CN102372655B - Carbonyl tetraamine compound and preparation method thereof - Google Patents
Carbonyl tetraamine compound and preparation method thereof Download PDFInfo
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- CN102372655B CN102372655B CN201010263280.7A CN201010263280A CN102372655B CN 102372655 B CN102372655 B CN 102372655B CN 201010263280 A CN201010263280 A CN 201010263280A CN 102372655 B CN102372655 B CN 102372655B
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Abstract
The invention relates to a carbonyl tetraamine compound and a preparation method thereof. The carbonyl tetraamine compound has a structure; R1 is alkyl, cycloalkyl or aryl, wherein the carbon number of the alkyl or cycloalkyl is 8 to 24, and the aryl is phenyl or substituted phenyl; R2 is alkylidene or arylidene, wherein the carbon number of the alkylidene is 2 to 12, and the arylidene is phenylene or biphenylene; and R3 is arylidene, alkylidene or cyclohexylidene, of which the carbon number is 6 to 30. The preparation method for the carbonyl tetraamine compound, which is provided by the invention, includes the following steps: diamine is slowly added into the organic solution of diisocyanate, the temperature is increased to 60 DEG C to 100 DEG C for reaction, monoamine is added, and reaction is carried out under 60 DEG C to 100 DEG C. The carbonyl tetraamine compound synthesized by the invention can be widely applied in agriculture, pharmaceuticals, explosive, tanning, flotation agents, pigments, petroleum products and other aspects.
Description
Technical field
The present invention relates to a kind of carbonyl tetraamine compound and preparation method thereof.
Background technology
Carboxamide, its molecular formula contains following structure :-NH-CO-NH-.Carboxamide is the pure organic compound (1773) extracting from slop the earliest, is also first organic compound (1828 years) by synthetic in laboratory.Its molecular formula is H
2n-CO-NH
2, molecular weight is 60.06, claims again urea or carbonyl diamine, is commonly called as urea.Carboxamide has very weak alkalescence, can react with strong acid and generate salt, but can not check with litmus paper.Carboxamide can be hydrolyzed under the existence of acid, alkali or urease.Plant and many microorganisms can produce urease, and the carboxamide imposing in soil is absorbed by plants after hydrolysis under this kind of enzyme exists.
Carboxamide is the nitrogenous fertilizer that nitrogen content is the highest, mainly as chemical fertilizer.Industrial also as the raw material of manufacturing urea-formaldehyde resin, urethane, melamine formaldehyde resin, at aspects such as medicine, explosive, process hides, flotation agent, pigment and petroleum products dewaxings, also have and do widely way.
CN1087025C, in base oil, reacts with organic amine with excessive isocyanic ester, then in water and unreacted isocyanic ester, continues to be warming up to 130～200 ℃, and the carbonyl diamine that has obtained high dropping point i.e. two urea greases.
At present, the carboxamide of prior art synthesized only limits to carbonyl diamine, also the synthetic method of unexposed phosphinylidyne tetramine.
Summary of the invention
The invention provides a kind of carbonyl tetraamine compound.
The present invention also provides the preparation method of phosphinylidyne Four Modernizations compound.
Carbonyl tetraamine compound provided by the invention has following structure:
R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, preferably 10～18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1～C3 alkyl or halogen replace.
R wherein
2can be alkylidene group or arylidene, the carbon number of alkylidene group can be 2～12, preferably 2～8, and arylidene can be phenylene or biphenylene.
R wherein
3can be that carbon number is 6～30, preferably 6～20 arylidene, alkylidene group or cycloalkylidene, preferably at least one in tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene and hexylidene.
The preparation method of carbonyl tetraamine compound provided by the invention, comprising: in the organic solution of vulcabond, slowly add diamines, be warming up to 60 ℃～100 ℃ and react, add monoamine, at 60 ℃～100 ℃, react.
Specifically, carbonyl tetraamine compound provided by the invention can be prepared as follows: in the organic solution of vulcabond, slowly add diamines, be warming up to 60 ℃～100 ℃, preferably 70～85 ℃, react to solid matter and no longer increase, add monoamine, at 60 ℃～100 ℃, preferably 70～85 ℃, react to solid matter and no longer increase, washing, filters, dry.
Wherein, the mol ratio of vulcabond and monoamine and diamines is vulcabond: monoamine: diamines=2: 2: 1.
Wherein, the speed that adds of diamines is the 0.05ml～0.2ml of being per second, preferably 0.05ml～0.1ml.
Two-step reaction of the present invention carries out very soon, conventionally can within 3min minute, complete, and is controlled at 30min left and right and can makes reaction thoroughly complete.
React complete, product is washed, filter, dry.Filtration unit can adopt centrifugal, suction filtration device, washs solvent used and can select toluene, sherwood oil (90～120 cut) etc., wash 3～5 times, then in baking oven 60 ℃～100 ℃ dry, place 12h left and right.
Said monoamine can be aliphatic amide, aliphatic cyclic amine or arylamine, and structural formula is R
1-NH
2, R wherein
1can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, preferably 10～18, and aryl can be the phenyl of phenyl or replacement, the phenyl that preferably phenyl or C1～C3 alkyl or halogen replace.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, preferably 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, propylene diamine, 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, preferably 6～20 arylidene, alkylidene group or cycloalkylidene, preferred tolyl, methyldiphenyl base, dicyclohexyl methyl, an xylylene, hexylidene etc.For example described vulcabond can be tolylene diisocyanate (TDI), methyldiphenyl group diisocyanate (MDI), 1,6-hexylidene diisocyanate (HDI), dicyclohexyl methyl vulcabond (HMDI), or at least one in an xylylene vulcabond (XDI) etc.
In said organic solution, contain boiling point at the organic solvent of 30～120 ℃, described organic solvent can be arene, as benzene,toluene,xylene etc.; Also can be fat hydrocarbon, as pentane, hexane, octane etc.; Can also be alicyclic hydrocarbon type, as hexanaphthene, pimelinketone, toluene pimelinketone etc., preferred benzene,toluene,xylene etc.Vulcabond, monoamine or diamines under normal temperature being solid, be preferably first dissolved in organic solvent, so that reactant fully contacts.
The carbonyl tetraamine compound of synthesized of the present invention, in agricultural, can be used as chemical fertilizer, the industrial raw material that also can be used as manufacturing urea-formaldehyde resin, urethane, melamine formaldehyde resin, also has been widely used at aspects such as medicine, explosive, process hides, flotation agent, pigment and petroleum productss.
Accompanying drawing explanation
Fig. 1 is the infrared analysis spectrogram of the phosphinylidyne tetramine of embodiment 1 preparation.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of the phosphinylidyne tetramine of embodiment 1 preparation.
Fig. 3 is the Electrospray Ionization Mass Spectrometry spectrogram of the phosphinylidyne tetramine of embodiment 1 preparation.
Embodiment
Embodiment 1
First, by toluene and 29.58 grams of MDI Hybrid Heating to 50 ℃, slowly add 3.56 grams of diamines, be warming up to 80 ℃, after reaction 30min, by toluene and 31.87 grams of stearylamine Hybrid Heating to 60 ℃, join in said mixture, be warming up to 80 ℃, reaction 30min, washing, filters, dry.
Reaction formula:
In formula, R
1for CH
3(CH
2)
17, R
2for-(CH
2)
2-, R
3for
Fig. 1 is the infrared analysis spectrogram of the phosphinylidyne tetramine of embodiment 1 preparation.As can be seen from the figure, 3310～3323cm
-1the peak at place is in urea molecule-the stretching vibration absorption peak of NH-, and 1630cm
-1the peak at place is in urea molecule-vibration absorption peak of CO-.This shows that preparation feedback occurs.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of phosphinylidyne tetramine.In order to determine the exactness of infrared analysis result, in experiment, again adopted nucleus magnetic resonance (
13cNMR) analysis means carries out qualitative analysis to product, and as can be seen from the figure, the peak of δ=155HZ left and right is in urea molecule-chemical shift of CO-.This shows that preparation feedback occurs really.
Fig. 3 is phosphinylidyne tetramine Electrospray Ionization Mass Spectrometry spectrogram.As can be seen from the figure the mass-to-charge ratio of sample is 1100.4m/z.In this and preparation feedback, the relative molecular mass of target product carbonyl tetraamine compound matches, and in conjunction with infrared and nmr analysis result, can determine that experiment synthesized carbonyl tetraamine compound, and product purity approaches 100%.
Embodiment 2
First, by toluene and 16.76 grams of TDI Hybrid Heating to 40 ℃, slowly add 3.93 grams of propylene diamine, be warming up to 70 ℃, after reaction 30min, by toluene and 39.31 grams of amino dodecane Hybrid Heating to 50 ℃, join in said mixture, be warming up to 70 ℃, reaction 30min, washing, filters, dry.
Embodiment 3
First, by toluene and 25.04 grams of HDI Hybrid Heating to 45 ℃, slowly add 16.10 grams of phenylenediamines, be warming up to 75 ℃, after reaction 30min, by toluene and 13.87 grams of aniline Hybrid Heating to 55 ℃, join in said mixture, be warming up to 75 ℃, reaction 30min, washing, filters, dry.
Claims (10)
1. a preparation method for carbonyl tetraamine compound, comprising: in the organic solution of vulcabond, slowly add diamines, be warming up to 60 ℃～100 ℃, react to solid matter and no longer increase, add monoamine, at 60 ℃～100 ℃, react to solid matter and no longer increase, said monoamine structural formula is R
1-NH
2, R wherein
1be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl is 8～24, and aryl is the phenyl of phenyl or C1～C3 alkyl or halogen replacement; Said diamines structural formula is NH
2-R
2-NH
2, R wherein
2be alkylidene group or arylidene, the carbon number of alkylidene group is 2～12, and arylidene is phenylene or biphenylene; Said vulcabond structure is OCN-R
3-NCO, R
3that carbon number is 6～30 arylidene, alkylidene group or cycloalkylidene; In said organic solution, contain boiling point at the organic solvent of 30～120 ℃.
2. according to preparation method claimed in claim 1, comprising, in the organic solution of vulcabond, slowly add diamines, be warming up to 70～85 ℃, react to solid matter and no longer increase, add monoamine, at 70～85 ℃, react to solid matter and no longer increase, washing, filters, dry.
3. according to the preparation method described in claim 1 or 2, wherein, vulcabond is vulcabond with the mol ratio of reacting of monoamine and diamines: monoamine: diamines=2:2:1.
4. according to the preparation method described in claim 1 or 2, wherein the speed that adds of diamines is 0.05ml～0.2ml per second.
5. according to preparation method claimed in claim 1, R wherein
1the phenyl that phenyl or C1～C3 alkyl or halogen replace, or the carbon number alkyl or cycloalkyl that is 10～18.
6. according to preparation method claimed in claim 1, 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.
7. according to preparation method claimed in claim 1, wherein, said diamines is selected from Ursol D, O-Phenylene Diamine, 4,4, the aromatic amine of-benzidine and/or be selected from quadrol, propylene diamine, 1, the straight-chain fatty amine of 6-hexanediamine.
8. according to preparation method claimed in claim 1, wherein, R
3that carbon number is 6～20 arylidene, alkylidene group or cycloalkylidene.
9. according to preparation method claimed in claim 1, wherein, described vulcabond is selected from tolylene diisocyanate, methyldiphenyl group diisocyanate, hexamethylene vulcabond, dicyclohexyl methyl vulcabond, or at least one in an xylylene vulcabond.
10. according to preparation method claimed in claim 1, wherein, described organic solvent is selected from least one in benzene,toluene,xylene, pentane, hexane, octane, hexanaphthene, pimelinketone, toluene pimelinketone.
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