CN102372656A - Carbonylhexamine compound and preparation method thereof - Google Patents
Carbonylhexamine compound and preparation method thereof Download PDFInfo
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- CN102372656A CN102372656A CN2010102633015A CN201010263301A CN102372656A CN 102372656 A CN102372656 A CN 102372656A CN 2010102633015 A CN2010102633015 A CN 2010102633015A CN 201010263301 A CN201010263301 A CN 201010263301A CN 102372656 A CN102372656 A CN 102372656A
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Abstract
The invention relates to a carbonylhexamine compound and a preparation method thereof. The structure of the carbonylhexamine compound is shown as below, wherein R1 is C8-24 alkyl, C8-24 cycloalkyl or aryl, the aryl is phenyl or substituted phenyl; R2 is C2-12 alkylidene or arylidene, the arylidene is phenylene or biphenylene; and R3 is C6-30 arylidene, alkylidene or cycloalkylene. The synthesized carbonylhexamine compound has wide applications in agriculture, medicines, explosives, tanning, flotation agents, pigments, petroleum products and other aspects.
Description
Technical field
The present invention relates to a kind of phosphinylidyne hexamine compound and preparation method thereof.
Background technology
Carboxamide, its molecular formula contains following structure :-NH-CO-NH-.Carboxamide is a pure organic cpds (1773) that from slop, extracts the earliest, also is first organic cpds (1828 years) by synthetic in the laboratory.Its molecular formula is H
2N-CO-NH
2, molecular weight is 60.06, claims urea or carbonyl diamine again, is commonly called as urea.Carboxamide has very weak alkalescence, can generate salt with the strong acid reaction, but can not check with litmus paper.Hydrolysis can take place in carboxamide in the presence of acid, alkali or urease.Plant and many mikrobes can produce urease, impose on carboxamide in the soil and be in the presence of this kind of enzyme after the hydrolysis, by plant absorbing.
Carboxamide is the highest nitrogenous fertilizer of nitrogen content, mainly as chemical fertilizer.Also as the raw material of making urea-formaldehyde resin, urethane, melamine formaldehyde resin, work way is widely arranged also at aspects such as medicine, explosive, process hides, flotation agent, pigment and petroleum products dewaxings in the industry.
CN1087025C in base oil, with the reaction of excessive isocyanic ester and organic amine, again in the water with unreacted isocyanic ester, continue to be warming up to 130～200 ℃, the carbonyl diamine that has obtained high dropping point i.e. two urea greases.At present, prior art institute synthetic carboxamide only limits to carbonyl diamine, the compound method of also unexposed phosphinylidyne hexamine.
Summary of the invention
The present invention provides a kind of phosphinylidyne hexamine compound.
The present invention also provides the preparation method of phosphinylidyne hexamine compound.
Phosphinylidyne hexamine compound provided by the invention has following structure:
R wherein
1Can be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, and is preferred 10～18, and aryl can be phenyl or substituted phenyl, preferred phenyl or C1～C3 alkyl or the substituted phenyl of halogen.
R wherein
2Can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, and is preferred 2～8, and arylidene can be phenylene or biphenylene.
R wherein
3Can be that carbon number is 6～30, preferred 6～20 arylidene, alkylidene group or cycloalkylidene, at least a in preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and the hexylidene.
The preparation method of phosphinylidyne hexamine compound provided by the invention comprises:
(1) in the organic solution of vulcabond, slowly adds monoamine, be warming up to 60 ℃～100 ℃ and react;
(2) in the product of step (1), add diamines, react at 60 ℃～100 ℃;
(3) the slow organic solution that adds vulcabond in the product of step (2) is reacted at 60 ℃～100 ℃.
Specifically, phosphinylidyne hexamine compound provided by the invention can prepare as follows:
(1) in the organic solution of vulcabond, slowly adds monoamine, be warming up to 60 ℃～100 ℃, preferred 70～85 ℃, react to solid matter and no longer increase;
(2) in the product of step (1), add diamines,, preferred 70～85 ℃, react to solid matter and no longer increase at 60 ℃～100 ℃;
(3) in the product of step (2), slowly add the organic solution of vulcabond, at 60 ℃～100 ℃, preferred 70～85 ℃ are reacted, and react to solid matter and no longer increase, and washing is filtered, dry getting final product.
The mol ratio of vulcabond and monoamine is 1: 1 in the step (1).
The mol ratio of the monoamine that adds in diamines that adds in the step (2) and the step (1) is 1: 1.
The mol ratio of the diamines in vulcabond in the step (3) and the step (2) is 1: 2.
The adding speed of monoamine is that per second is 0.05ml～0.2ml in the step (1), preferred 0.05ml～0.1ml.
The adding speed of vulcabond is per second 0.05ml～0.2ml in the step (3), preferred 0.05ml～0.1ml.
Three-step reaction according to the invention carries out very soon, can within 3min minute, accomplish usually, is controlled at reaction is thoroughly accomplished.
Reaction finishes, and product is washed, and filters drying.Filtration unit can adopt centrifugal, suction filtration device washs used solvent and can select toluene, sherwood oil (90～120 cut) etc. for use, washs 3～5 times, and 60 ℃～100 ℃ dryings in baking oven are then placed about 12h and got final product.
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1Can be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, and is preferred 10～18, and aryl can be phenyl or substituted phenyl, preferred phenyl or C1～C3 alkyl or the substituted phenyl of halogen.Preferred monoamine can be the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide, para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine, stearylamine.
Said diamines can be aliphatic amide or arylamine, and structural formula is NH
2-R
2-NH
2, R wherein
2Can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, and is preferred 2～8, and arylidene can be phenylene or biphenylene.Preferred diamines can be to be selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from quadrol, tn, 1, the straight-chain fatty amine of 6-hexanediamine.
Said vulcabond structure is OCN-R
3-NCO, R
3Can be that carbon number is 6～30, preferred 6～20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene, hexylidene etc.For example said vulcabond can be tolylene diisocyanate (TDI); Methyldiphenyl group diisocyanate (MDI), hexamethylene vulcabond (HDI); Dicyclohexyl methyl vulcabond (HMDI), or at least a in the xylylene vulcabond (XDI) etc.
Contain boiling point in the said organic solution at 30～120 ℃ organic solvent, said organic solvent can be an arene, like benzene,toluene,xylene etc.; Also can be fat hydrocarbon, like pentane, hexane, octane etc.; Can also be alicyclic hydrocarbon type, like hexanaphthene, pimelinketone, toluene pimelinketone etc., preferred benzene,toluene,xylene etc., preferably be dissolved into earlier in the organic solvent, down for solid vulcabond, monoamine or diamines for normal temperature so that reactant fully contacts.
Institute of the present invention synthetic phosphinylidyne tetramine compound; Can be used as chemical fertilizer on the agricultural; Also can be used as the raw material of making urea-formaldehyde resin, urethane, melamine formaldehyde resin in the industry, also have been widely used at aspects such as medicine, explosive, process hides, flotation agent, pigment and petroleum productss.
Description of drawings
Fig. 1 is the infrared analysis spectrogram of the phosphinylidyne hexamine of embodiment 1 preparation.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of the phosphinylidyne hexamine of embodiment 1 preparation.
Fig. 3 is the electrospray ionization mass spectrum analysis of spectra of the phosphinylidyne hexamine of embodiment 1 preparation.
Embodiment
Embodiment 1
Earlier with toluene and 23.07 gram MDI Hybrid Heating to 50 ℃, toluene and 24.85 restrains stearylamine Hybrid Heating to 60 ℃, slowly joins in the said mixture, is warming up to 80 ℃; Reaction 30min adds 5.54 gram quadrols fast, 80 ℃ of constant temperature, reaction 30min; Toluene and 11.54 gram MDI Hybrid Heating to 50 ℃ slowly join in the said mixture 80 ℃ of constant temperature, reaction 30min; Washing is filtered, dry getting final product.
The preparation feedback formula:
In the formula, R
1Be CH
3(CH
2)
17-, R
2For-(CH
2)
2-, R
3For
Fig. 1 is the infrared analysis spectrogram of the phosphinylidyne hexamine of embodiment 1 preparation.As can be seen from the figure, 3310～3323cm
-1The peak at place is in the urea molecule-the stretching vibration absorption peak of NH-, and 1630cm
-1The peak at place is in the urea molecule-vibration absorption peak of CO-.This shows that preparation feedback takes place.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of phosphinylidyne hexamine.In order to confirm infrared analysis result's exactness, adopted once more in the experiment nucleus magnetic resonance (
13CNMR) analysis means carries out qualitative analysis to product, and as can be seen from the figure, the peak about δ=155HZ is in the urea molecule-chemical shift of CO-.This shows that preparation feedback takes place really.
Fig. 3 is a phosphinylidyne hexamine electrospray ionization mass spectrum analysis of spectra.As can be seen from the figure the mass-to-charge ratio of sample is 1411.0m/z.The relative molecular mass of title product phosphinylidyne hexamine compound matches in this and the preparation feedback, in conjunction with infrared and nmr analysis result, can confirm that experiment synthesized phosphinylidyne hexamine compound, and product purity is near 100%.
Embodiment 2
Earlier with toluene and 13.91 gram TDI Hybrid Heating to 40 ℃, toluene and 32.62 restrains amino dodecane Hybrid Heating to 50 ℃, slowly joins in the said mixture, is warming up to 70 ℃; Reaction 30min adds 6.52 gram tn fast, 70 ℃ of constant temperature, reaction 30min; Toluene and 6.59 gram TDI Hybrid Heating to 40 ℃ slowly join in the said mixture 70 ℃ of constant temperature, reaction 30min; Washing is filtered, dry getting final product.
Embodiment 3
Earlier with toluene and 16.69 gram HDI Hybrid Heating to 45 ℃, toluene 3.86 restrains aniline Hybrid Heating to 55 ℃, slowly joins in the said mixture, is warming up to 75 ℃; Reaction 30min adds 16.1 gram phenylenediamines fast, 75 ℃ of constant temperature, reaction 30min; Toluene and 8.35 gram HDI Hybrid Heating to 45 ℃ slowly join in the said mixture 75 ℃ of constant temperature, reaction 30min; Washing is filtered, dry getting final product.
Claims (18)
1. phosphinylidyne hexamine compound has following structure:
Wherein, R
1Be alkyl, naphthenic base or aryl, wherein the carbon number of alkyl or cycloalkyl is 8～24, and aryl is phenyl or substituted phenyl; R
2Be alkylidene group or arylidene, wherein the carbon number of alkylidene group is 2～12, and arylidene is phenylene or biphenylene; R
3Be that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
2. according to the described compound of claim 1, R wherein
1Be phenyl or C1～C3 alkyl or the substituted phenyl of halogen, or carbon number is 10～18 alkyl or cycloalkyl.
3. according to the described compound of claim 1, wherein, R
2The carbon number of middle alkylidene group is 2～8.
4. according to the described compound of claim 1, wherein, R
3Be selected from least a in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and the hexylidene.
5. the preparation method of a phosphinylidyne hexamine compound comprises:
(1) in the organic solution of vulcabond, slowly adds monoamine, be warming up to 60 ℃～100 ℃ and react;
(2) in the product of step (1), add diamines, react at 60 ℃～100 ℃;
(3) the slow organic solution that adds vulcabond in the product of step (2) is reacted at 60 ℃～100 ℃.
6. according to the described preparation method of claim 5, comprising,
(1) in the organic solution of vulcabond, slowly adds monoamine, be warming up to 70～85 ℃, react to solid matter and no longer increase;
(2) in the product of step (1), add diamines,, react to solid matter and no longer increase at 70～85 ℃;
(3) in the product of step (2), slowly add the organic solution of vulcabond, react at 70～85 ℃, react to solid matter and no longer increase, drying is filtered in washing.
7. according to claim 5 or 6 described preparing methods, wherein, the reaction mol ratio of vulcabond and monoamine is 1: 1 in the step (1); The mol ratio of the monoamine that adds in diamines that adds in the step (2) and the step (1) is 1: 1; The reaction mol ratio of the diamines in vulcabond in the step (3) and the step (2) is 1: 2.
8. according to claim 5 or 6 described preparing methods, the adding speed of monoamine is per second 0.05ml～0.2ml in the step (1), and the adding speed of vulcabond is per second 0.05ml～0.2ml in the step (3).
9. according to claim 5 or 6 described preparing methods, wherein, said monoamine structural formula is R
1-NH
2, R wherein
1Be alkyl, naphthenic base or aryl, the carbon number of alkyl or cycloalkyl is 8～24, and aryl is phenyl or substituted phenyl.
10. according to the described preparation method of claim 9, R wherein
1Be phenyl or C1～C3 alkyl or the substituted phenyl of halogen, or carbon number is 10～18 alkyl or cycloalkyl.
11. according to claim 5 or 6 described preparing methods, wherein, said monoamine is the arylamine that is selected from aniline, m-chloro aniline, p-Chlorobenzoic acid amide and/or para-totuidine, and/or is selected from the aliphatic amide of amino dodecane, tetradecy lamine, cetylamine and/or stearylamine.
12. according to claim 5 or 6 described preparing methods, wherein, said diamines structural formula is NH
2-R
2-NH
2, R wherein
2Be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, and arylidene is phenylene or biphenylene.
13. according to claim 5 or 6 described preparing methods, wherein, said diamines is selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from quadrol, tn, 1, the straight-chain fatty amine of 6-hexanediamine.
14. according to claim 5 or 6 described preparing methods, wherein, said vulcabond structure is OCN-R
3-NCO, R
3Be that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene.
15. according to the described preparation method of claim 14, wherein, R
3Be that carbon number is 6～20 arylidene, alkylidene group or cycloalkylidene.
16. according to claim 5 or 6 described preparing methods, wherein, said vulcabond is selected from tolylene diisocyanate; The methyldiphenyl group diisocyanate, the hexamethylene vulcabond; Dicyclohexyl methyl vulcabond, or at least a in the xylylene vulcabond.
17., wherein, contain boiling point in the said organic solution at 30～120 ℃ organic solvent according to claim 5 or 6 described preparing methods.
18. according to the described preparation method of claim 17, wherein, said organic solvent is selected from least a in benzene,toluene,xylene, pentane, hexane, octane, hexanaphthene, pimelinketone, the toluene pimelinketone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111373A (en) * | 2013-03-06 | 2013-05-22 | 徐州凯米克新材料有限公司 | Preparation method of ethanediamine shrinkage salicylaldehyde Schiff base chelate flotation agent |
| CN110915808A (en) * | 2019-11-08 | 2020-03-27 | 万达集团股份有限公司 | Production process of bactericide without organic chlorine |
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| KR20010086703A (en) * | 2000-03-02 | 2001-09-15 | 임준영 | Process for preparing effects-controlled fertilizer and the product therefrom |
| EP1199291A1 (en) * | 2000-10-17 | 2002-04-24 | Agra Dünger GmbH | Coated chemical product and process for making the coated chemical product |
| CN101168601A (en) * | 2006-10-17 | 2008-04-30 | 气体产品与化学公司 | Crosslinkers for improving stability of polyurethane foams |
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2010
- 2010-08-26 CN CN201010263301.5A patent/CN102372656B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3243372A (en) * | 1961-01-24 | 1966-03-29 | Chevron Res | Greases thickened with polyurea |
| US4089899A (en) * | 1975-04-22 | 1978-05-16 | Fertilizers & Chemicals Limited | Fertilizer compound of the ureaform type and a method for the production thereof |
| US4661276A (en) * | 1982-06-30 | 1987-04-28 | Chevron Research Company | Grease composition |
| CN1112135A (en) * | 1994-03-17 | 1995-11-22 | 拜尔公司 | Method of producing polyurethanes and/or polyurethane ureas which are optionally cellular |
| KR20010086703A (en) * | 2000-03-02 | 2001-09-15 | 임준영 | Process for preparing effects-controlled fertilizer and the product therefrom |
| EP1199291A1 (en) * | 2000-10-17 | 2002-04-24 | Agra Dünger GmbH | Coated chemical product and process for making the coated chemical product |
| CN101168601A (en) * | 2006-10-17 | 2008-04-30 | 气体产品与化学公司 | Crosslinkers for improving stability of polyurethane foams |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111373A (en) * | 2013-03-06 | 2013-05-22 | 徐州凯米克新材料有限公司 | Preparation method of ethanediamine shrinkage salicylaldehyde Schiff base chelate flotation agent |
| CN110915808A (en) * | 2019-11-08 | 2020-03-27 | 万达集团股份有限公司 | Production process of bactericide without organic chlorine |
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