous solution on the metal surface, and drying to obtain the passivation film, wherein the silane oligomer can improve the corrosion resistance and the high-temperature yellowing resistance of the passivation film. Further, the metal includes a hot dip galvanized steel sheet (strip), an electrogalvanized steel sheet (strip), an aluminized silicon steel sheet (strip), an aluminized zinc steel sheet (strip), and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. The hydrolysate solution of the silane coupling agent is synthesized without adopting an organic solvent and has mild conditions;
2. The silane oligomer aqueous solution obtained by the method has good storage stability;
3. The silane oligomer aqueous solution prepared by copolymerization of the silane coupling agents based on different organic functional groups is used as a metal surface treatment agent for metal corrosion prevention, so that the passivation film has good corrosion resistance and high-temperature yellowing resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples.
All the raw materials in the following examples or comparative examples of the present invention were commercially available unless otherwise specified.
Example 1
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
(1) Adding 1g of 85wt% phosphoric acid and 74g of deionized water into a reaction bottle, uniformly dropwise adding 25g of 3- (2, 3-glycidoxy) propyl trimethoxy silane into the reaction bottle within 1h under the condition of stirring at 30 ℃, refluxing the reactant at 90 ℃ for 1h after the dropwise adding is finished, and cooling the reactant to 40 ℃ after the refluxing is finished to obtain a clear and transparent epoxy silane coupling agent hydrolysate solution A1;
(2) 25g of 85wt% phosphoric acid and 50g of deionized water are added into another reaction bottle, 25g of 3-aminopropyl triethoxysilane is evenly added into the reaction bottle in a dropwise manner within 1h under the condition of stirring at 30 ℃, the reactant is refluxed for 1h at 90 ℃ after the dropwise addition, and the reactant is cooled to 40 ℃ after the reflux is completed, so that a clear and transparent aminosilane coupling agent hydrolysate solution B1 is obtained;
(3) Uniformly mixing 50g of the epoxy silane coupling agent hydrolysate solution A1 obtained in the step (1) and 50g of the aminosilane coupling agent hydrolysate solution B1 obtained in the step (2), heating to 60 ℃, and preserving heat for 1h to perform ring-opening polymerization reaction to obtain a clear and transparent silane oligomer aqueous solution C1; the reaction taking place in this step is as follows:
Example 2
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
(1) Adding 1g of 85wt% phosphoric acid and 74g of deionized water into a reaction bottle, uniformly dropwise adding 25g of beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane into the reaction bottle within 1h under the condition of stirring at 30 ℃, refluxing the reactant at 90 ℃ for 1h after the dropwise adding is finished, and cooling the reactant to 40 ℃ after the refluxing is finished to obtain a clear and transparent epoxy silane coupling agent hydrolysate solution A2;
(2) Adding 25g of 85wt% phosphoric acid and 50g of deionized water into another reaction bottle, uniformly dropwise adding 25g of 3-aminopropyl trimethoxy silane into the reaction bottle within 1h under the condition of stirring at 30 ℃, refluxing the reactants at 90 ℃ for 1h after the dropwise adding, and cooling the reactants to 40 ℃ after the refluxing is finished to obtain a clear and transparent aminosilane coupling agent hydrolysate solution B2;
(3) And (2) uniformly mixing 50g of the epoxy silane coupling agent hydrolysate solution A2 obtained in the step (1) and 50g of the aminosilane coupling agent hydrolysate solution B2 obtained in the step (2), heating to 60 ℃, and preserving the heat for 1h to perform ring-opening polymerization reaction to obtain a clear and transparent silane oligomer aqueous solution C2.
Example 3
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
(1) Adding 1g of hydroxyethylidene diphosphonic acid powder and 74g of deionized water into a reaction bottle, uniformly dripping 25g of 3- [ (2, 3) -glycidoxy ] propyl methyl diethoxysilane into the reaction bottle in 1h under the condition of stirring at 30 ℃, refluxing the reactants at 90 ℃ for 1h after the dripping is finished, and cooling the reactants to 40 ℃ after the refluxing is finished to obtain a clear and transparent hydrolysate solution A3 of the epoxy silane coupling agent;
(2) Adding 25g of hydroxyethylidene diphosphonic acid powder and 50g of deionized water into another reaction bottle, uniformly dropwise adding 25g of 3-aminopropyl methyl dimethoxy silane into the reaction bottle within 1h under the condition of stirring at 30 ℃, refluxing reactants for 1h at 90 ℃ after the dropwise adding is finished, and cooling the reactants to 40 ℃ after the refluxing is finished to obtain a clear and transparent aminosilane coupling agent hydrolysate solution B3;
(3) And (3) uniformly mixing 50g of the epoxy silane coupling agent hydrolysate solution A3 obtained in the step (1) and 50g of the aminosilane coupling agent hydrolysate solution B3 obtained in the step (2), heating to 60 ℃, and preserving the heat for 1h to perform ring-opening polymerization reaction to obtain a clear and transparent silane oligomer aqueous solution C3.
Example 4
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
50g of the epoxy silane coupling agent hydrolysate solution A1 obtained in the step (1) in the example 1 and 50g of the aminosilane coupling agent hydrolysate solution B3 obtained in the step (2) in the example 3 are uniformly mixed, the temperature is raised to 60 ℃, and the temperature is kept for 1h for ring-opening polymerization reaction, so that a clear and transparent silane oligomer aqueous solution C4 is obtained.
Example 5
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
50g of the epoxy silane coupling agent hydrolysate solution A2 obtained in the step (1) in the example 2 and 50g of the aminosilane coupling agent hydrolysate solution B1 obtained in the step (2) in the example 1 are uniformly mixed, the temperature is raised to 60 ℃, the temperature is kept for 1h, and the ring-opening polymerization reaction is carried out, so that a clear and transparent silane oligomer aqueous solution C5 is obtained.
Example 6
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
50g of the epoxy silane coupling agent hydrolysate solution A3 obtained in the step (1) in the example 3 and 50g of the aminosilane coupling agent hydrolysate solution B2 obtained in the step (2) in the example 2 are uniformly mixed, the temperature is raised to 60 ℃, the heat is preserved for 1h for ring-opening polymerization reaction, and a clear and transparent silane oligomer aqueous solution C6 is obtained.
Example 7
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
uniformly mixing 66g of the epoxy silane coupling agent hydrolysate solution A1 obtained in the step (1) in the embodiment 1 and 33g of the aminosilane coupling agent hydrolysate solution B2 obtained in the step (2) in the embodiment 2, heating to 60 ℃, and preserving heat for 1h to perform ring-opening polymerization reaction to obtain a clear and transparent silane oligomer aqueous solution C7; this step occurs as follows:
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
60g of the epoxy silane coupling agent hydrolysate solution A2 obtained in the step (1) in the example 2 and 40g of the aminosilane coupling agent hydrolysate solution B3 obtained in the step (2) in the example 3 are uniformly mixed, the temperature is raised to 60 ℃, the temperature is kept for 1h, and the ring-opening polymerization reaction is carried out, so that a clear and transparent silane oligomer aqueous solution C8 is obtained.
Example 9
A preparation method of a silane oligomer aqueous solution for metal protection comprises the following steps:
55g of the hydrolysate solution A3 of the epoxy silane coupling agent obtained in the step (1) in the example 3 and 45g of the hydrolysate solution B1 of the aminosilane coupling agent obtained in the step (2) in the example 1 are uniformly mixed, the temperature is raised to 60 ℃, the heat is preserved for 1h for ring-opening polymerization reaction, and a clear and transparent aqueous solution C9 of the silane oligomer is obtained.
Evaluation of the effect of the silane oligomer of the present invention applied to metal passivation treatment:
The hot dip galvanized steel sheet is used as a substrate to be passivated, and the passivation treatment method of the hot dip galvanized steel sheet comprises the following steps:
The solid contents of the silane oligomer aqueous solutions C1 to C9 prepared in examples 1 to 9 were respectively adjusted to 10% as passivation working solutions, the silane oligomer aqueous solutions were coated on the cleaned galvanized steel sheet using 8 μm wire rods, and then the galvanized steel sheet was placed in an oven at 260 ℃ for 6 seconds to obtain passivated galvanized steel sheets, the film thickness of the passivation film on the galvanized steel sheet being 0.8 μm.
And then carrying out corrosion resistance detection and high-temperature yellowing resistance detection on the passivated galvanized steel sheet.
(1) And (3) corrosion resistance detection: and (3) evaluating neutral salt fog, wherein a salt fog test is carried out according to national standard GB/T10125-2012 artificial atmosphere corrosion test salt fog test, the test temperature is 35+/-2 ℃, the NaCl concentration is 50+/-5 g/L, the time that the white rust area of each passivated galvanized steel sheet is more than 5% is recorded, the white rust area of the surface of the galvanized steel sheet after 120 hours is required to be less than or equal to 5%, and otherwise, the corrosion resistance is judged to be unqualified.
(2) High temperature resistance yellowing performance detection: and (3) placing the passivated galvanized steel sheet in an oven at 300 ℃ for 30 minutes, measuring the color difference change delta E before and after baking by using a color difference meter after cooling to room temperature, wherein the delta E is required to be less than 3, and otherwise, judging that the high-temperature yellowing resistance is unqualified.
The test results are shown in table 1 below:
the passivation working fluids of comparative examples 1 to 7 in table 1 above are respectively:
Comparative example 1 was a passivation working solution prepared by directly using the epoxy silane hydrolysate solution A1 obtained in step (1) of example 1 of the present invention, and adjusting the solid content to 10%;
comparative example 2 is an epoxy silane hydrolysate solution A2 obtained in the step (1) in the example 2 of the present invention, and the solution A2 is used as a passivation working solution after the solid content is adjusted to 10%;
Comparative example 3 is an epoxy silane hydrolysate solution A3 obtained in step (1) in example 3 of the present invention, and the solution A3 is used as a passivation working solution after the solid content is adjusted to 10%;
comparative example 4 is an aminosilane coupling agent hydrolysate solution B1 obtained in step (2) of example 1 of the present invention directly, and the hydrolysate solution B was used as a passivation working solution after the solid content was adjusted to 10%;
Comparative example 5 is an aminosilane coupling agent hydrolysate solution B2 obtained in step (2) of example 2 of the present invention, which was used as a passivation working solution after having its solid content adjusted to 10%;
Comparative example 6 is an aminosilane coupling agent hydrolysate solution B3 obtained in step (2) of example 3 of the present invention directly, and the hydrolysate solution B was used as a passivation working solution after the solid content was adjusted to 10%;
comparative example 7 was an organic-inorganic composite chromium-free passivating agent DS980-10B produced by applicant company, and the passivating working solution was obtained by adjusting the solid content to 10%.
As can be seen from the test data in the table 1, the silane oligomer aqueous solution provided by the invention is used as the passivation treatment liquid of the galvanized steel sheet, and the formed passivation film has good corrosion resistance and high-temperature yellowing resistance. While the corrosion resistance of each of comparative examples 1 to 6 was not satisfactory, the high temperature yellowing resistance of comparative examples 4 to 7 was not higher than 300 ℃.
In addition, the silane oligomer provided by the invention is applied to the treatment of electrogalvanized steel plates, aluminized zinc steel plates and aluminized silicon steel plates, and has good corrosion resistance and high-temperature yellowing resistance. Therefore, the silane oligomer aqueous solution prepared by the invention can be used as passivation solution for hot dip galvanized steel plates (bands), electrogalvanized steel plates (bands), aluminized silicon steel plates (bands) and aluminized zinc steel plates (bands), and the formed passivation film has good corrosion resistance and high-temperature yellowing resistance.
Claims (10)
1. A method for preparing an aqueous solution of a silane oligomer for metal protection, comprising the steps of:
(1) Mixing water and acid, dropwise adding an epoxy silane coupling agent, and fully hydrolyzing and reacting a silicon oxygen group on the epoxy silane coupling agent at the pH of between 0 and 2 and between 0 and 100 ℃ in a system to obtain an epoxy silane coupling agent hydrolysate solution;
(2) Mixing water and acid, dropwise adding an aminosilane coupling agent, and fully hydrolyzing silicon oxygen groups on the aminosilane coupling agent at the pH of between 0 and 2 and between 0 and 100 ℃ to obtain an aminosilane coupling agent hydrolysate solution;
(3) Mixing the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent, preserving heat for 0.5-2 h at 50-90 ℃, and carrying out ring-opening polymerization reaction on epoxy groups on the hydrolysate of the epoxy silane coupling agent and amino groups on the hydrolysate of the amino silane coupling agent to obtain an aqueous solution of the silane oligomer;
the acid in step (1) and step (2) is each independently selected from one of phosphoric acid or organic phosphonic acid.
2. The method according to claim 1, wherein the pH in the system of step (1) is=1.0±0.5, and the pH in the system of step (2) is=1.0±0.5.
3. The method according to claim 1, wherein in the step (1), the epoxysilane coupling agent comprises at least one of 3- (2, 3-epoxypropoxy) propyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- [ (2, 3) -epoxypropoxy ] propylmethyldiethoxysilane; and/or
In the step (2), the aminosilane coupling agent comprises at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, N- (N-butyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane and 3-aminopropyl methyldimethoxysilane; and/or
The acid in step (1) and step (2) is selected from any one of 85wt% phosphoric acid, phytic acid, aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid and diethylenetriamine penta-methylene phosphonic acid.
4. A process according to any one of claims 1 to 3, wherein in step (1), the mass ratio of the acid to the hydrolysate solution of the epoxy silane coupling agent is from 0.5% to 5%, preferably from 1% to 2%, more preferably 1%; the mass ratio of the epoxy silane coupling agent to the hydrolysate solution of the epoxy silane coupling agent is 5-50%, preferably 20-30%, more preferably 25%; and/or
In the step (2), the mass ratio of the acid to the aminosilane coupling agent hydrolysate solution is 5-30%, preferably 20-30%, more preferably 25%; the mass ratio of the acid to the aminosilane coupling agent is 1:1; and/or
In the step (3), the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent are mixed according to the mass ratio of 1:1-2:1.
5. A production method according to any one of claims 1 to 3, wherein the epoxysilane coupling agent in step (1) is 3- (2, 3-glycidoxy) propyltrimethoxysilane or 3- (2, 3-glycidoxy) propyltriethoxysilane, the aminosilane coupling agent in step (2) is 3-aminopropyl trimethoxysilane or 3-aminopropyl triethoxysilane, and the epoxysilane coupling agent hydrolysate solution and the aminosilane coupling agent hydrolysate solution are mixed in a mass ratio of 2:1 in step (3).
6. The preparation method according to any one of claims 1 to 3, wherein in the step (1), an epoxy silane coupling agent is dripped at 0 to 40 ℃ for 0.5 to 2 hours, after dripping, reactants are refluxed at 90 ℃ for 1 hour, and after the reflux is completed, the reactants are cooled to below 40 ℃ to obtain a clear and transparent hydrolysate solution of the epoxy silane coupling agent; and/or
In the step (2), an aminosilane coupling agent is dripped at the temperature of between 0 and 40 ℃ for 0.5 to 2 hours, after the dripping is finished, reactants are refluxed at the temperature of 90 ℃ for 1 hour, and after the refluxing is finished, the reactants are cooled to below 40 ℃ to obtain a clear and transparent aminosilane coupling agent hydrolysate solution; and/or
In the step (3), after the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent are mixed, the temperature is raised to 50-70 ℃, and the heat is preserved for 1-2 hours, so that a clear and transparent silane oligomer aqueous solution is obtained.
7. The preparation method of claim 6, wherein in the step (1), the epoxy silane coupling agent is dripped at 30 ℃ for 1h, after dripping, reactants are refluxed at 90 ℃ for 1h, and after refluxing, the reactants are cooled to below 40 ℃ to obtain clear and transparent hydrolysate solution of the epoxy silane coupling agent; and/or
In the step (2), an aminosilane coupling agent is dropwise added at 30 ℃ for 1h, after the dropwise addition is completed, reactants are refluxed at 90 ℃ for 1h, and after the reflux is completed, the reactants are cooled to below 40 ℃ to obtain a clear and transparent aminosilane coupling agent hydrolysate solution; and/or
In the step (3), after the hydrolysate solution of the epoxy silane coupling agent and the hydrolysate solution of the amino silane coupling agent are mixed, the temperature is raised to 60 ℃, and the heat is preserved for 1h, so that a clear and transparent silane oligomer aqueous solution is obtained.
8. Use of an aqueous solution of a silane oligomer prepared according to the method of any one of claims 1 to 7 for metal protection.
9. The use according to claim 8, wherein the passivation film is obtained after the aqueous solution of the silane oligomer prepared by the method according to any one of claims 1 to 7 is coated on the metal surface and dried, and the silane oligomer can improve the corrosion resistance and the high temperature yellowing resistance of the passivation film.
10. The use according to claim 8, wherein the metal comprises any one of a hot dip galvanized steel, an electrogalvanized steel, an aluminized silicon steel and an aluminized zinc steel.
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