CN102372656B - Carbonylhexamine compound and preparation method thereof - Google Patents
Carbonylhexamine compound and preparation method thereof Download PDFInfo
- Publication number
- CN102372656B CN102372656B CN201010263301.5A CN201010263301A CN102372656B CN 102372656 B CN102372656 B CN 102372656B CN 201010263301 A CN201010263301 A CN 201010263301A CN 102372656 B CN102372656 B CN 102372656B
- Authority
- CN
- China
- Prior art keywords
- vulcabond
- preparation
- react
- monoamine
- diamines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 Carbonylhexamine 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 after hydrolysis, to be absorbed by plants 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, also have at aspects such as medicine, explosive, process hides, flotation agent, pigment and petroleum products dewaxings 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 DEG C, has obtained i.e. two urea greases of carbonyl diamine of high dropping point.At present, the carboxamide of prior art synthesized only limits to carbonyl diamine, also the synthetic method of unexposed phosphinylidyne hexamine.
Summary of the invention
The invention provides a kind of Carbonylhexamine compound.
The present invention also provides the preparation method of Carbonylhexamine compound.
Carbonylhexamine 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 Carbonylhexamine compound provided by the invention, comprising:
(1) in the organic solution of vulcabond, slowly add monoamine, be warming up to 60 DEG C~100 DEG C and react;
(2) in the product of step (1), add diamines, react at 60 DEG C~100 DEG C;
(3) to the organic solution that slowly adds vulcabond in the product of step (2), react at 60 DEG C~100 DEG C.
Specifically, Carbonylhexamine compound provided by the invention can be prepared as follows:
(1) in the organic solution of vulcabond, slowly add monoamine, be warming up to 60 DEG C~100 DEG C, preferably 70~85 DEG C, react to solid matter and no longer increase;
(2) in the product of step (1), add diamines, at 60 DEG C~100 DEG C, preferably 70~85 DEG C, react to solid matter and no longer increase;
(3) to the organic solution that slowly adds vulcabond in the product of step (2), at 60 DEG C~100 DEG C, preferably 70~85 DEG C are reacted, and react to solid matter and no longer increase, and washing, filters, dry.
In step (1), the mol ratio of vulcabond and monoamine is 1: 1.
The mol ratio of the monoamine adding in the diamines adding in step (2) and step (1) is 1: 1.
The mol ratio of the diamines in the vulcabond in step (3) and step (2) is 1: 2.
In step (1), the speed that adds of monoamine is the 0.05ml~0.2ml of being per second, preferably 0.05ml~0.1ml.
In step (3), the speed that adds of vulcabond is 0.05ml~0.2ml per second, preferably 0.05ml~0.1ml.
Three-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 DEG C~100 DEG C 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, preferably 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 DEG C, 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.For the vulcabond, monoamine or the diamines that under normal temperature are 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.
Brief description of the drawings
Fig. 1 is the infrared analysis spectrogram of the phosphinylidyne hexamine prepared of embodiment 1.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of the phosphinylidyne hexamine prepared of embodiment 1.
Fig. 3 is the Electrospray Ionization Mass Spectrometry spectrogram of the phosphinylidyne hexamine prepared of embodiment 1.
Embodiment
Embodiment 1
First, by toluene and 23.07 grams of MDI Hybrid Heating to 50 DEG C, toluene and 24.85 grams of stearylamine Hybrid Heating to 60 DEG C, slowly join in said mixture, be warming up to 80 DEG C, reaction 30min, adds 5.54 grams of quadrols fast, 80 DEG C of constant temperature, reaction 30min, toluene and 11.54 grams of MDI Hybrid Heating to 50 DEG C, slowly join in said mixture, 80 DEG C of constant temperature, reaction 30min, washing, filter, dry.
Preparation feedback 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 hexamine prepared of embodiment 1.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 hexamine.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 hexamine Electrospray Ionization Mass Spectrometry spectrogram.As can be seen from the figure the mass-to-charge ratio of sample is 1411.0m/z.In this and preparation feedback, the relative molecular mass of target product Carbonylhexamine compound matches, and in conjunction with infrared and nmr analysis result, can determine that experiment synthesized Carbonylhexamine compound, and product purity approaches 100%.
Embodiment 2
First, by toluene and 13.91 grams of TDI Hybrid Heating to 40 DEG C, toluene and 32.62 grams of amino dodecane Hybrid Heating to 50 DEG C, slowly join in said mixture, be warming up to 70 DEG C, reaction 30min, adds 6.52 grams of propylene diamine fast, 70 DEG C of constant temperature, reaction 30min, toluene and 6.59 grams of TDI Hybrid Heating to 40 DEG C, slowly join in said mixture, 70 DEG C of constant temperature, reaction 30min, washing, filter, dry.
Embodiment 3
First, by toluene and 16.69 grams of HDI Hybrid Heating to 45 DEG C, 3.86 grams of aniline Hybrid Heating to 55 DEG C of toluene, slowly join in said mixture, be warming up to 75 DEG C, reaction 30min, adds 16.1 grams of phenylenediamines fast, 75 DEG C of constant temperature, reaction 30min, toluene and 8.35 grams of HDI Hybrid Heating to 45 DEG C, slowly join in said mixture, 75 DEG C of constant temperature, reaction 30min, washing, filter, dry.
Claims (9)
1. a preparation method for Carbonylhexamine compound, comprising:
(1) in the organic solution of vulcabond, slowly add monoamine, be warming up to 60 DEG C~100 DEG C, 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 60 DEG C~100 DEG C;
(3), to the organic solution that slowly adds vulcabond in the product of step (2), react to solid matter and no longer increase at 60 DEG C~100 DEG C;
Wherein, in step (1), vulcabond is 1: 1 with the mol ratio of reacting of monoamine; The mol ratio of the monoamine adding in the diamines adding in step (2) and step (1) is 1: 1; Vulcabond in step (3) is 1: 2 with the mol ratio of reacting of the diamines in step (2), and 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 DEG C.
2. according to preparation method claimed in claim 1, comprising,
(1) in the organic solution of vulcabond, slowly add monoamine, be warming up to 70~85 DEG C, react to solid matter and no longer increase;
(2) in the product of step (1), add diamines, at 70~85 DEG C, react to solid matter and no longer increase;
(3) to the organic solution that slowly adds vulcabond in the product of step (2), react at 70~85 DEG C, react to solid matter and no longer increase, washing, filters, dry.
3. according to the preparation method described in claim 1 or 2, in step (1), the speed that adds of monoamine is 0.05m1~0.2ml per second, and in step (3), the speed that adds of vulcabond is 0.05ml~0.2ml per second.
4. 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.
5. 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.
6. 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.
7. according to preparation method claimed in claim 1, wherein, R
3that carbon number is 6~20 arylidene, alkylidene group or cycloalkylidene.
8. 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.
9. 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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010263301.5A CN102372656B (en) | 2010-08-26 | 2010-08-26 | Carbonylhexamine compound and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201010263301.5A CN102372656B (en) | 2010-08-26 | 2010-08-26 | Carbonylhexamine compound and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102372656A CN102372656A (en) | 2012-03-14 |
CN102372656B true CN102372656B (en) | 2014-08-20 |
Family
ID=45791944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201010263301.5A Active CN102372656B (en) | 2010-08-26 | 2010-08-26 | Carbonylhexamine compound and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102372656B (en) |
Families Citing this family (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 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3243372A (en) * | 1961-01-24 | 1966-03-29 | Chevron Res | Greases thickened with polyurea |
IL47144A (en) * | 1975-04-22 | 1978-06-15 | Chem & Phosphates Ltd | Fertilizer compound the ureaform type and a method for the production thereof |
US4661276A (en) * | 1982-06-30 | 1987-04-28 | Chevron Research Company | Grease composition |
DE4409042A1 (en) * | 1994-03-17 | 1995-09-21 | Bayer Ag | Process for the production of optionally cellular polyurethanes and / or polyurethane ureas |
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 |
US8552078B2 (en) * | 2006-10-17 | 2013-10-08 | Air Products And Chemicals, Inc. | Crosslinkers for improving stability of polyurethane foams |
-
2010
- 2010-08-26 CN CN201010263301.5A patent/CN102372656B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN102372656A (en) | 2012-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108570149B (en) | Method for preparing polythiourea by multicomponent polymerization of isonitrile, sulfur and amine and application of polythiourea | |
CN102372656B (en) | Carbonylhexamine compound and preparation method thereof | |
CN113087681B (en) | Cyclic polyurea molecule, preparation method and application thereof | |
CN101168547B (en) | Method for synthesizing monomolecular phosphorus-nitrogen expansion type fire retardant | |
CN102372655B (en) | Carbonyl tetraamine compound and preparation method thereof | |
CN105085910A (en) | Intrinsically flame retardant bio-based benzoxazine resin and preparation method thereof | |
CN103012847A (en) | Efficient nitrogen and phosphorus fire retardant for epoxy resin and preparation method of efficient nitrogen and phosphorus fire retardant | |
CA2724066C (en) | Method for producing bicyclic guanidines by use of a cyclic thiourea | |
CN102372654B (en) | Carbonyl octoamine compound and preparation method thereof | |
CN106977469A (en) | A kind of synthetic method of deuterated HMX | |
Wang et al. | Effective synthesis of dimethylhexane-1, 6-dicarbamate from 1, 6-hexanediamine and dimethyl carbonate using 3-amino-1, 2, 4-triazole potassium as a solid base catalyst at ambient temperature | |
Hua et al. | Research on controllable degradation of sulfonylurea herbicides | |
CN108084228B (en) | It is a kind of to contain nitrogen, the compound of three kinds of ignition-proof elements of phosphorus and bromine, preparation method and application | |
CN102040532A (en) | Preparation method of polypropylene beta crystalline nucleating agent | |
Malwitz et al. | Amine catalysis of polyurethane foams | |
CN101792466A (en) | Method for catalytically synthesizing dicycloethyl phosphite ester by using ionic liquid | |
CN101245010B (en) | Method for producing civil dinitrotoluene | |
Çaylı et al. | Isothiocyanate derivatives of soybean oil triglycerides: Synthesis, characterization, and polymerization with polyols and polyamines | |
Wang et al. | Synthesis and fungicidal activity of 1, 3, 4-oxadiazole substituted acylthioureas | |
CN100334131C (en) | Process for preparing polyester-base thiourea resin | |
CN105646813B (en) | A kind of reactive flame retardant and preparation method thereof applied to polyurethane material | |
CN101531630B (en) | Asymmetric chiral double-Schiff base simple synthesizing method | |
CN102249930B (en) | Method for synthesizing 3,3',5,5'-dimethyl-4,4'-diaminodiphenylmethane | |
CN110218164A (en) | Bis- (the fluoro- 2,6- dinitrophenyl of 3,4,5- tri-) urea of energetic material 1,3- and its preparation method and application | |
US3094538A (en) | Carbonatopropyl dicarbamates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |