CN114957045B - Method for preparing pentanedicarbamate - Google Patents

Abstract

The invention provides a method for preparing pentanedicarbamate, which comprises the following steps: mixing a carbonylation agent and an amine substrate, and then mixing the mixture with an organic base catalyst to carry out carbonylation reaction to obtain a glutaraldehyde formate product; wherein the amine substrate comprises an aliphatic amine substrate or an aromatic amine substrate, and the organic base catalyst comprises any one or a combination of at least two of potassium phosphate, ethanolamine, tetramethylguanidine or triethylamine; the method takes cheap potassium phosphate as a catalyst, so that the conversion rate of the pentamethylene diamine reaches 100%, the selectivity of the pentamethylene dicarbamate is not less than 82%, and the method has the advantages of low catalyst price, mild reaction conditions and short reaction time, and is suitable for industrial popularization.

Description

A kind of method for preparing pentamethylene dicarbamate

technical field

The invention belongs to the field of organic catalysis, in particular to a method for preparing pentamethylene dicarbamate.

Background technique

Carbamate is a very important organic synthesis intermediate, which is not only widely used in the manufacture of agricultural pesticides, herbicides and drug synthesis, but also can be used as an important precursor for non-phosgene synthesis of polyurethane in industry. The foamed plastics, coatings, adhesives, synthetic leather, elastic fibers, etc. and their products are widely used in the fields of construction, transportation, mining, machinery, printing, light industry and agriculture. So far, there have been many synthetic processes related to carbamate, such as the reaction of carbamoyl chloride and alcohol in the early stage, and the reaction of carbonyl chloride and amine, but these processes require the use of highly toxic phosgene, which is very serious for environmental pollution. , is listed as a prohibited process in the world.

At present, it mainly focuses on the following routes: the reductive carbonylation method of nitro compounds, the oxidative carbonylation method of amines and the amination method of dimethyl carbonate. In addition to the above methods, alkyl carbamate and amine compounds can also be used. Synthetic carbamate, compared with the previous methods, the catalytic route is more environmentally friendly, the utilization rate of raw materials is high, the process is simple, the hidden danger of safety production is low, the price is relatively low, and the activity is also high. It is a very promising development. Non-phosgene route.

CN102015808B discloses a urethanization reaction catalyst and a method of using the urethanization reaction catalyst to manufacture a metal compound-free urethane compound. The urethanization reaction catalyst catalyzes isocyanate compounds, In particular, the reaction of an aliphatic isocyanate and a hydroxyl-containing compound is useful in forming a carbamate without affecting the properties of the carbamate, and the catalyst can be easily removed from the carbamate obtained, The catalyst is a catalyst used to react a hydroxyl-containing compound and an isocyanate compound to produce a carbamate, and is selected from (A) supporting a metal oxide (A-2) on the surface of a metal oxide carrier (A-1). ) or a non-metallic compound (A-3) and a composite metal oxide formed, (B) zeolite, and (C) a heteropolyacid formed of at least one solid acid catalyst in the urethane reaction catalyst, The catalyst contains metal ions, which are difficult to separate from the product.

WO/2022/041502 discloses a preparation method of 1,5-pentanediisocyanate, comprising the following steps: (1) mixing 1,5-pentanediamine, a carbonylating agent, a first solvent and a carbonylation reaction catalyst, Carrying out solid-liquid separation to obtain a 1,5-pentanedicarbamate reaction solution; (2) purifying the 1,5-pentanedicarbamate reaction solution and mixing it with a second solvent for pyrolysis reaction to obtain 1, 5-pentamethylene diisocyanate; the catalyst used in the preparation method is a metal salt, and the separation of the product needs to be additionally carried out, and the steps are relatively cumbersome.

CN113603613A discloses a catalytic synthesis method of pentamethylenediamine, adding pentamethylenediamine and a carbonylating agent to dissolve in a solvent, and performing a catalytic synthesis reaction through a titanium dioxide catalyst. The catalytic synthesis reaction not only makes the conversion rate of pentamethylenediamine It reaches 100%, the selectivity of pentamethylene dicarbamate is more than 90%, and it also has the advantages of mild conditions, short reaction time, no pollution, and low requirements for equipment, but the inorganic catalyst may leave impurity ions in the reactants.

The catalytic synthesis method of pentamethylenedicarbamate disclosed in the prior art often has insufficient separation of inorganic catalysts or requires additional separation, and the catalyst is expensive and the steps are cumbersome. Therefore, it is urgent to develop a cheaply synthesized pentamethylenedicarbamate The catalytic synthesis method of formate is suitable for industrial production.

Contents of the invention

Aiming at the problems of cumbersome production process and incomplete separation of catalysts in the prior art, the present invention proposes a method for preparing pentamethylene dicarbamate, which uses an inexpensive organic catalyst to participate in the carbonylation reaction, thereby improving reaction efficiency and product purity .

For reaching this purpose, the present invention adopts following technical scheme:

The invention provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mixing a carbonylating agent and an amine substrate, and then mixing with an organic base catalyst for a carbonylation reaction to obtain a pentamethylene dicarbamate product;

Wherein, the amine substrate includes an aliphatic amine substrate or an aromatic amine substrate, and the organic base catalyst includes any one or at least two of potassium phosphate, ethanolamine, tetramethylguanidine or triethylamine combination.

The present invention uses a cheap organic base as a catalyst, so that the reactant amine substrate is almost completely converted, and at the same time, the selectivity of pentamethylene dicarbamate is improved. Compared with the inorganic catalyst, the organic catalyst also has the advantages of low price and mild conditions. , the advantage of short reaction time, and the preferred organic base of the present invention can also be applied to compound substrates such as aliphatic amines and aromatic amines, and its wide range of uses makes it suitable for industrial applications; the organic base catalyst of the present invention includes phosphoric acid Any one or a combination of at least two of potassium, ethanolamine, tetramethylguanidine or triethylamine, wherein a typical but non-limiting combination is a combination of potassium phosphate and ethanolamine, a combination of potassium phosphate and tetramethylguanidine, The combination of potassium phosphate and triethylamine, the combination of tetramethylguanidine and ethanolamine, etc., are not limited to the listed combinations, and other unlisted combinations within this range are also applicable.

Preferably, the molar ratio of the carbonylating agent to the amine substrate is (2-15):1, such as 2:1, 3:1, 5:1, 8:1, 10:1, 12:1 1 or 15:1, but not limited to the listed values, other unlisted values within this range are also applicable.

Preferably, the aliphatic amine substrate includes pentamethylenediamine and/or hexamethylenediamine.

Preferably, the aromatic amine substrate includes aniline.

Preferably, the carbonylating agent includes any one or a combination of at least two of dimethyl carbonate, methyl carbamate, diethyl carbonate or ethylene carbonate, wherein a typical but non-limiting combination is dicarbonate A combination of methyl ester and methyl carbamate, a combination of dimethyl carbonate and diethyl carbonate, a combination of dimethyl carbonate and ethylene carbonate, or a combination of diethyl carbonate and methyl carbamate, etc., but not limited to The listed combinations, other unlisted combinations within the range are also applicable.

Preferably, for amine substrates, the equivalent of organic base catalyst used is 5-35%, such as 5%, 10%, 15%, 20%, 25%, 30% or 35%, but not limited to the listed The numerical value of , other unlisted numerical values in this numerical range are also applicable, preferably 10-25%.

The consumption of organic base catalyst of the present invention is preferably 5～35% of amine substrate mass ratio, and its advantage is that can react efficiently and rapidly, and catalyst is less than this content, and reaction is not carried out completely, and catalyst content is too high and will Lead to its own alkaline hydrolysis product, the selected ratio of the present invention can greatly improve the conversion rate and selectivity.

Preferably, the reaction time of the carbonylation reaction is 0.5-24h, such as 0.5h, 1h, 2h, 3h, 5h, 10h, 12h, 18h, 20h or 24h, but not limited to the listed values, the Other unlisted numerical values within the numerical range are also applicable, preferably 3 to 12h.

Preferably, the reaction temperature of the carbonylation reaction is 25-150°C, for example, 25°C, 60°C, 85°C, 100°C, 125°C or 150°C, but not limited to the listed values, the value range Other values not listed in the above are also applicable, preferably 50-85°C.

Preferably, the reaction pressure of the carbonylation reaction is 0-2MPa, for example, it can be 0MPa, 0.5MPa, 1MPa, 1.5MPa or 2MPa, but it is not limited to the listed values, and other unlisted values within this range are the same Applicable, preferably 0.5-1.5MPa.

Preferably, the carbonylating agent and the amine substrate are also mixed with the first solvent before the reaction.

Preferably, the first solvent includes any one or a combination of at least two of methanol, ethanol, water or dimethyl carbonate, wherein a typical but non-limiting combination is a combination of methanol and ethanol, a combination of methanol and water Combinations, combinations of water and dimethyl carbonate, etc., but not limited to the listed combinations, other unlisted combinations within this range are also applicable; when the carbonylating agent is dimethyl carbonate, the first solvent is not dicarbonate methyl ester.

Preferably, the molar ratio of the first solvent to the amine substrate is (3-50):1, such as 3:1, 5:1, 8:1, 10:1, 12:1, 15:1 1, 18:1, 20:1, 30:1 or 50:1, but not limited to the listed values, other unlisted values within the range are also applicable.

The present invention adopts the first solvent, and preferred type and proportioning, its advantage is that the solvent of described type can provide or the solution carrier needed by acid or alkali, provides good environment for the transfer between ions, and then adds catalyst And after the substrate, the reaction is carried out faster, more products are obtained, and the yield of the product is improved.

Preferably, the methanol produced by the carbonylation reaction is excluded.

Preferably, the way of removing methanol includes feeding gas or distillation.

Preferably, the type of gas introduced includes nitrogen.

Preferably, after the carbonylation reaction, a second solvent is added to the reaction liquid obtained from the carbonylation reaction, and the mixture is left to stand until crystals are precipitated and separated to obtain a pentamethylene dicarbamate product.

Preferably, the second solvent includes any one or a combination of at least two of chlorobenzene, o-dichlorobenzene, methanol or ethanol, wherein a typical but non-limiting combination is a combination of chlorobenzene and o-dichlorobenzene , the combination of chlorobenzene and methanol, the combination of chlorobenzene and ethanol, etc., but are not limited to the listed combinations, and other unlisted combinations within this range are also applicable.

Preferably, the volume ratio of the second solvent to the reaction liquid obtained after the carbonylation reaction is (1-8):1.

The invention adopts the second solvent to further dissolve the products in the mixed solution after the reaction, and further obtain more products in the subsequent separation, thereby increasing the yield.

Preferably, the standing temperature is -20°C to 50°C, such as -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C or 50°C, but not limited to Numerical values listed, other unlisted numerical values within the numerical range are also applicable.

Preferably, the standing time is 1-10h, for example, 1h, 2h, 3h, 5h, 8h or 10h, but it is not limited to the listed values, and other unlisted values within this range are also applicable.

Preferably, the separation method includes filtration.

As a preferred technical solution of the present invention, the method comprises the following steps:

Mix carbonylation agent, amine substrate and first solvent, then mix with organic base catalyst, 0.5~24h carbonylation reaction occurs at 25~150℃, 0~2MPa, keep stirring during the reaction process, and at the same time pass nitrogen or Methanol produced by the reaction was removed by distillation. A second solvent is added to the reaction liquid obtained by the carbonylation reaction, and the mixture is left to stand at -20 to 50°C for 1 to 10 hours until crystals are precipitated and filtered to obtain a pentamethylene dicarbamate product.

Wherein, the amine substrates include aliphatic amine substrates or aromatic amine substrates, the aliphatic amine substrates include pentamethylenediamine and/or hexamethylenediamine, and the aromatic amine substrates include aniline. Described carbonylating agent comprises any one or the combination of at least two in dimethyl carbonate, methyl carbamate, diethyl carbonate or ethylene carbonate, and the molar ratio of described carbonylating agent and amine substrate is (2～15):1. The first solvent includes any one or a combination of at least two of methanol, ethanol, water, tetrahydrofuran, dimethyl carbonate or acetonitrile. The organic base catalyst includes any one or a combination of at least two of potassium phosphate, ethanolamine, tetramethylguanidine or triethylamine. For amine substrates, the equivalent weight of the organic base catalyst used is 5-35%. The second solvent includes any one or a combination of at least two of chlorobenzene, o-dichlorobenzene, methanol or ethanol, and the volume ratio of the added second solvent to the reaction solution obtained after the carbonylation reaction is ( 1～8):1.

Compared with prior art, the beneficial effect of the present invention is:

(1) A kind of method for preparing pentamethylene dicarbamate provided by the present invention uses organic bases as catalysts, which is cheap and easy to get, reduces production costs, and has good industrialization prospects;

(2) A kind of method for preparing pentamethylene dicarbamate provided by the invention adopts dimethyl carbonate to replace phosgene, the reaction conditions are mild, pollution-free, the operation process is simple and convenient, and the potential safety hazard is small;

(3) A method for preparing pentamethylenedicarbamate provided by the present invention, the yield of the target product methyl pentamethylenedicarbamate is ≥ 82%, and the crystallization separation method used makes the obtained product purity ≥ 99%.

Detailed ways

In order to facilitate understanding of the present invention, the present invention enumerates the following examples. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

The technical solutions of the present invention will be further described below through specific embodiments.

In a specific embodiment, the invention provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix carbonylation agent, amine substrate and first solvent, then mix with organic base catalyst, 0.5~24h carbonylation reaction occurs at 25~150℃, 0~2MPa, keep stirring during the reaction process, and at the same time pass nitrogen or Distill to remove the methanol produced by the reaction; add a second solvent to the reaction liquid obtained by the carbonylation reaction, and stand at -20 to 50°C for 1 to 10 hours until crystals are precipitated and filtered to obtain the pentamethylene dicarbamate product;

Wherein, the amine substrates include aliphatic amine substrates or aromatic amine substrates, the aliphatic amine substrates include pentamethylenediamine and/or hexamethylenediamine, and the aromatic amine substrates include aniline; Described carbonylating agent comprises any one or the combination of at least two in dimethyl carbonate, methyl carbamate, diethyl carbonate or ethylene carbonate, and the molar ratio of described carbonylating agent and amine substrate is ( 2～15): 1; described first solvent comprises any one or the combination of at least two in methanol, ethanol, water or dimethyl carbonate, and the molar ratio of described first solvent and amine substrate is ( 3～50): 1; described organic base catalyst comprises potassium phosphate, ethanolamine, any one or the combination of at least two in tetramethylguanidine or triethylamine, for amine substrate, used organic base catalyst equivalent is 5% to 35%; the second solvent includes any one or a combination of at least two of chlorobenzene, o-dichlorobenzene, methanol or ethanol, and the reaction liquid obtained after the carbonylation reaction between the added second solvent The volume ratio is (1-8):1.

It should be clear that the adoption of the processes provided by the embodiments of the present invention or the replacement or change of conventional data all fall within the scope of protection and disclosure of the present invention.

Example 1

The present embodiment provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix dimethyl carbonate, pentamethylenediamine and water at a molar ratio of 10:1:8, and then add potassium phosphate whose mass ratio is 10% of the mass of PDA, and a carbonylation reaction occurs for 6 hours at 90°C and 1 MPa, and the reaction process lasts Stir while feeding nitrogen to remove the methanol generated by the reaction; after the reaction, heat until the solid dissolves, add water to the reaction liquid obtained by the carbonylation reaction, and the volume ratio of water to the reaction mixture is 4:1, 10 Stand at ℃ for 4h to precipitate crystals and filter to obtain pentamethylene dicarbamate product.

Example 2

The present embodiment provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix dimethyl carbonate, pentamethylenediamine and ethanol at a molar ratio of 6:1:50, then add triethylamine with a mass ratio of 5% by mass of PDA, and a carbonylation reaction occurs for 5 hours at 40°C and 1.5MPa. The reaction process Continuously stirring in the middle, while introducing nitrogen gas to remove the methanol produced by the reaction; after the reaction, heat until the solid dissolves, add o-dichlorobenzene in the reaction liquid obtained by the carbonylation reaction, and the mixture of o-dichlorobenzene and the reaction mixture The volume ratio was 2:1, and it was allowed to stand at 0°C for 2 hours until crystals were precipitated and filtered to obtain the pentamethylenedicarbamate product.

Example 3

The present embodiment provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix dimethyl carbonate, pentamethylenediamine and methanol at a molar ratio of 10:1:3, then add potassium phosphate whose mass ratio is 35% of the PDA mass, and a carbonylation reaction occurs for 6 hours at 70°C and 0.5MPa. During the reaction Continue to stir and distill at the same time to remove the methanol produced by the reaction; after the reaction, heat until the solid dissolves, add water to the reaction liquid obtained by the carbonylation reaction, the volume ratio of water to the reaction mixture is 4:1, 10 Stand at ℃ for 4h to precipitate crystals and filter to obtain pentamethylene dicarbamate product.

Example 4

The present embodiment provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix dimethyl carbonate, pentamethylenediamine and water at a molar ratio of 20:1:20, then add tetramethylguanidine with a mass ratio of 10% by mass of PDA, and a carbonylation reaction occurs for 6 hours at 130°C, and the reaction process lasts Stir while feeding 1MPa nitrogen to remove the methanol produced by the reaction; after the reaction, heat until the solid dissolves, add o-dichlorobenzene in the reaction solution obtained by the carbonylation reaction, and add o-dichlorobenzene and the mixture of o-dichlorobenzene and the reaction mixture The volume ratio was 8:1, and it was allowed to stand at 50°C for 10 h until crystals were precipitated and filtered to obtain the pentamethylene dicarbamate product.

Example 5

The present embodiment provides a kind of method for preparing pentamethylene dicarbamate, described method comprises the following steps:

Mix dimethyl carbonate, pentamethylenediamine and ethanol at a molar ratio of 4:1:4, then add ethanolamine with a mass ratio of 5% of PDA mass, and carbonylation reaction occurs for 6 hours at 90°C and 1MPa, and keep stirring during the reaction , and distill at the same time to remove the methanol produced by the reaction; after the reaction, heat until the solid dissolves, add methanol to the reaction solution obtained by the carbonylation reaction, the volume ratio of methanol to the reaction mixture is 3:1, statically at 20°C Set aside for 5h to precipitate crystals and filter to obtain pentamethylene dicarbamate product.

Example 6

The present embodiment provides a method for preparing pentamethylenedicarbamate. The difference between the method and Example 1 is that, before the reaction starts, dimethyl carbonate and pentamethylenediamine are mixed in a molar ratio of 10:1:55. and water.

Example 7

The present embodiment provides a method for preparing pentamethylenedicarbamate. The difference between the method and Example 1 is that before the reaction starts, dimethyl carbonate and pentamethylenediamine are mixed in a molar ratio of 10:1:2. and water.

Example 8

This embodiment provides a method for preparing pentamethylene dicarbamate. The difference between the method and Example 1 is that before the reaction starts, potassium phosphate with a mass ratio of 3% by mass of PDA is added.

Example 9

This embodiment provides a method for preparing pentamethylenedicarbamate. The difference between the method and Example 1 is that before the reaction starts, potassium phosphate with a mass ratio of 40% of the PDA mass is added.

Comparative example 1

This comparative example provides a method for preparing pentamethylene dicarbamate. The difference between the method and Example 1 is that the titanium dioxide catalyst in CN113603613A is used for the reaction, and the reaction conditions are the same as those in the specific embodiment.

The resulting product is subjected to compositional analysis, and the specific analysis conditions are as follows:

Column model RTX-5; initial column temperature is 50°C, keep for 1min, raise to 150°C at 20°C/min, keep for 1min, then rise to 220°C at 20°C/min, keep at 220°C for 12min; control mode is pressure control, The pressure is 110kPa, the purge flow rate is 3mL/min, the split ratio is 25; the gasification temperature is 250°C.

For the pentamethylenedicarbamate obtained by the preparation methods of the above-mentioned Examples 1-9 and Comparative Example 1, the reaction solution was absorbed for chromatographic analysis at 85° C., and the yield was calculated. The relevant indicators of the yield are shown in Table 1.

Table 1

It can be seen from Table 1 that:

(1) comprehensive embodiment 1-5 can find out, a kind of method for preparing pentamethylene dicarbamate provided by the invention, with carbonylating agent and amine substrate as reactant, adopts organic base substance as catalyzer, At the same time, a solvent is added to assist the reaction, the catalytic effect is good, the product purity is high, the conversion rate of pentamethylenediamine is 100%, the yield of pentamethylenedicarbamate is ≥ 82%, and the purity of pentamethylenedicarbamate is ≥ 99%;

(2) comprehensive embodiment 1 and embodiment 6-7 can find out, the ratio of the first solvent and pentamethylenediamine in embodiment 1 is 10:1, and the first solvent and pentamethylenediamine in embodiment 6 and embodiment 7 The ratio of amine is respectively 55:1 and 2:1; The pentamethylenediamine transformation rate of embodiment 1 is 100%, and the pentamethylenedicarbamate yield is 99%, and the pentamethylenedicarbamate product purity is 99%, And the conversion rate of pentamethylenediamine of embodiment 6 and embodiment 7 is respectively 90% and 90%, pentamethylene dicarbamate yield is only respectively 72% and 78%, and pentamethylene dicarbamate product purity is only respectively respectively 95% and 95%, thus showing that the preferred ratio of the first solvent of the present invention and pentamethylenediamine makes the reaction process faster, and the purity and yield of pentamethylenedicarbamate are higher;

(3) comprehensive embodiment 1 and embodiment 8-9 can find out, the quality that adds catalyst in embodiment 1 is 10% of PDA quality, and the quality that adds catalyst in embodiment 8 and embodiment 9 is respectively 10% of PDA quality 3% and 40%; the pentamethylene dicarbamate yield of embodiment 1 is 99%, and the pentamethylene dicarbamate product purity is 99%, and the pentamethylene dicarbamate yield of embodiment 8 and embodiment 9 The yield is only 69% and 56% respectively, and the product purity of pentamethylene dicarbamate is only 93% and 90% respectively, which shows that the present invention adopts the preferred addition amount of catalyst to improve the reaction yield and product purity;

(4) comprehensive embodiment 1 and comparative example 1 can find out, add and adopt organic base catalyst in embodiment 1, and comparative example adopts titanium dioxide inorganic catalyst; The acid ester yield is 99%, and the pentamethylenediamine product purity is 99%, while the pentamethylenediamine transformation rate of comparative example 1 is only 55%, and the pentamethylenedicarbamate yield is only 14%, and the pentamethylenediamine The purity of the carbamate products is only 90%, which shows that the present invention uses organic bases to catalyze the reaction, which improves the conversion rate of pentamethylenediamine, and also improves the yield and purity of pentamethylenedicarbamate.

In summary, a method for preparing pentamethylenedicarbamate provided by the present invention uses an organic base to catalyze the reaction to generate a pentamethylenedicarbamate product, which has a good catalytic effect, high product purity, and mild reaction conditions, suitable for Industrial production use.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, and those skilled in the art should understand that any person skilled in the art should be aware of any disclosure in the present invention Within the technical scope, easily conceivable changes or substitutions all fall within the scope of protection and disclosure of the present invention.

Claims (26)

1. A process for the preparation of pentanedicarbamates, the process comprising the steps of:

mixing a carbonylation agent and an amine substrate, and then mixing the mixture with an organic base catalyst to carry out carbonylation reaction to obtain a glutaraldehyde formate product;

wherein the amine substrate comprises an aliphatic amine substrate or an aromatic amine substrate, and the organic base catalyst comprises any one or a combination of at least two of potassium phosphate, ethanolamine, tetramethylguanidine or triethylamine;

the carbonylation agent is dimethyl carbonate.

2. The method according to claim 1, wherein the molar ratio of the carbonylation agent to the amine substrate is (2 to 15): 1.

3. The method according to claim 1, wherein the fatty amine based substrate comprises pentanediamine and/or hexanediamine.

4. The method of claim 1, wherein the aromatic amine based substrate comprises aniline.

5. The method according to claim 1, wherein the equivalent weight of the organic base catalyst used is 5 to 35% for the amine substrate.

6. The method according to claim 5, wherein the equivalent weight of the organic base catalyst used is 10 to 25% for the amine-based substrate.

7. The process according to claim 1, wherein the reaction time of the carbonylation reaction is 0.5 to 24h.

8. The method according to claim 7, wherein the reaction time of the carbonylation reaction is 3 to 12h.

9. The process according to claim 1, wherein the reaction temperature of the carbonylation reaction is 25 to 150 ℃.

10. The process according to claim 9, wherein the reaction temperature of the carbonylation reaction is 50 to 85 ℃.

11. The method according to claim 1, wherein the reaction pressure of the carbonylation reaction is 0 to 2MPa.

12. The process of claim 11, wherein the carbonylation reaction is carried out at a pressure of 0.5 to 1.5mpa.

13. The method of claim 1, wherein the carbonylation agent and the amine substrate are further combined with a first solvent prior to reacting.

14. The method of claim 13, wherein the first solvent comprises any one of methanol, ethanol, or water, or a combination of at least two thereof.

15. The method according to claim 13, wherein the molar ratio of the first solvent to the amine substrate is (3 to 50): 1.

16. The process of claim 1, wherein the carbonylation reaction is maintained under agitation.

17. A process according to claim 1, wherein methanol produced by the carbonylation reaction is removed.

18. The method of claim 17, wherein the means for removing methanol comprises sparging or distillation.

19. The method of claim 18, wherein the introduced gas species comprises nitrogen.

20. The method according to claim 1, wherein after the carbonylation reaction, a second solvent is added to the reaction solution obtained by the carbonylation reaction, and the mixture is allowed to stand until crystals are precipitated and separated, thereby obtaining the product of the pentamethylenedicarbamate.

21. The method of claim 20, wherein the second solvent comprises any one of chlorobenzene, o-dichlorobenzene, methanol or ethanol, or a combination of at least two thereof.

22. The method according to claim 20, wherein the volume ratio of the second solvent to the reaction solution obtained after the carbonylation reaction is (1 to 8): 1.

23. The method according to claim 20, wherein the temperature of the standing is-20 to 50 ℃.

24. The method as claimed in claim 20, wherein the standing time is 1 to 10 hours.

25. The method of claim 20, wherein the means of separating comprises filtering.

26. Method according to claim 1, characterized in that it comprises the following steps:

mixing a carbonylation agent, an amine substrate and a first solvent, mixing with an organic base catalyst, carrying out carbonylation reaction for 0.5 to 24h at the temperature of 25 to 150 ℃ and under the pressure of 0 to 2MPa, continuously stirring in the reaction process, and simultaneously introducing nitrogen or distilling to remove methanol generated by the reaction; adding a second solvent into the reaction liquid obtained by the carbonylation reaction, standing for 1 to 10 hours at the temperature of-20 to 50 ℃ until crystals are precipitated, and filtering to obtain a glutaraldehyde ester product;

wherein the amine substrate comprises an aliphatic amine substrate or an aromatic amine substrate, the aliphatic amine substrate comprises pentanediamine and/or hexanediamine, and the aromatic amine substrate comprises aniline; the carbonylation agent is dimethyl carbonate, and the molar ratio of the carbonylation agent to the amine substrate is (2 to 15) to 1; the first solvent comprises any one or a combination of at least two of methanol, ethanol or water, and the molar ratio of the first solvent to the amine substrate is (3-20): 1; the organic base catalyst comprises any one or a combination of at least two of potassium phosphate, ethanolamine, tetramethylguanidine or triethylamine, and for amine substrates, the equivalent weight of the used organic base catalyst is 5 to 35%; the second solvent comprises any one or a combination of at least two of chlorobenzene, o-dichlorobenzene, methanol or ethanol, and the volume ratio of the added second solvent to a reaction liquid obtained after carbonylation reaction is (1-8): 1.