CN104650126B - A kind of secondary methylol boric acid ester compound of TTA and preparation method thereof - Google Patents
A kind of secondary methylol boric acid ester compound of TTA and preparation method thereof Download PDFInfo
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- CN104650126B CN104650126B CN201310598358.4A CN201310598358A CN104650126B CN 104650126 B CN104650126 B CN 104650126B CN 201310598358 A CN201310598358 A CN 201310598358A CN 104650126 B CN104650126 B CN 104650126B
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- tta
- boric acid
- methylol
- ester compound
- acid ester
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- -1 methylol boric acid ester compound Chemical group 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 238000010992 reflux Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- 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
- 239000003054 catalyst Substances 0.000 claims description 4
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229960003511 macrogol Drugs 0.000 claims description 3
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 3
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005299 abrasion Methods 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 2
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- RYMMGWFFSFXBIQ-UHFFFAOYSA-N hydroxymethoxyboronic acid Chemical group OCOB(O)O RYMMGWFFSFXBIQ-UHFFFAOYSA-N 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000002242 deionisation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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- Lubricants (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses secondary methylol boric acid ester compound of a kind of TTA and preparation method thereof, it is characterized in that：After TTA is reacted with formaldehyde in the presence of acid catalyst and phase transfer catalyst, esterification is carried out after its product is purified with boric acid again, then further acid esterification reaction is carried out with monohydroxyalkyl group primary amine, after moisture is distilled off, the secondary methylol boric acid ester compound of TTA is made；By functional group and reaction, the secondary methylol boric acid ester compound of synthesizing methyl benzotriazole introduces methine and hydroxyalkyl, and through acid esterification, adds water solubility, and with antifriction and abrasion resistance；Synthetic is the eluting group combined containing two or more with metal in a kind of corrosion inhibiter of organic heterocyclic, molecule, can play excellent anti-rust action.
Description
Technical field
The present invention relates to rust-inhibiting additive synthesis technical field, the secondary methylol boric acid of espespecially a kind of TTA
Ester compounds and preparation method thereof.
Background technology
With the development of mechanical industry, the application of rust-inhibiting additive is constantly expanding, water-based metal working fluid because
There is excellent cooling, cleaning, rust-preventing characteristic, economy and security, be developed rapidly, and extensive use
In metal processing sectors such as cutting, grinding, calendering, punching press and tapping, rust-inhibiting additive is the important set of water-based metal working fluid
Into part, with the development and application of organic rust preventing additive, inorganic salts rust-inhibiting additive is gradually substituted, and practical is organic
Rust-inhibiting additive is the organic compound by easily providing the atom of lone pair electrons or the active group of unsaturated bond containing N, O, S, P etc. mostly
Thing, carboxyl is natural organic ligand, is the essential groups combined with metal, and the size of its corrosion inhibition depends primarily on molecule
Structure, key effect is played to Molecular Adsorption in metal surface.
TTA is a kind of heterocyclic corrosion inhibiter, passes through functional group and reaction, synthesizing methyl benzene a pair of horses going side by side three
The secondary methylol boric acid ester compound of nitrogen azoles, makes to contain more than two eluting groups in its molecule, adds water solubility, and lead to
Cross physical absorption and be chemisorbed on metal surface and form the diaphragm aligned, so as to more effectively slow down and suppress metal
Corrosion.
The content of the invention
It is an object of the invention to provide a kind of secondary methylol boric acid ester compound of TTA and its preparation
Method.
The present invention technical solution be：To achieve these goals, technical solution of the invention is：Methylbenzene
After parallel triazole and formaldehyde are reacted in the presence of acid catalyst and phase transfer catalyst, after its product is purified again with boron
Acid carries out esterification, then further carries out acid esterification reaction with monohydroxyalkyl group primary amine, after moisture is distilled off,
The secondary methylol boric acid ester compound of TTA is made, specifically comprises the steps of：
1) is using water as solvent, in the presence of acid catalyst and phase transfer catalyst, TTA（Ⅰ）With formaldehyde
（Ⅱ）In at 10~30 DEG C carry out reaction 3~5 hours, reaction mass by precipitation, after filtering, then spend hot deionised water carry out it is molten
Solution, suction filtration removes unreacted reactant, and filtrate removes moisture through vacuum distillation, and methylolation benzotriazole compound is made（Ⅲ）,
Its main chemical reactions is：
2) is using toluene as water entrainer, the methine derivative of TTA（Ⅲ）And boric acid（Ⅳ）, in catalysis
In the presence of agent, in heating reflux reaction 2~3 hours at 110~130 DEG C, the methine borate of TTA is made
Change intermediate product（Ⅴ）, its main chemical reactions is：
3) is using toluene as water entrainer, the methine acid esterification intermediate product of TTA（Ⅴ）With single hydroxyl
Kiber alkyl amine, in continuing heating reflux reaction at 110~130 DEG C, the water of oil water separator separation generation reacts 2~4 hours
Afterwards, vacuum distillation removes toluene, and the secondary methylol boric acid ester compound of TTA is made（Ⅵ）, its primary chemical is anti-
It should be：
In formula, R is the lower alkylenes such as ethylidene, propylidene, isopropylidene, butylidene or isobutylidene.
Described TTA, formaldehyde, the mol ratio of boric acid and monohydroxyalkyl group primary amine are the ﹕ 1~1.2 of 1 ﹕ 1~2：2
~2.4.
The preferred Macrogol 600 of described phase transfer catalyst, polyethylene glycol-800 and cetomacrogol 1000；Its consumption is
The 2%~5% of TTA quality.
A kind of secondary methylol boric acid ester compound of TTA of the present invention and preparation method thereof, its feature and excellent
Putting is：By functional group and reaction, the secondary methylol boric acid ester compound of synthesizing methyl benzotriazole introduces methine
And hydroxyalkyl, and through acid esterification, water solubility is added, and with antifriction and abrasion resistance；Synthetic is a kind of organic heterocyclic
Corrosion inhibiter, the eluting group combined containing two or more with metal in molecule can play excellent anti-rust action；Reaction process
Simply, it is adapted to industrialized production.
Embodiment
Embodiment 1
In the four-hole bottle equipped with agitating device, reflux condensate device and thermometer, 100mL water is added, 4 grams of sulphur is added
Acid catalyst and 1.5 grams of phase transfer catalyst Macrogol 600, the TTA and 38% formaldehyde of 31 grams of addition
36.5 grams of solution, in carrying out reaction 3~4 hours at 10~30 DEG C, reaction mass is by precipitation, after filtering, then gone with 100mL from
Sub- hot water is dissolved, and suction filtration removes unreacted reactant, and filtrate removes moisture through vacuum distillation, and methylolation benzotriazole is made
Compound；100mL toluene is added into four-hole bottle as water entrainer, the boric acid of 17 grams of addition, in the presence of a catalyst, in 110
Heating reflux reaction 2~3 hours at~130 DEG C, are made the methine acid esterification intermediate product of TTA；Again to
Single ethoxy primary amine of 34 grams of addition in four-hole bottle, in continuing heating reflux reaction at 110~130 DEG C, oil water separator is separated
The water of generation, after reacting 2~4 hours, stops reaction, vacuum distillation removes toluene, and the secondary hydroxyl first of TTA is made
Ylboronic acid ester.
Embodiment 2
In the four-hole bottle equipped with agitating device, reflux condensate device and thermometer, 110mL water is added, 4 grams of sulphur is added
Acid catalyst and 1.2 grams of phase transfer catalyst polyethylene glycol-800, the TTA and 38% formaldehyde of 34 grams of addition
30 grams of solution, in carrying out reaction 3.5~4.5 hours at 10~30 DEG C, reaction mass is by precipitation, after filtering, then is gone with 150mL
Hot deionised water is dissolved, and suction filtration removes unreacted reactant, and filtrate removes moisture through vacuum distillation, and parallel three nitrogen of methylolation benzene are made
Azole compounds；100mL toluene is added into four-hole bottle as water entrainer, 17.5 grams of boric acid is added, in the presence of a catalyst, in
Heating reflux reaction 2~3 hours at 110~130 DEG C, are made the methine acid esterification intermediate product of TTA；
42 grams of single hydroxyl isopropyl primary amine is added into four-hole bottle again, in continuing heating reflux reaction, water-oil separating at 110~130 DEG C
The water of device separation generation, after reacting 2~4 hours, stops reaction, vacuum distillation removes toluene, and TTA is made
Secondary methylol borate.
Embodiment 3
In the four-hole bottle equipped with agitating device, reflux condensate device and thermometer, 130mL water is added, 5 grams of sulphur is added
Acid catalyst and 0.8 gram of phase transfer catalyst cetomacrogol 1000, the TTA and 38% formaldehyde of 37 grams of addition
23 grams of solution, in carrying out reaction 4~5 hours at 10~30 DEG C, reaction mass after filtering, then uses 150mL deionizations by precipitation
Hot water is dissolved, and suction filtration removes unreacted reactant, and filtrate removes moisture through vacuum distillation, and methylolation benzotriazole is made
Compound；120mL toluene is added into four-hole bottle as water entrainer, the boric acid of 17.2 grams of addition, in the presence of a catalyst, in 110
Heating reflux reaction 2~3 hours at~130 DEG C, are made the methine acid esterification intermediate product of TTA；Again to
Single ethoxy primary amine of 34 grams of addition in four-hole bottle, in continuing heating reflux reaction at 110~130 DEG C, oil water separator is separated
The water of generation, after reacting 2~4 hours, stops reaction, vacuum distillation removes toluene, and the secondary hydroxyl first of TTA is made
Ylboronic acid ester.
Described above, embodiment is only that the preferred embodiment of the present invention is described, not to the present invention's
Scope is defined, on the premise of the spirit of the technology of the present invention is not departed from, skill of this area engineers and technicians to the present invention
In various modifications and improvement that art scheme is made, the protection domain that claims of the present invention determination all should be fallen into.
Claims (2)
1. a kind of preparation method of the secondary methylol boric acid ester compound of TTA, it is characterized in that：It is specific include with
Lower step：
1) is using water as solvent, in the presence of acid catalyst and phase transfer catalyst, and TTA is with formaldehyde in 10~30
Carry out reacting 3~5 hours at DEG C, reaction mass is by precipitation, after filtering, then spend hot deionised water and dissolved, suction filtration is removed
Unreacted reactant, filtrate removes moisture through vacuum distillation, and methylolation benzotriazole compound is made, and its structural formula is：
；
2) is using toluene as water entrainer, the methine derivative and boric acid of TTA, in the presence of a catalyst, in
Heating reflux reaction 2~3 hours at 110~130 DEG C, are made the methine acid esterification intermediate product of TTA,
Its structural formula is：
；
3) is using toluene as water entrainer, the methine acid esterification intermediate product and monohydroxyalkyl group primary amine of TTA,
In continuing heating reflux reaction at 110~130 DEG C, oil water separator separates the water of generation, after reacting 2~4 hours, vacuum distillation
Toluene is removed, the secondary methylol boric acid ester compound of TTA is made, its structural formula is：
；
In formula, R is ethylidene, propylidene, isopropylidene, butylidene or isobutylidene.
2. a kind of preparation method of the secondary methylol boric acid ester compound of TTA according to claim 1,
It is characterized in that：Described TTA, formaldehyde, the mol ratio of boric acid and monohydroxyalkyl group primary amine are the ﹕ 1~1.2 of 1 ﹕ 1~2：
2~2.4；The preferred Macrogol 600 of described phase transfer catalyst, polyethylene glycol-800 and cetomacrogol 1000；Its consumption is first
The 2%~5% of base benzotriazole quality.
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| 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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| JP6181403B2 (en) * | 2013-04-04 | 2017-08-16 | ユシロ化学工業株式会社 | Water-soluble functional fluid with rot resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| Title |
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| 含氮杂环硼酸酯的合成及其摩擦学性能;柴多里，等;《润滑与密封》;20091231;第34卷(第12期);第18-21页 * |
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