CN105732530A - 2,4,6-tri(amino acid)-1,3,5-triazine hydramine salts, and preparation method and application thereof - Google Patents

2,4,6-tri(amino acid)-1,3,5-triazine hydramine salts, and preparation method and application thereof Download PDF

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Publication number
CN105732530A
CN105732530A CN201610058232.1A CN201610058232A CN105732530A CN 105732530 A CN105732530 A CN 105732530A CN 201610058232 A CN201610058232 A CN 201610058232A CN 105732530 A CN105732530 A CN 105732530A
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tri
triazines
preparation
acidic group
amino acidic
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Chinese (zh)
Inventor
宋扬扬
吴珉
刘军
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Shaanxi Research Design Institute of Petroleum and Chemical Industry
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Shaanxi Research Design Institute of Petroleum and Chemical Industry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/70—Other substituted melamines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring containing nitrogen and carbon only
    • C10M133/42—Triazines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to 2,4,6-tri(amino acid)-1,3,5-triazine hydramine salts disclosed as Structural Formula (I), and a preparation method and application thereof. The preparation method comprises the following steps: carrying out thermostatic reaction on amino acids in a mole ratio of 1:3.3 under the action of Lewis base at a certain temperature for 24 hours, filtering to remove inorganic salts, recovering the filtrate under reduced pressure, dissolving the obtained residue in sodium hydroxide, slowly and dropwisely hydrochloric acid with the pH value of 1 until abundant precipitates separate out, standing, and filtering, wherein the obtained filter cake is 2,4,6-tri(amino acid)-1,3,5-triazine; and mixing the 2,4,6-tri(amino acid)-1,3,5-triazine with hydramine in a mole ratio of 1:(1-3), and reacting at the constant temperature of 40 DEG C for 1 hour until the reaction solution becomes clear, thereby preparing the 2,4,6-tri(amino acid)-1,3,5-triazine hydramine salts. The method has the advantages of simple synthesis process and high synthesis efficiency, avoids the problem of cyanuric chloride hydrolysis in the reaction, and is suitable for multiple reactions using cyanuric chloride as the substrate, The obtained product is biodegradable, can be widely used in different types of water-based cutting fluids, and has favorable antirust and lubricating effects.

Description

2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt and its preparation method and application
Technical field
The present invention relates to a kind of amine salt, be specifically related to 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt and its preparation method and application.
Background technology
Along with processing technique and the development of rapidoprint in machining industry, traditional cutting fluid can not meet the highest machining level and the requirement of green manufacturing, therefore cutting fluid and additive thereof have proposed the requirement of more Gao Gengxin.
2,4,6-tri-(6-aminocaprolc acid base)-1,3,5-triazines is as a kind of very important water-based antirust, and because of synthetic method difficulty, product purity is low, and domestic application is less.Patent CN101973949A discloses " one kettle way " and prepares this compound in aqueous, and technological operation is simple, pollutes little, but have ignored Cyanuric Chloride hydrolysis problem, and productivity is extremely low.One of raw material 6-aminocaprolc acid dissolubility difference in organic solvent is also unfavorable for that reaction is carried out.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, it is an object of the invention to provide 2, 4, 6-tri-(amino acidic group)-1, 3, 5-triazine alcohol amine salt and its preparation method and application, aminocaproic acid is replaced to react with aminoacid, on the one hand it is soluble in organic solvent and is beneficial to reaction, on the other hand additive is nontoxic after decomposing is beneficial to environmental conservation, organic solution is reacted, overcome same type compound 2, 4, 6-tri-(amino caproyl)-1, 3, 5-triazine preparation difficulty, the problem that the hydrolysis of raw material Cyanuric Chloride is serious, avoid substep method of substitution complex procedures of intermittently heating simultaneously, be not suitable for quantity-produced trouble, organic solvent can be recycled in a large number simultaneously, reduce cost payout, can large-scale industrial production.
To achieve these goals, the technical scheme is that
2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt that structure formula (I) represents, it is characterised in that
,
R shown in structure formula (I) is H ,-CH2CH2COOH。
The preparation method of above-mentioned 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt, it is characterised in that comprise the following steps:
1) by Cyanuric Chloride, aminoacid dissolves in organic solvent according to the ratio 1:3.3 of the amount of material, adds a certain amount of lewis base, is warming up to uniform temperature, isothermal reaction 24h, and thin layer chromatography detection, without raw material Cyanuric Chloride, terminates reaction；
2) gained reactant liquor is cooled to room temperature, is filtered to remove inorganic salt, and filtrate decompression recycles and reuses, and directly adds sodium hydroxide solution in reaction bulb and dissolves, is slowly added dropwise to there being a large amount of Precipitation with the hydrochloric acid of pH=1, stands and filter.Gained filter cake is 2,4,6-tri-(amino acidic group) 1,3,5-triazines；
3) products therefrom is without being dried, and directly mixes according to mass ratio 1:1-3 with hydramine, and constant temperature 40 DEG C reaction 1h, question response liquid becomes clarification, and reaction terminates, and obtains multifunction additive 2,4,6-tri-(amino acidic group)-1,3,5-triazines ethanolamine salts.
Described organic solvent is one or several the mixture in toluene, dimethylbenzene, DMF, Isosorbide-5-Nitrae-dioxane.
Described aminoacid is the one in glycine, glutamic acid.
Described lewis base is the one in sodium carbonate, sodium hydroxide, potassium carbonate.
Described uniform temperature is 40-80 DEG C.
Described hydramine is the one in monoethanolamine, diethanolamine, triethanolamine.
Described 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt can use separately as water-based antirust in water-base cutting fluid, improve the antirust index of cutting fluid.
The invention has the beneficial effects as follows:
In this programme, described aminoacid is can be glutamic acid, glycine, the readily soluble organic solvent of aminoacid used, it is to avoid two phase reaction, and productivity can be greatly improved.
In this programme, described lewis base is the one in sodium carbonate, sodium hydroxide, potassium carbonate.85% is can reach as acid binding agent, glutamic acid as raw material, productivity using potassium carbonate.
In this programme, described preparation method avoids the hydrolysis problem of Cyanuric Chloride in organic solvent, and isothermal reaction avoids the troublesome poeration of stepwise heating.Organic solvent recycles simultaneously, cost-effective, environmental protection.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further discussed below.
Embodiment 1
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt, comprises the steps:
Under room temperature, 0.1mol Cyanuric Chloride, 0.33mol glycine being dissolved in 500mL toluene, the potassium carbonate of 0.05mol, as acid binding agent, stirring, is to slowly warm up to 80 DEG C, isothermal reaction 24h, and thin layer chromatography detects substantially without raw material point.Being cooled to room temperature, be filtered to remove inorganic salt, filtrate decompression reclaims toluene, obtains nearly colorless viscous shape product.Adding sodium hydroxide solution in reaction bulb to dissolve, filter, the hydrochloric acid of filtrate pH=1 is slowly added dropwise to there being a large amount of Precipitation, stands and filters.Gained filter cake is 2,4,6-tri-(glycine base)-1,3,5-triazines, and filter cake is with respectively with a small amount of water and absolute ethanol washing, and product vacuum drying is weighed, productivity 85.2%.For obtaining high-purity compound, recrystallization operation can be carried out in ethanol, obtain nearly clear crystal.
The sign of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt:
Elementary analysis (%) C9H12N6O6: theoretical value: C 36.00, H 4.03, N 27.99, measured value C 36.10, H 4.06, N 27.80；
Infrared spectrum: IP(KBr, cm-1) ν: 3275,2875,2830,1526,1540；
Mass spectrum: m/z 301(M+H)；
1HNMR:(DMSO-d6,400MHz), δ: 4.2-4.5,11.0-11.3
Product obtained by said structure appraising datum confirms is 2,4,6-tri-(glycine base)-1,3,5-triazines.
Product 2,4, the performance of 6-tri-(glycine base)-1,3,5-triazines:
Outward appearance: white powdery solids；
Fusing point: 170-173 DEG C；
In actual application, products therefrom, without post processing, can be directly that 1:3 directly mixes with triethanolamine according to mass ratio, constant temperature 40 DEG C reaction 1h, question response liquid becomes clarification, and reaction terminates, and obtains multifunction additive 2,4,6-tri-(amino acidic group)-1,3,5-triazines ethanolamine salt.
Embodiment 2
The multifunction additive 2 that Example 2 prepares, 4,6-tri-(glycine base)-1,3,5-triazine ethanolamine salt, prepares the aqueous solution of 0.05%, 0.1%, 0.2%, 0.3% and 0.5% respectively, according to the method for regulation in GB6144-2010, using monolithic rust prevention test to test its rustless property, result is as shown in the table:
It was found that when addition is 0.1%, be equivalent to the sodium nitrite of 3%, addition is little, favorable rust preventing effect, can substitute for the sub-sodium main antirust agent as water-base cutting fluid completely.

Claims (8)

1. 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt that structure formula (I) represents, it is characterised in that
,
R shown in structure formula (I) is H ,-CH2CH2COOH。
2. 2 described in claim 1, the preparation method of 4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt, it is characterised in that comprise the following steps:
1) by Cyanuric Chloride, aminoacid dissolves in organic solvent according to the ratio 1:3.3 of the amount of material, adds a certain amount of lewis base, is warming up to uniform temperature, isothermal reaction 24h, and thin layer chromatography detection, without raw material Cyanuric Chloride, terminates reaction；
2) gained reactant liquor is cooled to room temperature, it is filtered to remove inorganic salt, filtrate decompression recycles and reuses, and directly adds sodium hydroxide solution in reaction bulb and dissolves, is slowly added dropwise to there being a large amount of Precipitation with the hydrochloric acid of pH=1, stand and filter, gained filter cake is 2,4,6-tri-(amino acidic groups) 1,3,5-triazines；
3) products therefrom is without being dried, and directly mixes according to mass ratio 1:1-3 with hydramine, and constant temperature 40 DEG C reaction 1h, question response liquid becomes clarification, and reaction terminates, and obtains multifunction additive 2,4,6-tri-(amino acidic group)-1,3,5-triazines ethanolamine salts.
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt the most according to claim 2, it is characterised in that described organic solvent is one or several the mixture in toluene, dimethylbenzene, DMF, Isosorbide-5-Nitrae-dioxane.
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt the most according to claim 2, it is characterised in that described aminoacid is the one in glycine, glutamic acid.
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt the most according to claim 2, it is characterised in that described lewis base is the one in sodium carbonate, sodium hydroxide, potassium carbonate.
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt the most according to claim 2, it is characterised in that described uniform temperature is 40-80 DEG C.
The preparation method of 2,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt the most according to claim 2, it is characterised in that described hydramine is the one in monoethanolamine, diethanolamine, triethanolamine.
8. 2 described in claim 1,4,6-tri-(amino acidic group)-1,3,5-triazines alcohol amine salt can use separately as water-based antirust in water-base cutting fluid, improve the antirust index of cutting fluid.
CN201610058232.1A 2016-01-28 2016-01-28 2,4,6-tri(amino acid)-1,3,5-triazine hydramine salts, and preparation method and application thereof Pending CN105732530A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108863967A (en) * 2018-09-11 2018-11-23 四川格鑫拓科技有限公司 A kind of triazine ring multi-quaternary ammonium salt antioxygen corrosion inhibiter and its preparation method and application
CN115679470A (en) * 2022-12-08 2023-02-03 胡洋兵 Flame-retardant polyester fiber fabric and preparation method thereof
CN116396795A (en) * 2023-04-06 2023-07-07 特浦朗克化工（营口）股份有限公司 Water-based environment-friendly flame-retardant hydraulic fluid and preparation method thereof

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CN1760352A (en) * 2005-11-10 2006-04-19 上海大学 Water based additive for metal machining liquid, and preparation method
CN101973949A (en) * 2010-11-17 2011-02-16 天津师范大学 Method for preparing 2,4,6-tri(amino caproyl)-1,3,5-triazine
CN104649990A (en) * 2013-11-26 2015-05-27 修建东 Triazinyl triamine ethanol glutarate and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
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CN1760352A (en) * 2005-11-10 2006-04-19 上海大学 Water based additive for metal machining liquid, and preparation method
CN101973949A (en) * 2010-11-17 2011-02-16 天津师范大学 Method for preparing 2,4,6-tri(amino caproyl)-1,3,5-triazine
CN104649990A (en) * 2013-11-26 2015-05-27 修建东 Triazinyl triamine ethanol glutarate and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108863967A (en) * 2018-09-11 2018-11-23 四川格鑫拓科技有限公司 A kind of triazine ring multi-quaternary ammonium salt antioxygen corrosion inhibiter and its preparation method and application
CN115679470A (en) * 2022-12-08 2023-02-03 胡洋兵 Flame-retardant polyester fiber fabric and preparation method thereof
CN115679470B (en) * 2022-12-08 2024-05-24 普宁市耿晟织造有限公司 Flame-retardant polyester fiber fabric and preparation method thereof
CN116396795A (en) * 2023-04-06 2023-07-07 特浦朗克化工（营口）股份有限公司 Water-based environment-friendly flame-retardant hydraulic fluid and preparation method thereof
CN116396795B (en) * 2023-04-06 2024-02-02 特浦朗克材料科技(营口)股份有限公司 Water-based environment-friendly flame-retardant hydraulic fluid and preparation method thereof

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Application publication date: 20160706