CN102372655B - Carbonyl tetraamine compound and preparation method thereof - Google Patents

Abstract

其中，R¹是烷基、环烷基或芳基，其中烷基或环烷基的碳数为8～24，芳基是苯基或取代的苯基；R²是亚烷基或亚芳基，其中亚烷基的碳数为2～12，亚芳基是亚苯基或亚联苯基；R³是碳数为6～30的亚芳基、亚烷基或亚环烷基。本发明提供的碳酰四胺化合物的制备方法包括：向二异氰酸酯的有机溶液中缓慢加入二胺，升温至60℃～100℃进行反应，加入单胺，在60℃～100℃进行反应。本发明所合成的碳酰四胺化合物在农业、医药、炸药、制革、浮选剂、颜料和石油产品等方面有广泛的用途。The invention relates to a carbonamide compound and a preparation method thereof. Described carboxamide compound has following structure:

Among them, R ¹ is an alkyl group, a cycloalkyl group or an aryl group, wherein the carbon number of the alkyl group or cycloalkyl group is 8 to 24, and the aryl group is a phenyl or substituted phenyl group; R ² is an alkylene group or an arylene group A group, wherein the carbon number of the alkylene group is 2 to 12, and the arylene group is a phenylene group or a biphenylene group; ^R3 is an arylene group, an alkylene group or a cycloalkylene group with a carbon number of 6 to 30. The preparation method of the carbonamide compound provided by the invention comprises: slowly adding diamine to the organic solution of diisocyanate, raising the temperature to 60°C-100°C for reaction, adding monoamine, and reacting at 60°C-100°C. The carbonamide compound synthesized by the invention has wide applications in agriculture, medicine, explosives, tanning, flotation agent, pigment and petroleum products and the like.

Description

A kind of carbonamide compound and preparation method thereof

technical field

The invention relates to a carbonamide compound and a preparation method thereof.

Background technique

Carbonamide, whose molecular formula contains the following structure: -NH-CO-NH-. Carboxamide was the first pure organic compound extracted from human excrement (1773) and the first organic compound to be artificially synthesized in a laboratory (1828). Its molecular formula is H ₂ N-CO-NH ₂ , and its molecular weight is 60.06. It is also called urea or carbonamide, commonly known as urea. Carboxamides are very weakly basic and can react with strong acids to form salts, but cannot be tested with litmus paper. Carbonamide can be hydrolyzed in the presence of acid, alkali or urease. Plants and many microorganisms can produce urease, and the carbonamide applied to the soil is absorbed by plants after being hydrolyzed in the presence of this enzyme.

Carbonamide is the nitrogen fertilizer with the highest nitrogen content and is mainly used as a chemical fertilizer. In industry, it is also used as a raw material for the manufacture of urea-formaldehyde resin, polyurethane, and melamine-formaldehyde resin. It is also widely used in medicine, explosives, tanning, flotation agents, pigments, and dewaxing of petroleum products.

CN1087025C reacts excess isocyanate with organic amine in base oil, then neutralizes unreacted isocyanate with water, and continues to heat up to 130-200°C to obtain carbonamide grease with high dropping point, that is, diurea grease.

At present, the carbonamides synthesized in the prior art are limited to carbonamides, and the synthesis method of carbonamides has not been disclosed yet.

Contents of the invention

The invention provides a carbonamide compound.

The invention also provides a preparation method of the carbonyl tetra compound.

Carbonamide compound provided by the invention has following structure:

Wherein ^R can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl can be 8～24, preferably 10～18, aryl can be phenyl or substituted phenyl, preferably benzene or C1-C3 alkyl or halogen-substituted phenyl.

Wherein R ² can be an alkylene group or an arylene group, the carbon number of the alkylene group can be 2-12, preferably 2-8, and the arylene group can be a phenylene group or a biphenylene group.

Wherein ^R3 can be an arylene group, an alkylene group or a cycloalkylene group with a carbon number of 6 to 30, preferably 6 to 20, preferably tolyl, methyldiphenyl, dicyclohexylmethyl, metaphthalene at least one of methyl and hexamethylene.

The preparation method of carbonamide compound provided by the present invention comprises: slowly adding diamine to the organic solution of diisocyanate, raising the temperature to 60°C-100°C for reaction, adding monoamine, and reacting at 60°C-100°C.

Specifically, the carbonamide compound provided by the present invention can be prepared as follows: slowly add diamine to the organic solution of diisocyanate, heat up to 60°C-100°C, preferably 70-85°C, and react until the solid matter Add more, add monoamine, react at 60°C-100°C, preferably 70-85°C, until the solid matter no longer increases, wash, filter, and dry.

Wherein, the molar ratio of diisocyanate to monoamine and diamine is diisocyanate:monoamine:diamine=2:2:1.

Wherein, the adding speed of diamine is 0.05ml-0.2ml per second, preferably 0.05ml-0.1ml.

The two-step reaction of the present invention proceeds very quickly, and can usually be completed within 3 minutes, and the reaction can be completely completed by controlling it at about 30 minutes.

After the reaction was completed, the product was washed, filtered and dried. The filter device can be a centrifugal or suction filter device. The solvent used for washing can be toluene, petroleum ether (90-120 fraction), etc., washed 3-5 times, then dried in an oven at 60°C-100°C, and placed for about 12 hours. .

Said monoamine can be aliphatic amine, alicyclic amine or aromatic amine, and the structural formula is R ¹ -NH ₂ , wherein R ¹ can be alkyl, cycloalkyl or aryl, the carbon number of alkyl or cycloalkyl It can be 8-24, preferably 10-18. The aryl group can be phenyl or substituted phenyl, preferably phenyl or C1-C3 alkyl or halogen-substituted phenyl. Preferred monoamines may be aromatic amines selected from aniline, m-chloroaniline, p-chloroaniline, p-toluidine, and/or aliphatic amines selected from dodecylamine, tetradecylamine, hexadecylamine, octadecylamine.

The said diamine can be aliphatic amine or aromatic amine, the structural formula is NH ₂ -R ² -NH ₂ , wherein R ² can be an alkylene or arylene group, and the carbon number of the alkylene group can be 2-12, Preferably 2 to 8, and the arylene group may be phenylene or biphenylene. Preferred diamines may be aromatic amines selected from p-phenylenediamine, o-phenylenediamine, 4,4,-biphenylenediamine and/or selected from ethylenediamine, propylenediamine, 1,6-hexamethylenediamine straight-chain aliphatic amines.

The diisocyanate structure is OCN-R ³ -NCO, R ³ can be an arylene group, an alkylene group or a cycloalkylene group with a carbon number of 6-30, preferably 6-20, preferably tolyl, methyl di Phenyl, dicyclohexylmethyl, m-xylylene, hexylene, etc. For example, the diisocyanate can be toluene diisocyanate (TDI), methyl diphenyl diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), dicyclohexylmethyl diisocyanate (HMDI), or m- At least one of xylylene diisocyanate (XDI) and the like.

Said organic solution contains an organic solvent with a boiling point of 30-120°C, said organic solvent can be aromatic hydrocarbons, such as benzene, toluene, xylene, etc.; it can also be aliphatic hydrocarbons, such as pentane, hexane, Octane, etc.; it can also be alicyclic hydrocarbons, such as cyclohexane, cyclohexanone, toluene cyclohexanone, etc., preferably benzene, toluene, xylene, etc. For diisocyanates, monoamines or diamines that are solid at room temperature, it is best to dissolve them in an organic solvent first so that the reactants can fully contact.

The carbonamide compound synthesized by the present invention can be used as a chemical fertilizer in agriculture, and can also be used as a raw material for manufacturing urea-formaldehyde resin, polyurethane, and melamine-formaldehyde resin in industry. And petroleum products, etc. also have a wide range of uses.

Description of drawings

Fig. 1 is the infrared analysis spectrogram of the carbonamide prepared by embodiment 1.

Fig. 2 is the nuclear magnetic resonance analysis spectrogram of the carboxamide prepared in embodiment 1.

Fig. 3 is the electrospray mass spectrometry spectrogram of carboxamide prepared in embodiment 1.

Detailed ways

Example 1

First mix toluene and 29.58 grams of MDI and heat to 50°C, slowly add 3.56 grams of diamine, heat up to 80°C, and react for 30 minutes, mix toluene and 31.87 grams of octadecylamine and heat to 60°C, add to the above mixture, and heat up to 80°C, react for 30 minutes, wash, filter, and dry.

Reaction formula:

In the formula, R ¹ is CH ₃ (CH ₂ ) ₁₇ , R ² is -(CH ₂ ) ₂ -, R ³ is

Fig. 1 is the infrared analysis spectrogram of the carbonamide prepared by embodiment 1. It can be seen from the figure that the peak at 3310-3323cm ^-1 is the stretching vibration absorption peak of -NH- in urea molecules, and the peak at 1630cm ^-1 is the vibration absorption peak of -CO- in urea molecules. This indicates that a preparative reaction has occurred.

Fig. 2 is the nuclear magnetic resonance analysis spectrogram of carbonamide. In order to confirm the correctness of the infrared analysis results, the nuclear magnetic resonance ( ¹³ CNMR) analysis method was used again in the experiment to analyze the product qualitatively. It can be seen from the figure that the peak around δ=155HZ is the chemical compound of -CO- in the urea molecule. displacement. This indicates that the preparative reaction did occur.

Figure 3 is the electrospray mass spectrometry spectrum of carbomide. It can be seen from the figure that the mass-to-charge ratio of the sample is 1100.4m/z. This is consistent with the relative molecular mass of the target product carbonamide compound in the preparation reaction. Combining the results of infrared and nuclear magnetic analysis, it can be confirmed that the carbonamide compound was synthesized in the experiment, and the product purity is close to 100%.

Example 2

First mix toluene and 16.76 grams of TDI and heat to 40°C, slowly add 3.93 grams of propylenediamine, heat up to 70°C, and react for 30 minutes, mix toluene and 39.31 grams of dodecylamine and heat to 50°C, add to the above mixture, Raise the temperature to 70°C, react for 30 minutes, wash, filter and dry.

Example 3

First mix toluene and 25.04 g of HDI and heat to 45°C, slowly add 16.10 g of phenylenediamine, heat up to 75°C, and react for 30 minutes, mix toluene and 13.87 g of aniline and heat to 55°C, add to the above mixture, and heat up to React at 75°C for 30 minutes, wash, filter, and 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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