CN102336687B - Method for catalytically synthesizing carbamic acid hydroxyalkyl ester - Google Patents

Method for catalytically synthesizing carbamic acid hydroxyalkyl ester Download PDF

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CN102336687B
CN102336687B CN201010234184XA CN201010234184A CN102336687B CN 102336687 B CN102336687 B CN 102336687B CN 201010234184X A CN201010234184X A CN 201010234184XA CN 201010234184 A CN201010234184 A CN 201010234184A CN 102336687 B CN102336687 B CN 102336687B
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CN102336687A (en
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邓友全
郭晓光
石峰
彭奇龄
李健
尚建鹏
马昱博
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Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute
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Abstract

The invention discloses a method for catalytically synthesizing carbamic acid hydroxyalkyl ester. In the method, an epoxy compound, CO2 and organic amine are reacted in the presence of a catalyst to form corresponding carbamic acid hydroxyalkyl ester by one step, and the selectivity of the product is over 95 percent. The method has the advantages that: reaction conditions are mild, the operating process is simple, the reaction selectivity is high, raw materials are easy to recycle, the catalyst is easy to recover and has high reusability, the product has high purity, and the method belongs toa clean process and has practical application value.

Description

Catalyze and synthesize the method for hydroxyalkyl carbamate
Technical field
The invention belongs to a kind of method that catalyzes and synthesizes hydroxyalkyl carbamate, specifically, the present invention is under the effect of catalyzer, makes epoxy compounds, CO 2React with organic amine, a step generates the method for corresponding hydroxyalkyl carbamate.
Background technology
Hydroxyalkyl carbamate is an important intermediate of fine chemicals; it was widely used in synthesizing of materials such as agricultural chemicals, dyestuff, leather, ink, plant protection product, reactive thinner, radiation-curable composition, paint, varnish, tackiness agent and printing ink; it also can be used as one of the potential starting material of synthesis of polyurethane coating (US6646153 in addition; US4902754; US4902755; US4902756, US4902757).Industrial production hydroxyalkyl carbamate mainly adopts isocyanic ester and binary or polyvalent alcohol to prepare, its shortcoming be in the product easily the residual isocyanic ester that certain toxicity arranged, yield poorly and the purifying cost high.The synthetic of industrial isocyanic ester is by phosgenation, and this operational path is long, technical sophistication, and the cost of equipment height the more important thing is that phosgene toxicity is big, and a large amount of by-product HCl, environmental pollution is serious.Along with the reinforcement day by day of environmental requirement and the demand of the amino formic acid hydroxy alkyl ester of high purity, green synthesizing amino formic acid hydroxy alkyl ester has become the very important problem of chemical field.
Except isocyanic ester+binary or polyvalent alcohol synthetic route, two synthetic routes have mainly also been developed, i.e. carbonic acid diene ester+amino alcohol, cyclic carbonate+amine at present.Huybrechts etc., USP 6646153 uses organotin or zinc salt and additional a certain amount of alkali etc. as under catalyzer and alcohol or the condition of ketone as solvent, utilize divinyl carbonate, carbonic acid two propylene esters, carbonic acid dibutene ester etc. and some amido alcohol (for example hexylamine base ethanol, benzyl monoethanolamine, cyclohexylamino ethanol etc.) synthetic corresponding hydroxyalkyl carbamate of reaction, the main shortcoming of this process is that the cost of carbonic acid diene ester is higher relatively, catalyst toxicity big and is difficult to reclaim.Werner Blank etc., USP4820830 uses organotin or zinc salt etc. as under the catalyzer condition, utilize cyclic carbonate and some typical diamines (isophorone diamine, 2 for example, 2,4-trimethylammonium-hexamethylene-diamine, 2-ethyl-1,4-tetramethylene-diamine etc.) the synthetic corresponding hydroxyalkyl carbamate of reaction, the shortcoming of this process are similarly that the cyclic carbonate cost is higher relatively, catalyst toxicity big and difficult reclaim etc.
Consider greenhouse gases CO 2Aboundresources, safety and reason such as cheap are directly utilized CO 2The carbonyl source prepares hydroxyalkyl carbamate and had both saved cost, has simplified operating process again, gets more and more people's extensive concerning.Kojima etc. utilize organic secondary amine, CO 2With epoxy compounds under organoaluminum composition catalyst condition, a series of hydroxyalkyl carbamate of one-step synthesis (F.Kojima, et al., J.Am.Chem.Soc.1986,108,391-395).The shortcoming of this process is transformation frequency lower (being about 8mol/mol/h), target product selectivity lower (about 50-60%), is difficult to separate and reuse, limited its further industrial application.
Summary of the invention
The object of the present invention is to provide a kind of method that catalyzes and synthesizes hydroxyalkyl carbamate.
We replace homogeneous catalyst by working load type solid catalyst, utilize epoxy compounds activation CO 2And and the corresponding carbamate of organic amine one-step synthesis.
A kind of method that catalyzes and synthesizes hydroxyalkyl carbamate is characterized in that adopting a kind of supported solid catalyzer, with epoxy compounds, CO 2With organic amine as reactant, do not adding under any solvent condition, the control reaction pressure is 0.5-4MPa, temperature of reaction is 50～160 ℃, a step atomic economy reaction synthesizing amino formic acid hydroxy alkyl ester; Active ingredient in the described supported solid catalyzer is gold, and carrier is Fe 2O 3Or Fe 3O 4, gold is 1～10% to the quality loading of carrier.
In the catalyzer of the present invention, gold is 2～7% to the quality loading of carrier preferably.
We adopt the coprecipitation method preparation catalyzer.The concrete HAuCl that uses 34H 2O and Fe (NO 3) 39H 2O is as the precursor of preparation ferric oxide load gold catalyst, with Fe (NO 3) 39H 2O and HAuCl 34H 2O is soluble in water, drips Na then 2CO 3In the aqueous solution.Continue at ambient temperature to wear out after 1～2 hour, filtering precipitate uses this throw out of distilled water wash.Drying obtains brown solid, 280-320 ℃ of following roasting, obtains brown Au/Fe 2O 3Catalyzer.With Au/Fe 2O 3Catalyzer continues 380-420 ℃ of reduction under hydrogen atmosphere, obtains black Au/Fe 3O 4Catalyzer.
Its structural formula of the epoxy compounds of one of reactant of the present invention is:
Figure BSA00000196514000021
R wherein 1Represent H, Cl, Br ,-CH 3,-C 2H 5,-CH (CH 3) 2, n-C 3H 7, n-C 4H 9,-C (CH 3) 3,-CH 2CH (CH 3) 2Or-C 6H 5, R 2Represent H, Cl, Br ,-CH 3,-C 2H 5,-CH (CH 3) 2, n-C 3H 7, n-C 4H 9,-C (CH 3) 3,-CH 2CH (CH 3) 2Or-C 6H 5
The structural formula of the organic amine of one of reactant of the present invention is R 3-NH 2Or H 2N-R 3-NH 2, wherein
R 3Represent alkyl, carbonatoms is 1～10; Perhaps R 3Representation ring alkyl, structure is
Figure BSA00000196514000031
Perhaps R 3Represent aromatic base, structure is
Figure BSA00000196514000032
The building-up reactions of carbamate of the present invention for catalyst consumption, there is no special restriction, and the mass ratio of organic amine and catalyzer is preferably 1: 10～and 1: 100; The mol ratio of organic amine and epoxy compounds is preferably 1: 2～and 1: 10.
The building-up reactions of carbamate of the present invention, the preferred reaction times is 4～20 hours.
The present invention is catalyzer with ferriferous oxide load gold, directly utilizes CO 2With the reaction conditions gentleness; Catalyzer easily prepares, preservation, recovery and reusability are good; Product is easily separated and transformation frequency is high (240mol/mol/h), because highly selective (more than 99%) does not have other by products substantially, be synthesizing amino formic acid hydroxy alkyl ester perfect method, so it has better industrial application prospects.
Separation, the purge process in laboratory are as follows: after reaction finishes, emit CO after the cooling 2, open reactor, centrifugal recovery catalyzer can directly be reused; The filtrate achromaticity and clarification carries out air distillation to filtrate, and epoxy compounds reclaims, and can reuse.
The quantitative analysis of described purpose product carbamate can utilize Agilent 6820GC to finish, and this Agilent 6820GC has the kapillary (fid detector) of 30m * 0.25mm * 0.33 μ m.Or utilize Agilent 1120HPLC to finish, this Agilent 1120HPLC have for DDA detector and its moving phase be acetonitrile: tetrahydrofuran (THF)=55%: 45%, chromatographic column are Waters XTerra RP C18 (250 * 4.6mm, 5 μ m).Carbamate utilizes external standard method quantitative.The qualitative analysis of the product of described reaction and other possible byproduct, can utilize HP 6890/5973 GC-MS to finish, this HP 6890/5973 GC-MS has the capillary column of 30m * 0.25mm * 0.33 μ m and has the chem workstation of NIST spectra database.Or utilize 1H NMR (Bruker AMX FT 400-MHz) and 13It is qualitative that C NMR (Bruker AMX FT 100-MHz) carries out nuclear-magnetism to it.
Compare with reported method, the advantage of hydroxyalkyl carbamate synthetic method of the present invention is:
1. reaction conditions gentleness, reaction process are simple to operation;
2. reaction raw materials is recycled easily;
3. reaction preference height, by product is few, and non-corrosiveness gas produces.
4. catalyzer all is easy to separate with product.Catalyzer can be repeatedly used.
5. reaction utilizes cheap CO 2Environmental friendliness meets the Green Chemistry definition, satisfies the demand of new chemical industry.
Embodiment
Embodiment 1
Au/Fe 2O 3Preparation of catalysts
Use HAuCl 34H 2O and Fe (NO 3) 39H 2O is as the precursor of preparation ferric oxide load gold catalyst, and this Preparation of catalysts method is co-precipitation.Under violent stirring, with 20.2g Fe (NO 3) 39H 2O and 0.364g HAuCl 34H 2O is dissolved in the 50mL aqueous solution, drips 300mL (0.47mol/L) Na then 2CO 3In the aqueous solution.Continue at ambient temperature to wear out after 1～2 hour, filtering precipitate uses this throw out of 80～100mL distilled water wash about three times.Drying is 16 hours under 120 ℃, obtains brown solid, further 300 ℃ of following roastings 5 hours, obtains the brown Au/Fe of 4g 2O 3Catalyzer, i.e. catalyst A.
Embodiment 2
Au/Fe 3O 4Preparation of catalysts
With catalyzer 1 its in reduction under 400 ℃ of hydrogen atmospheres after 1 hour, the black Au/Fe that obtains 3O 4Catalyzer wherein comprises the Au of 5.05wt%, i.e. catalyst B.。
Embodiment 3
In the 100mL autoclave, add 9.3g (0.1mol) aniline, the 0.2g catalyst A, (17.4g 0.3mol), charges into CO to propylene oxide 20mL 2Pressure is 1.5MPa.Be that 100 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 8h, emit CO after being cooled to room temperature 2, open reactor, centrifugal recovery catalyst A can directly be reused; The filtrate achromaticity and clarification is got filtrate and is carried out gas chromatographic analysis.Under 25 ℃ of conditions filtrate is carried out air distillation, propylene oxide reclaims, and can reuse.The stratographic analysis result is transformation efficiency＞99% of aniline, and selectivity is greater than 99%, carbaniloyl isopropyl alcohol ester separation yield＞95%.By product is N-Virahol aniline, and the chromatogram yield is less than 1%.
Embodiment 4
In the 100mL autoclave, add 9.3g (0.1mol) aniline, the 0.2g catalyst B, (17.4g 0.3mol), charges into CO to propylene oxide 20mL 2Pressure is 1.5MPa.Be that 100 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 8h, emit CO after being cooled to room temperature 2, open reactor, centrifugal recovery catalyst B can directly be reused; The filtrate achromaticity and clarification is got filtrate and is carried out gas chromatographic analysis.Under 25 ℃ of conditions filtrate is carried out air distillation, propylene oxide reclaims, and can reuse.The stratographic analysis result is transformation efficiency＞99% of aniline, and selectivity is greater than 99%, carbaniloyl isopropyl alcohol ester separation yield＞95%.By product is N-Virahol aniline, and the chromatogram yield is less than 1%.
Embodiment 5
In the 100mL autoclave, add 11.6g (0.1mol) 1, the 6-hexanediamine, the 0.2g catalyst A, (17.4g 0.3mol), charges into CO to propylene oxide 20mL 2Pressure is 2.0MPa.Be that 110 ℃ and mixing speed are under the 600rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, open reactor, centrifugal recovery catalyst A can directly be reused, and filtrate is carried out stratographic analysis.Under 25 ℃ of conditions filtrate is carried out air distillation, propylene oxide reclaims, and can reuse.The stratographic analysis result is the transformation efficiency 96% of 1,6-hexanediamine, selectivity＞98%, 1, the own diamino acid isopropyl of 6-alcohol ester separation yield＞92%.By product is the own diamino acid isopropyl of 1-N-Virahol alcohol ester, and the chromatogram yield is less than 2%.
Embodiment 6
In the 100mL autoclave, add 11.6g (0.1mol) 1, the 6-hexanediamine, the 0.2g catalyst B, (17.4g 0.3mol), charges into CO to propylene oxide 20mL 2Pressure is 2.0MPa.Be that 110 ℃ and mixing speed are under the 600rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst B can directly reuse, and filtrate is carried out stratographic analysis.Under 25 ℃ of conditions filtrate is carried out air distillation, propylene oxide reclaims, and can reuse.The stratographic analysis result is the transformation efficiency 96% of 1,6-hexanediamine, selectivity＞99%, 1, the own diamino acid isopropyl of 6-alcohol ester separation yield＞95%.By product is the own diamino acid isopropyl of 1-N-Virahol alcohol ester, and the chromatogram yield is less than 1%.
Embodiment 7
In the 100mL autoclave, add 19.8g (0.1mol) 4,4 '-ditan diamines, 0.3 catalyst A, (17.2g 0.4mol), charges into CO to oxyethane 20mL 2Pressure is 2.0MPa.Temperature be 100 and mixing speed be under the 600rpm condition, reaction finishes behind the 12h, emits CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst A can directly reuse, and filtrate is carried out stratographic analysis.Under 10 ℃ of conditions filtrate is carried out air distillation, oxyethane reclaims, and can reuse.The stratographic analysis result is 4, the transformation efficiency 96% of 4 '-ditan diamines, selectivity＞99%, 4,4 '-ditan diamino acid ethanol ester separation yield＞94%.By product is 4-N-ethanol ditan diamino acid isopropyl alcohol ester, and the chromatogram yield is less than 1%.
Embodiment 8
In the 100mL autoclave, add 19.8g (0.1mol) 4,4 '-ditan diamines, 0.3 catalyst B, (17.2g 0.4mol), charges into CO to oxyethane 20mL 2Pressure is 2.0MPa.Temperature be 110 and mixing speed be under the 600rpm condition, reaction finishes behind the 12h, emits CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst B can directly reuse, and filtrate is carried out stratographic analysis.Under 10 ℃ of conditions filtrate is carried out air distillation, oxyethane reclaims, and can reuse.The stratographic analysis result is 4, the transformation efficiency 96% of 4 '-ditan diamines, selectivity＞98%, 4,4 '-ditan diamino acid ethanol ester separation yield＞92%.By product is 4-N-ethanol ditan diamino acid isopropyl alcohol ester, and the chromatogram yield is less than 2%.
Embodiment 9
In the 100mL autoclave, add 12.2g (0.1mol) 2, the 4-tolylene diamine, the 0.2g catalyst A, (28g 0.3mol), charges into CO to epoxy chloropropane 24mL 2Pressure is 2.0MPa.Be that 100 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst A can directly reuse, and filtrate is carried out stratographic analysis.Under 80 ℃ of conditions, filtrate is carried out underpressure distillation, reclaim epoxy chloropropane, can reuse.The stratographic analysis result is the transformation efficiency 95% of 2,4-tolylene diamine, selectivity 98%, 2,4-toluene diamino acid chloro isopropanol ester separation yield 90%.By product is 1-N-chloro isopropanol toluene diamino acid chloro isopropanol ester, chromatogram yield 2%.
Embodiment 10
In the 100mL autoclave, add 12.2g (0.1mol) 2, the 4-tolylene diamine, the 0.2g catalyst B, (28g 0.3mol), charges into CO to epoxy chloropropane 24mL 2Pressure is 2.0MPa.Be that 110 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst B can directly reuse, and filtrate is carried out stratographic analysis.Under 80 ℃ of conditions, filtrate is carried out underpressure distillation, reclaim epoxy chloropropane, can reuse.The stratographic analysis result is the transformation efficiency 95% of 2,4-tolylene diamine, selectivity 96%, 2,4-toluene diamino acid chloro isopropanol ester separation yield 88%.By product is 1-N-chloro isopropanol toluene diamino acid chloro isopropanol ester, chromatogram yield 4%.
Embodiment 11
In the 100mL autoclave, add 17g (0.1mol) isophorone diamine, the 0.3g catalyst A, (28g 0.3mol), charges into CO to epoxy chloropropane 24mL 2Pressure is 3.5MPa.Be that 100 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst A can directly reuse, and filtrate is carried out stratographic analysis.Under 80 ℃ of conditions filtrate is carried out underpressure distillation, epoxy chloropropane reclaims, and can reuse.The stratographic analysis result is the transformation efficiency 95% of isophorone diamine, selectivity＞97%, isophorone diamino acid chloro isopropanol ester separation yield＞91%.By product is the own diamino acid chloro isopropanol of 1-N-chloro isopropanol ester, and the chromatogram yield is less than 3%.
Embodiment 12
In the 100mL autoclave, add 17g (0.1mol) isophorone diamine, the 0.3g catalyst B, (28g 0.3mol), charges into CO to epoxy chloropropane 24mL 2Pressure is 2.0MPa.Be that 110 ℃ and mixing speed are under the 500rpm condition in temperature, finish behind the reaction 12h, emit CO after being cooled to room temperature 2, opening reactor, filtering recovering catalyst B can directly reuse, and filtrate is carried out stratographic analysis.Under 80 ℃ of conditions filtrate is carried out underpressure distillation, epoxy chloropropane reclaims, and can reuse.The stratographic analysis result is the transformation efficiency 95% of isophorone diamine, selectivity 96%, isophorone diamino acid chloro isopropanol ester separation yield 89%.By product is the own diamino acid chloro isopropanol of 1-N-chloro isopropanol ester, chromatogram yield 4%.
Though the present invention as above explains preferred embodiment, be not in order to limiting the present invention, therefore the protection domain of invention should be as the criterion with the claim scope of applying for a patent.

Claims (5)

1. a method that catalyzes and synthesizes hydroxyalkyl carbamate is characterized in that adopting a kind of supported solid catalyzer, with epoxy compounds, CO 2With organic amine as reactant, do not adding under any solvent condition, the control reaction pressure is 0.5-4MPa, temperature of reaction is 50～160 ℃, a step atomic economy reaction synthesizing amino formic acid hydroxy alkyl ester; Active ingredient in the described supported solid catalyzer is gold, and carrier is Fe 2O 3Or Fe 3O 4, gold is 1～10% to the quality loading of carrier; Its structural formula of epoxy compounds is:
Figure FSB00001071492200011
R wherein 1Represent H, Cl, Br ,-CH 3,-C 2H 5,-CH (CH 3) 2, n-C 3H 7, n-C 4H 9,-C (CH 3) 3,-CH 2CH (CH 3) 2Or-C 6H 5, R 2Represent H, Cl, Br ,-CH 3,-C 2H 5,-CH (CH 3) 2, n-C 3H 7, n-C 4H 9,-C (CH 3) 3,-CH 2CH (CH 3) 2Or-C 6H 5
The structural formula of organic amine is R 3-NH 2Or H 2N-R 3-NH 2, wherein
R 3Represent alkyl, carbonatoms is 1～10; Perhaps R 3Representation ring alkyl, structure is
Figure FSB00001071492200012
Perhaps R 3Represent aromatic base, structure is
Figure FSB00001071492200013
2. the method for claim 1 is characterized in that golden quality loading to carrier is 2～7% in the catalyzer.
3. the method for claim 1, the mass ratio that it is characterized in that organic amine and catalyzer is 1: 10～1: 100.
4. the method for claim 1, the mol ratio that it is characterized in that organic amine and epoxy compounds is 1: 2～1: 10.
5. the method for claim 1 is characterized in that the reaction times is 4～20 hours.
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