CN104650126A - Methylol boric acid ester compound of methylbenzotriazole and preparation method thereof - Google Patents
Methylol boric acid ester compound of methylbenzotriazole and preparation method thereof Download PDFInfo
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- CN104650126A CN104650126A CN201310598358.4A CN201310598358A CN104650126A CN 104650126 A CN104650126 A CN 104650126A CN 201310598358 A CN201310598358 A CN 201310598358A CN 104650126 A CN104650126 A CN 104650126A
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- Prior art keywords
- boric acid
- tolyltriazole
- methylol
- ester compound
- acid ester
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- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- -1 Methylol boric acid ester compound Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004327 boric acid Substances 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000010992 reflux Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 3
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 2
- 238000013270 controlled release Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Lubricants (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a methylol boric acid ester compound of methylbenzotriazole and a preparation method thereof. The preparation method is characterized in that methylbenzotriazole and formaldehyde react in the presence of an acid catalyst and a phase transfer catalyst; resultants are purified and purified resultants and boric acid undergo an esterification reaction; resultants and monohydroxyalkyl primary amine further undergo a boric acid esterification reaction; and after moisture is removed by distillation, the methylol boric acid ester compound of methylbenzotriazole is prepared. Through functional group replacement and reaction, the methylol boric acid ester compound of methylbenzotriazole is synthesized. By introducing a methenyl group and a hydroxyalkyl group and through boric acid esterification, water solubility is increased, and the methylol boric acid ester compound of methylbenzotriazole has wear resistance and abrasion resistance. The composition is an organic heterocyclic corrosion inhibitor. As two or more metal-binding controlled-release groups are contained in molecules, the methylol boric acid ester compound of methylbenzotriazole has an excellent antirust effect.
Description
Technical field
The present invention relates to rust-inhibiting additive synthesis technical field, secondary methylol boric acid ester compound of espespecially a kind of tolyltriazole and preparation method thereof.
Background technology
Along with the development of mechanical industry, the range of application of rust-inhibiting additive is in continuous expansion, water-based metal working fluid is because having excellent cooling, cleaning, rust-preventing characteristic, the advantage such as economy and security, be developed rapidly, and be widely used in cutting, grinding, calendering, the metal processing sectors such as punching press and tapping, rust-inhibiting additive is the important component part of water-based metal working fluid, along with the development and application of organic rust preventing additive, inorganic salts rust-inhibiting additive is substituted gradually, mostly practical organic rust preventing additive is by containing N, O, S, P etc. easily provide the organic compound of the atom of lone-pair electron or the active group of unsaturated link(age), carboxyl is natural organic ligand, it is the essential groups with melts combine, the size of its corrosion inhibition, depend primarily on molecular structure, in metallic surface, keying action is played to molecular adsorption.
Tolyltriazole is a kind of heterocyclic inhibiter; by functional group and reaction; the secondary methylol boric acid ester compound of synthesizing methyl benzotriazole; make in its molecule containing plural eluting group; add water-soluble; and by physical adsorption be chemisorbed on metallic surface and form the protective membrane aligned, thus more effectively slow down and suppress corrosion of metal.
Summary of the invention
Secondary methylol boric acid ester compound that the object of the present invention is to provide a kind of tolyltriazole and preparation method thereof.
Technical solution of the present invention is: to achieve these goals, technical solution of the present invention is: after tolyltriazole and formaldehyde react under acid catalyst and phase-transfer catalyst exist, its resultant carries out esterification with boric acid again after purifying, and then carry out acid esterification reaction with monohydroxyalkyl group primary amine further, after dephlegmate divides, the secondary methylol boric acid ester compound of obtained tolyltriazole, specifically comprises following steps:
1). take water as solvent, under acid catalyst and phase-transfer catalyst exist, tolyltriazole (I) and formaldehyde (II) carry out reaction 3 ~ 5 hours at 10 ~ 30 DEG C, reaction mass, through precipitation, after filtration, then spends hot deionised water and dissolves, suction filtration removing unreacted reactant, filtrate removes moisture through underpressure distillation, obtained methylolation benzotriazole compound (III), and its main chemical reactions is:
2). using toluene as water entrainer, the methine derivative (III) of tolyltriazole and boric acid (IV), in the presence of a catalyst, heating reflux reaction 2 ~ 3 hours at 110 ~ 130 DEG C, the methyne acid esterification intermediate product (V) of obtained tolyltriazole, its main chemical reactions is:
3). using toluene as water entrainer, the methyne acid esterification intermediate product (V) of tolyltriazole and monohydroxyalkyl group primary amine, heating reflux reaction is continued at 110 ~ 130 DEG C, water-and-oil separator is separated the water generated, react after 2 ~ 4 hours, underpressure distillation removing toluene, the secondary methylol boric acid ester compound (VI) of obtained tolyltriazole, its main chemical reactions is:
In formula, R is the lower alkylene such as ethylidene, propylidene, isopropylidene, butylidene or isobutylidene.
The mol ratio of described tolyltriazole, formaldehyde, boric acid and monohydroxyalkyl group primary amine is 1 ﹕ 1 ~ 2 ﹕ 1 ~ 1.2:2 ~ 2.4.
The preferred Polyethylene Glycol-600 of described phase-transfer catalyst, polyethylene glycol-800 and cetomacrogol 1000; Its consumption is 2% ~ 5% of tolyltriazole consumption.
Secondary methylol boric acid ester compound of a kind of tolyltriazole of the present invention and preparation method thereof, its feature and advantage are: by functional group and reaction, the secondary methylol boric acid ester compound of synthesizing methyl benzotriazole, introduce methyne and hydroxyalkyl, and through acid esterification, add water-soluble, and there is antifriction and abrasion resistance; Synthetics is a kind of inhibiter of organic heterocyclic, contains the eluting group of two or more and melts combine in molecule, can play excellent rust inhibition; Reaction process is simple, is applicable to suitability for industrialized production.
Embodiment
Embodiment 1
In the four-hole bottle that whipping appts, reflux condensate device and thermometer are housed, add 100mL water, add the sulfuric acid catalyst of 4 grams and the phase-transfer catalyst Polyethylene Glycol-600 of 1.5 grams, add the tolyltriazole of 31 grams and the formaldehyde solution 36.5 grams of 38%, reaction 3 ~ 4 hours is carried out at 10 ~ 30 DEG C, reaction mass is through precipitation, after filtration, dissolve with 100mL deionization hot water again, suction filtration removing unreacted reactant, filtrate removes moisture through underpressure distillation, obtained methylolation benzotriazole compound; In four-hole bottle, add 100mL toluene as water entrainer, add the boric acid of 17 grams, in the presence of a catalyst, heating reflux reaction 2 ~ 3 hours at 110 ~ 130 DEG C, the methyne acid esterification intermediate product of obtained tolyltriazole; In four-hole bottle, add single hydroxyethyl primary amine of 34 grams again, at 110 ~ 130 DEG C, continue heating reflux reaction, water-and-oil separator is separated the water generated, react after 2 ~ 4 hours, stopped reaction, underpressure distillation removing toluene, the secondary methylol boric acid ester of obtained tolyltriazole.
Embodiment 2
In the four-hole bottle that whipping appts, reflux condensate device and thermometer are housed, add 110mL water, add the sulfuric acid catalyst of 4 grams and the phase-transfer catalyst polyethylene glycol-800 of 1.2 grams, add the tolyltriazole of 34 grams and the formaldehyde solution 30 grams of 38%, reaction 3.5 ~ 4.5 hours is carried out at 10 ~ 30 DEG C, reaction mass is through precipitation, after filtration, dissolve with 150mL deionization hot water again, suction filtration removing unreacted reactant, filtrate removes moisture through underpressure distillation, obtained methylolation benzotriazole compound; In four-hole bottle, add 100mL toluene as water entrainer, add the boric acid of 17.5 grams, in the presence of a catalyst, heating reflux reaction 2 ~ 3 hours at 110 ~ 130 DEG C, the methyne acid esterification intermediate product of obtained tolyltriazole; In four-hole bottle, add single hydroxyl sec.-propyl primary amine of 42 grams again, at 110 ~ 130 DEG C, continue heating reflux reaction, water-and-oil separator is separated the water generated, react after 2 ~ 4 hours, stopped reaction, underpressure distillation removing toluene, the secondary methylol boric acid ester of obtained tolyltriazole.
Embodiment 3
In the four-hole bottle that whipping appts, reflux condensate device and thermometer are housed, add 130mL water, add the sulfuric acid catalyst of 5 grams and the phase-transfer catalyst cetomacrogol 1000 of 0.8 gram, add the tolyltriazole of 37 grams and the formaldehyde solution 23 grams of 38%, reaction 4 ~ 5 hours is carried out at 10 ~ 30 DEG C, reaction mass is through precipitation, after filtration, dissolve with 150mL deionization hot water again, suction filtration removing unreacted reactant, filtrate removes moisture through underpressure distillation, obtained methylolation benzotriazole compound; In four-hole bottle, add 120mL toluene as water entrainer, add the boric acid of 17.2 grams, in the presence of a catalyst, heating reflux reaction 2 ~ 3 hours at 110 ~ 130 DEG C, the methyne acid esterification intermediate product of obtained tolyltriazole; In four-hole bottle, add single hydroxyethyl primary amine of 34 grams again, at 110 ~ 130 DEG C, continue heating reflux reaction, water-and-oil separator is separated the water generated, react after 2 ~ 4 hours, stopped reaction, underpressure distillation removing toluene, the secondary methylol boric acid ester of obtained tolyltriazole.
The above; embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under the prerequisite of spirit not departing from the technology of the present invention; the various distortion that this area engineering technical personnel make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (2)
1. the secondary methylol boric acid ester compound and preparation method thereof of a tolyltriazole, it is characterized in that: after tolyltriazole and formaldehyde react under acid catalyst and phase-transfer catalyst exist, its resultant carries out esterification with boric acid again after purifying, and then carry out acid esterification reaction with monohydroxyalkyl group primary amine further, after dephlegmate divides, the secondary methylol boric acid ester compound of obtained tolyltriazole, specifically comprises following steps:
1). take water as solvent, under acid catalyst and phase-transfer catalyst exist, tolyltriazole and formaldehyde carry out reaction 3 ~ 5 hours at 10 ~ 30 DEG C, reaction mass is through precipitation, after filtration, then spend hot deionised water and dissolve, suction filtration removing unreacted reactant, filtrate removes moisture through underpressure distillation, obtained methylolation benzotriazole compound;
2). using toluene as water entrainer, the methine derivative of tolyltriazole and boric acid, in the presence of a catalyst, heating reflux reaction 2 ~ 3 hours at 110 ~ 130 DEG C, the methyne acid esterification intermediate product of obtained tolyltriazole;
3). using toluene as water entrainer, the methyne acid esterification intermediate product of tolyltriazole and monohydroxyalkyl group primary amine, heating reflux reaction is continued at 110 ~ 130 DEG C, water-and-oil separator is separated the water generated, react after 2 ~ 4 hours, underpressure distillation removing toluene, the secondary methylol boric acid ester compound of obtained tolyltriazole.
2. the secondary methylol boric acid ester compound and preparation method thereof of a kind of tolyltriazole according to claim 1, is characterized in that: the mol ratio of described tolyltriazole, formaldehyde, boric acid and monohydroxyalkyl group primary amine is 1 ﹕ 1 ~ 2 ﹕ 1 ~ 1.2:2 ~ 2.4; The preferred Polyethylene Glycol-600 of described phase-transfer catalyst, polyethylene glycol-800 and cetomacrogol 1000; Its consumption is 2% ~ 5% of tolyltriazole consumption.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310598358.4A CN104650126B (en) | 2013-11-25 | 2013-11-25 | A kind of secondary methylol boric acid ester compound of TTA and preparation method thereof |
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| CN201310598358.4A CN104650126B (en) | 2013-11-25 | 2013-11-25 | A kind of secondary methylol boric acid ester compound of TTA and preparation method thereof |
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| CN104650126A true CN104650126A (en) | 2015-05-27 |
| CN104650126B CN104650126B (en) | 2017-08-25 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201658A (en) * | 2013-04-04 | 2014-10-27 | ユシロ化学工業株式会社 | Water soluble functional fluid with putrefaction resistance |
| CN104232245A (en) * | 2013-06-24 | 2014-12-24 | 中国石油天然气股份有限公司 | Preparation of water-soluble boron-containing antirust agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014201658A (en) * | 2013-04-04 | 2014-10-27 | ユシロ化学工業株式会社 | Water soluble functional fluid with putrefaction resistance |
| CN104232245A (en) * | 2013-06-24 | 2014-12-24 | 中国石油天然气股份有限公司 | Preparation of water-soluble boron-containing antirust agent |
Non-Patent Citations (1)
| Title |
|---|
| 柴多里，等: "含氮杂环硼酸酯的合成及其摩擦学性能", 《润滑与密封》 * |
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