CN114262302B - Method for synthesizing diisocyanate trimer, catalyst and preparation method thereof - Google Patents
Method for synthesizing diisocyanate trimer, catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for synthesizing diisocyanate trimer, a catalyst and a preparation method thereof. The method for synthesizing the diisocyanate trimer comprises the steps of taking diisocyanate as a raw material, and carrying out polymerization reaction in the presence of a catalyst to obtain the diisocyanate trimer, wherein the catalyst comprises a supported ionic liquid, the carrier is a silicon-based mesoporous material, the ionic liquid is an organic guanidine salt ionic liquid, and the organic guanidine salt ionic liquid is chemically bonded on the carrier. The organic guanidine salt ionic liquid comprisesStructural unit and R 6 ‑COO ‑ The structural unit, the organic guanidine salt ionic liquid is chemically bonded on the carrier through the silane coupling agent. The synthesis method of the diisocyanate trimer has the advantages of low reaction temperature, good catalytic selectivity, high yield and capability of obtaining a transparent colorless diisocyanate trimer product with low viscosity.
Description
Technical Field
The invention relates to a method for synthesizing diisocyanate trimer, a catalyst and a preparation method thereof.
Background
The amount of diisocyanate required is large, for example hexamethylene diisocyanate is the most important species of aliphatic diisocyanate and accounts for about 60% of the total demand for aliphatic diisocyanate. However, hexamethylene diisocyanate is relatively volatile and toxic, and most of the hexamethylene diisocyanate monomers are further processed into hexamethylene diisocyanate polymers. The isocyanurate ring of the hexamethylene diisocyanate trimer has the advantages of stable structure and difficult decomposition at high temperature, so that the hexamethylene diisocyanate trimer has the advantages of good heat stability, good wear resistance, good corrosion resistance and the like, and is widely used as a polyurethane curing agent in the fields of furniture, automobile industry, aviation industry, sports equipment and the like.
For the synthesis of the trimer from diisocyanates, a choice of catalyst is more investigated.
Shaojun et al, in the second phase of volume 13 of polyurethane industry 1998, disclose the synthesis of HDI trimer using an N-hydroxyalkyl quaternary ammonium base as the catalyst for the reaction, and the NCO content of the obtained trimer was 23.11% and the product yield was 31.12% when the mass fraction of the catalyst was 0.3%. The NCO content of the trimer obtained in U.S. Pat. No. 3,182 was 19% by using an aromatic quaternary ammonium salt as a catalyst, and the yield was 49.1%. Zhang Jie et al, in the coating industry, volume 45, phase 9, disclose a process for preparing HDI trimers using quaternary ammonium carboxylates of different structures as catalysts with a catalytic selectivity of about 53%. However, the quaternary ammonium base and the quaternary ammonium salt have poor thermal stability, are extremely easy to decompose at high temperature, have poor dispersibility of the catalyst, are easy to aggregate into blocks after being added into a reaction kettle, cause partial inactivation of the catalyst or overhigh local concentration, finally cause poor reaction uniformity, easily generate white jelly and cause turbidity of the product.
US patent 5905151 discloses a lithium salt of an aliphatic or aromatic carboxylic acid as a catalyst, but the reaction temperature needs to be set to 125-250 ℃, the reaction temperature is too high, the product viscosity is large, and in addition, the catalyst brings metal ions to affect the usability of the trimer product.
US patent 4960848 discloses the use of quaternary ammonium fluorides as catalysts which are easy to remove completely, which are low in refining costs and which produce catalytically low colour trimer products. However, the viscosity of the obtained product is high, the viscosity of the product rises rapidly along with the decrease of the NCO content, and meanwhile, the trimer product also has turbidity.
Disclosure of Invention
In view of the shortcomings and drawbacks of the prior art, the present invention provides an improved method for synthesizing diisocyanate trimers, which can be carried out at low temperatures, has good catalytic selectivity, and is capable of obtaining a low viscosity, transparent colorless diisocyanate trimer product.
The invention also provides a novel catalyst for the method for synthesizing the diisocyanate trimer, which has good thermal stability, good catalytic selectivity when used for the method for synthesizing the diisocyanate trimer, high quality of the obtained trimer product, high recycling times of the catalyst, and good catalytic effect after repeated use.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the method takes diisocyanate as a raw material, and carries out polymerization reaction in the presence of a catalyst to obtain diisocyanate trimer, wherein the catalyst comprises a supported ionic liquid, a carrier is a silicon-based mesoporous material, the ionic liquid is an organic guanidine salt ionic liquid, and the organic guanidine salt ionic liquid is chemically bonded on the carrier.
Further, the silicon-based mesoporous material is one or a combination of a plurality of MCM type molecular sieves, SBA type molecular sieves, HMS type molecular sieves, MSU type molecular sieves, ZSM type molecular sieves, KIT type molecular sieves and USY type molecular sieves;
preferably, the silicon-based mesoporous material is one or a combination of more selected from MCM-41 type molecular sieves, SBA-16 type molecular sieves and HMS type molecular sieves.
Further, the organic guanidine salt ionic liquid comprisesStructural unit and R 6 -COO - Structural unit, wherein R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H or C 1 -C 10 Is a group comprising an alkyl group,R 6 -COO - selected from C 2 -C 6 Organic acid radicals of (2);
further preferably, R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 Or C 6 H 13 ，R 6 -COO - Selected from lactate, acetate, propionate, butyrate or isobutyrate.
In some embodiments of the present invention, the organoguanidinium ionic liquid is chemically bound to the support by a silane coupling agent, preferably the silane coupling agent is a combination of one or more selected from the group consisting of 3-chloropropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloroethyltriethoxysilane, 2-chloroethyltrimethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropyldiethoxymethylsilane, 2-chloroethylmethyldimethoxysilane, 2-chloromethyldimethylethoxysilane and 3-chloropropyldimethylethoxysilane.
In some embodiments of the invention, the organoguanidine salt ionic liquid is selected from the group consisting of N, N, N ', N' -tetramethylguanidine lactate ionic liquid, N, N, N ', N', N '-pentamethylguanidine acetate ionic liquid, N, a combination of one or more of N, N' -tetramethyl-N "-butylguanidine propionate ionic liquid and N, N '-dimethyl-N, N' -diethylguanidine lactate ionic liquid.
The inventor discovers that the organic guanidine salt ionic liquid loaded by the silicon-based mesoporous material through chemical bonding can be used as a catalyst for synthesizing diisocyanate trimer, and after the silicon-based mesoporous material is loaded, especially through chemical bonding, the catalytic efficiency of the organic guanidine salt ionic liquid catalyst is increased, the catalytic selectivity is improved, and the viscosity of the trimer product is reduced and is colorless. The three nitrogen atoms of the cations of the organic guanidine salt ionic liquid in the catalyst are conjugated, positive charges are distributed on the three nitrogen atoms and on the central carbon, so that the organic guanidine salt ionic liquid has better thermal stability compared with quaternary ammonium salt and quaternary phosphonium salt, the ionic liquid is immobilized on the silicon-based mesoporous material through a covalent bond by adopting a chemical bonding method, the combination between the ionic liquid and the silicon-based mesoporous material is firmer, the ionic liquid is not easy to fall off, the prepared supported organic guanidine salt ionic liquid is more stable, the recycling performance is good, the recycling frequency is high, and meanwhile, the organic guanidine salt ionic liquid is supported between pore channels of the silicon-based mesoporous material, so that the thermal stability of the catalyst is further improved. In addition, the organic guanidine salt ionic liquid in the catalyst has high catalytic activity, high temperature is not needed in the reaction, and the reaction condition is mild.
In some embodiments of the invention, the organoguanidinium ionic liquid comprises from 5 to 30%, preferably from 7 to 20% of the mass of the catalyst.
Further, the mass ratio of the catalyst to the diisocyanate is 0.01% to 5%, preferably 0.05% to 1%.
In some embodiments of the invention, the diisocyanate is selected from aliphatic diisocyanates or aromatic diisocyanates, the aliphatic diisocyanates are combinations of one or more selected from hexamethylene diisocyanate, isophorone diisocyanate and 4, 4-dicyclohexylmethane diisocyanate, and the aromatic diisocyanates are combinations of one or more selected from toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, p-xylylene diisocyanate, dimethylbiphenyl diisocyanate and naphthalene diisocyanate.
In some embodiments of the invention, the method of synthesizing a diisocyanate trimer comprises the steps of:
1) Adding the diisocyanate and the catalyst to a reaction vessel;
2) Heating to the reaction temperature of 20-100 ℃, preferably 30-60 ℃, reacting for 2-10 hours, preferably 3-8 hours, measuring the-NCO content in the reaction liquid, and adding a terminator to terminate the reaction when the NCO content is reduced to 15-40%;
3) And after the heat preservation is carried out for a certain time, the temperature of the reaction system is reduced, the catalyst is filtered, and the obtained filtrate is subjected to two-stage thin film distillation separation to obtain the diisocyanate trimer.
Further, the terminator is selected from one or more of benzoyl chloride, phosphoric acid, p-hexanesulfonate and dimethyl sulfate, preferably benzoyl chloride;
further, the addition mass of the terminator is 0.01% -2%, preferably 0.05% -1% of the mass of the aliphatic diisocyanate.
In some embodiments of the invention, the incubation time is from 0.2 to 5 hours, preferably from 0.5 to 2 hours.
In some embodiments of the invention, in the two-stage membrane distillation separation, the primary membrane separation pressure is 500-2000 Pa, the temperature is 100-170 ℃, the secondary membrane separation pressure is 50-1000 Pa, and the temperature is 100-140 ℃.
Further, the filtered catalyst is recycled.
Preferably, the diisocyanate is selected from hexamethylene diisocyanate, and the synthetic method has the following reaction formula:
the invention also provides a preparation method of the catalyst, which comprises the following steps:
1) Carrying out surface modification on the silicon-based mesoporous material by adopting a silane coupling agent to obtain a surface-modified silicon-based mesoporous material;
2) Reacting organic guanidine with the silicon-based mesoporous material subjected to surface modification to obtain the silicon-based mesoporous material modified by the organic guanidine;
3) And reacting the organic guanidine modified silicon-based mesoporous material with organic acid to obtain the catalyst.
Further, the structural formula of the organic guanidine isWherein R is 1 、R 2 、R 3 、R 4 、R 5 Each of which is a single pieceIndependently selected from H or C 1 -C 10 Preferably R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 Or C 6 H 13 The organic acid is selected from C 2 -C 6 Preferably, the organic acid is selected from lactic acid, acetic acid, propionic acid, butyric acid or isobutyric acid.
In some embodiments of the present invention, the silane coupling agent is selected from one or more of 3-chloropropyl triethoxysilane, 3-chloropropyl trimethoxysilane, 2-chloroethyl triethoxysilane, 2-chloroethyl trimethoxysilane, 3-chloropropyl dimethoxymethylsilane, 3-chloropropyl diethoxymethylsilane, 2-chloroethyl methyldimethoxysilane, 2-chloromethyldimethylethoxysilane, and 3-chloropropyl dimethylethoxysilane.
In some embodiments of the invention, the mass ratio of the silane coupling agent to the silicon-based mesoporous material is 0.5 to 2, preferably 0.8 to 1.2; and/or the mass ratio of the organic guanidine to the surface-modified silicon-based mesoporous material is 0.1-1, preferably 0.2-0.5; and/or the mass ratio of the organic acid to the organic guanidine modified silicon-based mesoporous material is 0.05-0.5, preferably 0.1-0.3.
In some embodiments of the present invention, the step 1) is performed in an organic solvent and under nitrogen atmosphere, and the reaction is performed for 4-8 hours at a temperature of 80-120 ℃, wherein the organic solvent in the step 1) is selected from one or more of chlorobenzene, toluene, xylene and ethyl acetate, preferably toluene; and/or, the step 2) is carried out in an organic solvent and under nitrogen atmosphere, and the reaction is carried out for 15-35 hours at the temperature of 80-120 ℃, wherein the organic solvent in the step 2) is selected from one or more of chlorobenzene, toluene, xylene and ethyl acetate, and toluene is preferred; and/or, the step 3) is carried out in an organic solvent, the reaction temperature is 15-35 ℃, the reaction time is 2-4h, and the organic solvent in the step 3) is selected from one or a combination of more of cyclohexane, ethanol, methanol, acetonitrile and acetone, preferably ethanol.
In some embodiments of the invention, the method of preparing the catalyst comprises the steps of:
(1) Weighing a certain amount of 3-chloropropyl triethoxysilane and a silicon-based mesoporous material, putting the materials into a reaction bottle, adding a certain amount of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 4-8 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 3-10 hours to obtain the silicon-based mesoporous material with the surface modified, wherein the reaction formula is shown as follows:
(2) Dissolving organic guanidine in toluene solution, adding a certain amount of surface modified silicon-based mesoporous material, stirring at 95 ℃ for reaction for 15-35 hours under the protection of nitrogen, filtering after the reaction, washing for several times by diethyl ether, and vacuum drying at 80 ℃ for 4-8 hours to obtain the organic guanidine modified silicon-based mesoporous material, wherein the reaction formula is as follows:
(3) Adding the organic guanidine modified silicon-based mesoporous material into a certain amount of ethanol, uniformly mixing, dropwise adding a certain amount of organic acid, stirring for 2-4 hours at room temperature, filtering after the reaction is finished, washing for several times by using ethanol, and vacuum drying for 3-10 hours at 100 ℃ to obtain the catalyst, wherein the reaction formula is as follows:
compared with the prior art, the invention has the following advantages:
the synthesis method of the diisocyanate trimer has the advantages of low reaction temperature, good reaction selectivity, high yield and capability of obtaining a transparent colorless diisocyanate trimer product with low viscosity.
The catalyst has good thermal stability, high catalytic activity and high reaction selectivity of trimer synthesis, and the synthesis reaction does not need high temperature; the catalyst has good dispersibility, is not easy to adhere to the surfaces of a reaction kettle and a stirring paddle in the reaction process, and the diisocyanate trimer product prepared by the catalyst has low viscosity, is colorless and transparent, and obviously improves the quality of the trimer product; and the catalyst is convenient to recycle and apply, the catalytic performance is not obviously reduced after the catalyst is applied for more than 20 times.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The loading of catalyst in each of the examples below = active component mass/(active component mass + support mass) ×100%.
Example 1
1) Preparation of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by MCM-41 molecular sieve through chemical bonding
(1) Weighing 100g of 3-chloropropyl triethoxysilane and 100g of MCM-41 molecular sieve, putting into a reaction bottle, adding 500ml of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 6 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 5 hours to obtain the silicon-based mesoporous material with the modified surface.
(2) 25g of N, N' -tetramethyl guanidine is dissolved in 250ml of toluene solution, 100g of the silicon-based mesoporous material with surface modified is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, the mixture is washed with diethyl ether for several times, and the mixture is dried in vacuum at 80 ℃ for 4 hours to obtain the organic guanidine modified silicon-based mesoporous material.
(3) Adding the organic guanidine modified silicon-based mesoporous material into 400ml of ethanol, dropwise adding 20g of lactic acid, stirring for 3 hours at room temperature, filtering after the reaction is finished, washing for several times by using ethanol, and vacuum drying for 5 hours at 100 ℃ to obtain 114.5g of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by the MCM-41 molecular sieve through chemical bonding, wherein the loading capacity of the catalyst is 12.7%.
2) Synthesis of diisocyanate trimer
1000g of hexamethylene diisocyanate HDI and 5g of the catalyst are added into a reaction vessel, stirred and heated to 35 ℃ under the protection of nitrogen, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added to stop the reaction, after the reaction is continued for 0.5 hour at the temperature, the temperature is reduced, the stirring is stopped, and the catalyst is filtered, so that the transparent colorless liquid is obtained. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 120 ℃.
Determining the content of-NCO in a product by titration of di-n-butylamine, analyzing the content of free hexamethylene diisocyanate in a sample by liquid chromatography, determining the viscosity of the product by a viscometer, determining the catalytic selectivity by gel permeation chromatography, wherein the calculation method of the catalytic selectivity is C Catalytic selectivity ＝W HDI trimer /(W HDI trimer +W HDI dimer +W HDI multimers ) 100%, where W HDI trimer 、W HDI dimer 、W HDI multimers The mass of the HDI trimer, the HDI dimer and the HDI multimer in the product are respectively.
The final product was found to have an NCO content of 23.5%, an HDI monomer content of 0.13%, a product viscosity of 1750 mPa.s, a product yield of 72.5% and a catalytic selectivity of 65.5%.
Example 2
1) Preparation of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by HMS type molecular sieve through chemical bonding
(1) Weighing 100g of 3-chloropropyl triethoxysilane and 100g of HMS molecular sieve, putting into a reaction bottle, adding 500ml of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 6 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 5 hours to obtain the silicon-based mesoporous material with the modified surface.
(2) 25g of N, N' -tetramethylguanidine is dissolved in 250ml of toluene solution, 100g of the dried product is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, washed with diethyl ether for several times, and dried for 4 hours at 80 ℃ in vacuum, so that the organic guanidine modified silicon-based mesoporous material is obtained.
(3) Adding the product into 400ml of ethanol, dropwise adding 20g of lactic acid, stirring at room temperature for 3 hours, filtering after the reaction is finished, washing with ethanol for several times, and vacuum drying at 100 ℃ for 5 hours to obtain 113g of N, N, N ', N' -tetramethylguanidine lactate ionic liquid catalyst loaded by HMS molecular sieve through chemical bonding, wherein the loading amount of the catalyst is 11.5%.
2) Synthesis of diisocyanate trimer
1000g of hexamethylene diisocyanate HDI monomer and 5.75g of the catalyst are added into a reaction vessel, stirred and heated to 40 ℃ under the protection of nitrogen, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added to stop the reaction, after the heat preservation reaction is continued for 0.5 hour, the temperature is reduced, the stirring is stopped, and the catalyst is filtered, so that the transparent colorless liquid is obtained. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 120 ℃. The final product was found to have an NCO content of 23.1%, an HDI monomer content of 0.15%, a product viscosity of 1870 mPa.s, a product yield of 70.5% and a catalytic selectivity of 64.2%.
Example 3
1) Preparation of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by SBA-16 molecular sieve through chemical bonding
(1) Weighing 100g of 3-chloropropyl triethoxysilane and 100g of SBA-16 molecular sieve, putting into a reaction bottle, adding 500ml of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 6 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 5 hours to obtain the silicon-based mesoporous material with the modified surface.
(2) 25g of N, N' -tetramethylguanidine is dissolved in 250ml of toluene solution, 100g of the dried product is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, washed with diethyl ether for several times, and dried for 4 hours at 80 ℃ in vacuum, so that the organic guanidine modified silicon-based mesoporous material is obtained.
(3) Adding the product into 400ml of ethanol, dropwise adding 20g of lactic acid, stirring at room temperature for 3 hours, filtering after the reaction is finished, washing with ethanol for several times, and vacuum drying at 100 ℃ for 5 hours to obtain 113.8g of N, N, N ', N' -tetramethylguanidine lactate ionic liquid catalyst loaded by SBA-16 type molecular sieve through chemical bonding, wherein the loading capacity of the catalyst is 12.1%.
2) Synthesis of diisocyanate trimer
1000g of HDI monomer and 5.2g of the catalyst are added into a reaction vessel, stirred and heated to 40 ℃ under the protection of nitrogen, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added to stop the reaction, after the heat preservation reaction is continued for 0.5 hour, the temperature is reduced, the stirring is stopped, and the catalyst is filtered, so that transparent colorless liquid is obtained. The reaction liquid is subjected to a two-stage membrane distillation separation technology to obtain an HDI trimer product, wherein the first-stage membrane distillation separation pressure is 1kPa, the temperature is 120 ℃, the second-stage membrane distillation separation pressure is 100Pa, and the temperature is 120 ℃. The final product was determined to have an NCO content of 22.9%, an HDI monomer content of 0.15%, a product viscosity of 1930 mPa.s, a product yield of 68.5% and a catalytic selectivity of 64.7%.
Example 4
1) Preparation of N, N, N ', N ', N ' -pentamethylguanidine acetate ionic liquid catalyst loaded by MCM-41 molecular sieve through chemical bonding
(1) Weighing 100g of 3-chloropropyl triethoxysilane and 100g of MCM-41 molecular sieve, putting into a reaction bottle, adding 500ml of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 6 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 5 hours to obtain the silicon-based mesoporous material with the modified surface.
(2) 25g of N, N' -pentamethylguanidine is dissolved in 250ml of toluene solution, 100g of the dried product is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, washed by diethyl ether for several times, and vacuum dried for 4 hours at 80 ℃ to obtain the organic guanidine modified silicon-based mesoporous material.
(3) Adding the product into 400ml of ethanol, dropwise adding 20g of acetic acid, stirring at room temperature for 3 hours, filtering after the reaction is finished, washing with ethanol for several times, and vacuum drying at 100 ℃ for 5 hours to obtain 112g of N, N, N ', N ', N ' -pentamethylguanidine acetate ionic liquid catalyst loaded by MCM-41 molecular sieve through chemical bonding, wherein the loading capacity of the catalyst is 10.7%.
2) Synthesis of diisocyanate trimer
1000g of HDI monomer and 6g of N, N, N ', N ', N ' -pentamethylguanidine acetate ionic liquid catalyst loaded by MCM molecular sieve are added into a reaction vessel, stirring and heating are carried out under the protection of nitrogen, the temperature is raised to 40 ℃, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added for terminating the reaction, the reaction is continued for 0.5 hour after the heat preservation, cooling and stirring are stopped, and the catalyst is filtered, thus obtaining transparent colorless liquid. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, the temperature is 120 ℃, the NCO content of the final product is 23.3%, the HDI monomer content is 0.14%, the product viscosity is 1815 mPas, the product yield is 69.8%, and the catalytic selectivity is 65.1%.
Example 5
1) Preparation of N, N, N ', N ' -tetramethyl-N ' -butylguanidine propionate ionic liquid catalyst loaded by MCM-41 molecular sieves through chemical bonding
(1) 100g of 3-chloropropyl triethoxysilane and 100g of MCM-41 molecular sieve are weighed and put into a reaction bottle, 500ml of toluene is added as a reaction solvent, the reaction is stirred for 6 hours at 110 ℃ under the protection of nitrogen, after the reaction is finished, the reaction is cooled and filtered, the reaction product is washed by dichloromethane, and the product is dried in vacuum for 5 hours at 100 ℃. Obtaining the silicon-based mesoporous material with the surface modified.
(2) 25g of N, N '-tetramethyl-N' -butylguanidine is dissolved in 250ml of toluene solution, 100g of the dried product is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, the mixture is washed with diethyl ether for several times, and the mixture is dried in vacuum at 80 ℃ for 4 hours, so that the organic guanidine modified silicon-based mesoporous material is obtained.
(3) Adding the product into 400ml of ethanol, dropwise adding 20g of propionic acid, stirring at room temperature for 3 hours, filtering after the reaction is finished, washing with ethanol for several times, and vacuum drying at 100 ℃ for 5 hours to obtain 110.5g of N, N, N ', N ' -tetramethyl-N ' -butylguanidine propionate ionic liquid catalyst loaded by the MCM-41 molecular sieve through chemical bonding, wherein the loading capacity of the catalyst is 9.5%.
2) Synthesis of diisocyanate trimer
1000g of HDI monomer and 7.3g of the catalyst are added into a reaction vessel, stirred and heated to 40 ℃ under the protection of nitrogen, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added to stop the reaction, after the heat preservation reaction is continued for 0.5 hour, the temperature is reduced, the stirring is stopped, and the catalyst is filtered, so that transparent colorless liquid is obtained. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, the temperature is 120 ℃, the NCO content of the final product is 22.7%, the HDI monomer content is 0.15%, the product viscosity is 1960 mPas, the product yield is 68.7%, and the catalytic selectivity is 63.9%.
Example 6
1) The catalyst was prepared in the same manner as in example 1.
2) The synthesis process of the diisocyanate trimer is as follows:
1000g isophorone diisocyanate IPDI,5g N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by MCM-41 type molecular sieve in example 1 through chemical bonding are added into a reaction vessel, stirring and heating are carried out under the protection of nitrogen, the temperature is raised to 35 ℃, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 20%, 1g benzoyl chloride is added for stopping the reaction, the reaction is continued for 0.5 hour after the heat preservation, cooling is stopped, stirring is stopped, and the catalyst is filtered, thus obtaining transparent colorless liquid. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an IPDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 145 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 145 ℃.
Determining the content of-NCO in a product by titration of di-n-butylamine, analyzing the content of free isophorone diisocyanate in a sample by liquid chromatography, determining the viscosity of the product by a viscometer, determining the catalytic selectivity by gel permeation chromatography, and calculating the catalytic selectivity by C Catalytic selectivity ＝W IPDI trimer /(W IPDI trimer +W IPDI dimers +W IPDI multimers ) 100%, where W IPDI trimer 、W IPDI dimers 、W IPDI multimers The mass of the IPDI trimer, the IPDI dimer and the IPDI multimer in the product are respectively.
The final product was determined to have an NCO content of 17.5%, an IPDI monomer content of 0.2%, a product viscosity of 850 mPa.s, a product yield of 73.2% and a catalytic selectivity of 73.5%.
Example 7
1) The catalyst was prepared in the same manner as in example 1.
2) The synthesis process of the diisocyanate trimer is as follows:
1000g toluene diisocyanate TDI and 5g N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by MCM-41 type molecular sieve in example 1 through chemical bonding are added into a reaction vessel, stirring and heating are carried out under the protection of nitrogen, the temperature is raised to 35 ℃, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g benzoyl chloride is added for stopping the reaction, the reaction is continued for 0.5 hour after the heat preservation, cooling is stopped, stirring is stopped, and the catalyst is filtered, thus obtaining transparent colorless liquid. The TDI trimer product is obtained from the reaction liquid by a two-stage thin film distillation separation technology, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 115 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 115 ℃.
Determining the content of-NCO in a product by titration of di-n-butylamine, analyzing the content of free isophorone diisocyanate in a sample by liquid chromatography, determining the viscosity of the product by a viscometer, determining the catalytic selectivity by gel permeation chromatography, and calculating the catalytic selectivity by C Catalytic selectivity ＝W TDI trimer /(W TDI trimer +W TDI dimer +W TDI multimers ) 100%, where W TDI trimer 、W TDI dimer 、W TDI multimers The mass of TDI trimer, TDI dimer and TDI multimer in the product is respectively.
The final product was determined to have an NCO content of 22.0%, a TDI monomer content of 0.3%, a product viscosity of 2560 mPa.s, a product yield of 75.2% and a catalytic selectivity of 64.7%.
Example 8
1) Preparation of MCM-41 molecular sieves N, N '-dimethyl-N, N' -diethylguanidine lactate ionic liquid catalyst carried by chemical bonding
(1) Weighing 100g of 2-chloroethyl trimethoxy silane and 100g of MCM-41 molecular sieve, putting into a reaction bottle, adding 500ml of toluene as a reaction solvent, stirring at 110 ℃ for reaction for 6 hours under the protection of nitrogen, cooling and filtering after the reaction is finished, washing with dichloromethane, and vacuum drying the product at 100 ℃ for 5 hours to obtain the silicon-based mesoporous material with the modified surface.
(2) 25g of N, N '-dimethyl N, N' -diethyl guanidine is dissolved in 250ml of toluene solution, 100g of the surface modified silicon-based mesoporous material is added, the mixture is stirred and reacted for 26 hours at 95 ℃ under the protection of nitrogen, the mixture is filtered after the reaction is finished, the mixture is washed with diethyl ether for several times, and the mixture is dried in vacuum at 80 ℃ for 4 hours to obtain the organic guanidine modified silicon-based mesoporous material.
(3) Adding the organic guanidine modified silicon-based mesoporous material into 400ml of ethanol, dropwise adding 20g of lactic acid, stirring for 3 hours at room temperature, filtering after the reaction is finished, washing for several times by using ethanol, and vacuum drying for 5 hours at 100 ℃ to obtain 112.5g of N, N '-dimethyl N, N' -diethyl guanidine lactate ionic liquid catalyst loaded by the MCM-41 molecular sieve through chemical bonding, wherein the loading amount of the catalyst is 10%.
2) Synthesis of diisocyanate trimer
1000g of hexamethylene diisocyanate HDI and 6.35g of the catalyst are added into a reaction vessel, stirred and heated to 35 ℃ under the protection of nitrogen, the NCO content in the reaction liquid is measured to be reduced to 30% after the reaction is carried out for 4 hours, 1g of benzoyl chloride is added to stop the reaction, the reaction is continued for 0.5 hour after the heat preservation, the temperature is reduced, the stirring is stopped, and the catalyst is filtered to obtain transparent colorless liquid. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 120 ℃.
Determining the content of-NCO in a product by titration of di-n-butylamine, analyzing the content of free hexamethylene diisocyanate in a sample by liquid chromatography, determining the viscosity of the product by a viscometer, determining the catalytic selectivity by gel permeation chromatography, wherein the calculation method of the catalytic selectivity is C Catalytic selectivity ＝W HDI trimer /(W HDI trimer +W HDI dimer +W HDI multimers ) 100%, where W HDI trimer 、W HDI dimer 、W HDI multimers The mass of the HDI trimer, the HDI dimer and the HDI multimer in the product are respectively.
The final product was found to have an NCO content of 22.8%, an HDI monomer content of 0.15%, a product viscosity of 1850 mPa.s, a product yield of 69.7% and a catalytic selectivity of 63.5%.
Comparative example 1
1000g of HDI monomer and 0.64g of N, N' -tetramethyl guanidine lactate ionic liquid catalyst are added into a reaction vessel, stirring and heating are carried out under the protection of nitrogen, the temperature is raised to 35 ℃, after the reaction is carried out for 4 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added for stopping the reaction, the reaction is continued to be carried out for 0.5 hour, the temperature is reduced, stirring is stopped, the yellowish liquid is obtained, the reaction liquid is subjected to a two-stage thin film distillation separation technology, the HDI trimer product is obtained, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, the temperature is 120 ℃, the final product NCO content is measured to be 18.5%, the HDI monomer content is 0.15%, the product viscosity is 3580 mPas, the product yield is 54.3%, the catalytic selectivity is 48.5%, and the guanidine salt ionic liquid catalyst which is not loaded by a molecular sieve has low catalytic efficiency, the catalytic selectivity is poor, the viscosity is high, and the color is yellow.
Comparative example 2
The MCM-41 type molecular sieve in the catalyst in this comparative example was loaded with ionic liquid not by chemical bonding but by physical adsorption.
1) Preparation of MCM-41 molecular sieves N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst carried by physical adsorption
(1) 25g of N, N' -tetramethyl guanidine is dissolved in 250ml of toluene solution, 100g of MCM-41 molecular sieve is added, stirring reaction is carried out for 26 hours at 95 ℃ under the protection of nitrogen, filtering is carried out after the reaction is finished, diethyl ether is used for washing for several times, and vacuum drying is carried out for 4 hours at 80 ℃ to obtain the organic guanidine modified silicon-based mesoporous material.
(2) Adding the organic guanidine modified silicon-based mesoporous material into 400ml of ethanol, dropwise adding 20g of lactic acid, stirring for 3 hours at room temperature, filtering after the reaction is finished, washing for several times by using ethanol, and vacuum drying for 5 hours at 100 ℃ to obtain 109.5g of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid catalyst loaded by the MCM-41 molecular sieve through physical adsorption, wherein the loading capacity of the catalyst is 8.7%.
2) Synthesis of diisocyanate trimer
1000g of hexamethylene diisocyanate HDI and 7.3g of the catalyst are added into a reaction vessel, stirred and heated to 35 ℃ under the protection of nitrogen, after the reaction is carried out for 6 hours, the NCO content in the reaction liquid is measured to be reduced to about 30%, 1g of benzoyl chloride is added to stop the reaction, after the heat preservation reaction is continued for 0.5 hour, the temperature is reduced, the stirring is stopped, and the catalyst is filtered, so that the transparent colorless liquid is obtained. The reaction liquid is subjected to a two-stage thin film distillation separation technology to obtain an HDI trimer product, wherein the first-stage thin film distillation separation pressure is 1000Pa, the temperature is 120 ℃, the second-stage thin film distillation separation pressure is 100Pa, and the temperature is 120 ℃.
Determining the content of-NCO in a product by titration of di-n-butylamine, analyzing the content of free hexamethylene diisocyanate in a sample by liquid chromatography, determining the viscosity of the product by a viscometer, determining the catalytic selectivity by gel permeation chromatography, wherein the calculation method of the catalytic selectivity is C Catalytic selectivity ＝W HDI trimer /(W HDI trimer +W HDI dimer +W HDI multimers ) 100%, where W HDI trimer 、W HDI dimer 、W HDI multimers The mass of the HDI trimer, the HDI dimer and the HDI multimer in the product are respectively.
The final product was determined to have an NCO content of 19.2%, an HDI monomer content of 0.15%, a product viscosity of 2860 mPa.s, a product yield of 61.2% and a catalytic selectivity of 54.5%.
Example 9
Experiment for catalyst application:
the MCM-41 type molecular sieve filtered in example 1 was subjected to a mechanical experiment using a chemically bound supported N, N' -tetramethylguanidine lactate ionic liquid catalyst, and the data are shown in table 1 below, and the procedure for specific catalytic synthesis of diisocyanate trimer was the same as in example 1. Therefore, the catalyst can be repeatedly used for a plurality of times, and the catalytic activity is not obviously reduced after the catalyst is used for a plurality of times.
TABLE 1
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (21)
1. A method for synthesizing diisocyanate trimer, which takes diisocyanate as raw material and carries out polymerization reaction in the presence of catalyst, is characterized in that: the catalyst is a supported ionic liquid, wherein in the supported ionic liquid, a carrier is a silicon-based mesoporous material, the ionic liquid is an organic guanidine salt ionic liquid, and the organic guanidine salt ionic liquid is chemically bonded on the carrier; the organic guanidine salt ionic liquid is chemically bonded to the carrier through a silane coupling agent; the organic guanidine salt ionic liquid is prepared from
Structural unit and R 6 -COO - Structural unit composition, wherein R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H or C 1 -C 10 Alkyl of (a); the R is 6 -COO - Selected from lactate, acetate, propionate, butyrate or isobutyrate; the silicon-based mesoporous material is selected from one or a combination of a plurality of MCM type molecular sieves, SBA type molecular sieves, HMS type molecular sieves, MSU type molecular sieves, ZSM type molecular sieves, KIT type molecular sieves and USY type molecular sieves.
2. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the silicon-based mesoporous material is selected from one or a combination of a plurality of MCM-41 type molecular sieves, SBA-16 type molecular sieves and HMS type molecular sieves.
3. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 Or C 6 H 13 。
4. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the silane coupling agent is selected from one or more of 3-chloropropyl triethoxysilane, 3-chloropropyl trimethoxysilane, 2-chloroethyl triethoxysilane, 2-chloroethyl trimethoxysilane, 3-chloropropyl dimethoxy methylsilane, 3-chloropropyl diethoxymethylsilane, 2-chloroethyl methyldimethoxy silane, 2-chloromethyl dimethylethoxy silane and 3-chloropropyl dimethylethoxy silane.
5. A process for the synthesis of a diisocyanate trimer according to claim 1 or 3, characterised in that: the organic guanidine salt ionic liquid is selected from one or a combination of more of N, N, N ', N' -tetramethyl guanidine lactate ionic liquid, N, N, N ', N', N '-pentamethyl guanidine acetate ionic liquid, N, N, N', N '-tetramethyl-N' -butyl guanidine propionate ionic liquid and N, N '-dimethyl-N, N' -diethyl guanidine lactate ionic liquid.
6. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the organic guanidine salt ionic liquid accounts for 5-30% of the mass of the catalyst; and/or the mass ratio of the catalyst to the diisocyanate is 0.01-5%.
7. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the organic guanidine salt ionic liquid accounts for 7-20% of the mass of the catalyst; and/or the mass ratio of the catalyst to the diisocyanate is 0.05-1%.
8. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the diisocyanate is selected from aliphatic diisocyanate or aromatic diisocyanate, the aliphatic diisocyanate is selected from one or a combination of more than one of hexamethylene diisocyanate, isophorone diisocyanate and 4, 4-dicyclohexylmethane diisocyanate, and the aromatic diisocyanate is selected from one or a combination of more than one of toluene diisocyanate, diphenylmethane diisocyanate, terephthalene diisocyanate, dimethylbiphenyl diisocyanate and naphthalene diisocyanate.
9. The method for synthesizing a diisocyanate trimer according to claim 1, characterized in that: the method comprises the following steps:
1) Adding the diisocyanate and the catalyst to a reaction vessel;
2) Heating to the reaction temperature of 20-100 ℃, measuring the-NCO content in the reaction liquid after the reaction is carried out for 2-10 hours, and adding a terminator to terminate the reaction when the-NCO content is reduced to 15-40%;
3) And after the heat preservation is carried out for a certain time, the temperature of the reaction system is reduced, the catalyst is filtered, and the obtained filtrate is subjected to two-stage thin film distillation separation to obtain the diisocyanate trimer.
10. The method of synthesizing a diisocyanate trimer according to claim 9, characterized in that: and 2) heating to the reaction temperature of 30-60 ℃, measuring the-NCO content in the reaction liquid after the reaction is carried out for 3-8 hours, and adding a terminator to terminate the reaction when the-NCO content is reduced to 15% -40%.
11. The method of synthesizing a diisocyanate trimer according to claim 9, characterized in that: the terminator is selected from one or more of benzoyl chloride, phosphoric acid, p-hexanesulfonate and dimethyl sulfate; the addition mass of the terminator is 0.01% -2% of the mass of the diisocyanate.
12. The method of synthesizing a diisocyanate trimer according to claim 9, characterized in that: the terminator is benzoyl chloride; the addition mass of the terminator is 0.05-1% of the mass of the diisocyanate.
13. The method of synthesizing a diisocyanate trimer according to claim 9, characterized in that: the heat preservation time is 0.2-5 h; and/or, in the two-stage membrane distillation separation, the primary membrane separation pressure is 500-2000 Pa, the temperature is 100-170 ℃, the secondary membrane separation pressure is 50-1000 Pa, and the temperature is 100-150 ℃.
14. The method of synthesizing a diisocyanate trimer according to claim 9, characterized in that: the heat preservation time is 0.5-2 h.
15. A catalyst as claimed in any one of claims 1 to 14.
16. A method for preparing the catalyst of claim 15, wherein: the preparation method comprises the following steps:
1) Carrying out surface modification on the silicon-based mesoporous material by adopting a silane coupling agent to obtain a surface-modified silicon-based mesoporous material;
2) Reacting organic guanidine with the silicon-based mesoporous material subjected to surface modification to obtain the silicon-based mesoporous material modified by the organic guanidine;
3) Reacting the organic guanidine modified silicon-based mesoporous material with organic acid to obtain the catalyst; the structural formula of the organic guanidine isWherein R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H or C 1 -C 10 Alkyl of (a); the organic acid is selected from lactic acid, acetic acid, propionic acid, butyric acid or isobutyric acid.
17. The method for preparing a catalyst according to claim 16, wherein: the R is 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 Or C 6 H 13 The method comprises the steps of carrying out a first treatment on the surface of the And/or the silane coupling agent is selected from 3-chloropropyl triethoxysilane, 3-chloropropyl trimethoxysilane, 2-chloroethyl triethoxysilane, 2-chloroethyl trimethoxysilane, 3-chloropropyl dimethoxy methylsilane, 3-chloropropylOne or more of the group of diethoxymethylsilane, 2-chloroethyl methyldimethoxysilane, chloromethyldimethylethoxysilane and 3-chloropropyldimethylethoxysilane.
18. The method for preparing a catalyst according to claim 16, wherein: the mass ratio of the silane coupling agent to the silicon-based mesoporous material is 0.5-2; and/or the mass ratio of the organic guanidine to the surface-modified silicon-based mesoporous material is 0.1-1; and/or the mass ratio of the organic acid to the organic guanidine modified silicon-based mesoporous material is 0.05-0.5.
19. The method for preparing the catalyst according to claim 16, wherein: the mass ratio of the silane coupling agent to the silicon-based mesoporous material is 0.8-1.2; and/or the mass ratio of the organic guanidine to the surface-modified silicon-based mesoporous material is 0.2-0.5; and/or the mass ratio of the organic acid to the organic guanidine modified silicon-based mesoporous material is 0.1-0.3.
20. The method for preparing a catalyst according to claim 16, wherein: the step 1) is carried out in an organic solvent and under the nitrogen atmosphere, the reaction is carried out for 4-8 hours at the temperature of 80-120 ℃, and the organic solvent in the step 1) is selected from one or more of chlorobenzene, toluene, xylene and ethyl acetate; and/or, the step 2) is carried out in an organic solvent and under nitrogen atmosphere, the reaction is carried out for 15-35 hours at the temperature of 80-120 ℃, and the organic solvent in the step 2) is selected from one or more of chlorobenzene, toluene, xylene and ethyl acetate; and/or, the step 3) is carried out in an organic solvent, the reaction temperature is 15-35 ℃, the reaction time is 2-4h, and the organic solvent in the step 3) is selected from one or more of cyclohexane, ethanol, methanol, acetonitrile and acetone.
21. The method for preparing a catalyst according to claim 20, wherein: the organic solvent in the step 1) is toluene; and/or, the organic solvent in the step 2) is toluene; and/or, the organic solvent in the step 3) is ethanol.
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