JPH07501561A - Production of trimethylolpropane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Production of trimethylolpropane Technical field The present invention relates to the production of trimethylolpropane and particularly to the formula R'R"CHOH (wherein and R1 and R2 are independently hydrogen or an alkyl group having from 1 to about 5 carbon atoms. are, but - together have no more than 6 carbon atoms) n-butyraldehyde (NBA) in the presence of at least 20% lower alcohol L) and formaldehyde.

Background of the invention Conventional production of trimethylolpropane typically involves processing intended for purification. to obtain an aldol reaction product that can be hydrogenated over a hydrogenation catalyst with or without This requires the reaction of n-butyraldehyde and formaldehyde (usually in aqueous solution). Ru. Representative conventional techniques include U.S. Pat. Nos. 4,122,290 and 4,5. No. 14,578 (Immel et al.) and No. 4,594,461 (Merger et al.) (Nato), and these have been described in using a min catalyst. Traditional commercial methods are more or less Although satisfactory, the method of the present invention is even more effective and produces Things are even more pure.

Commercially, formaldehyde is available in two forms: paraformaldehyde. available in form or as an aqueous solution (referred to as aqueous formaldehyde) . Paraformaldehyde has the molecular formula: HO(CHI), )l (where n is 8 ~100) crystals consisting of a linear polymeric form of formaldehyde It is a natural solid. Aqueous formaldehyde is called formaldehyde in its monomeric form. and mainly exist. On the basis of neglect, it gradually reacts itself and polyses - Will form formaldehyde and paraformaldehyde.

This is usually inhibited by adding up to 15% methanol as a stabilizer. be done. “If formaldehyde is used after this, this Formaldehyde in the form of aldehyde or aqueous formaldehyde is particularly means permissible unless otherwise specified.

Klein in U.S. Pat. No. 3,076.854 teaches that alcohol, For example, solvent extraction with amyl alcohol, re-extraction with water, and solvent extraction in the presence of a strong acid. heated with tanol and passed through an ion exchange layer to remove metals. Thus, the treated trimethylolpropane is treated. Purification is done without trace as in the present invention. Not achieved by retaining.

In East German Patent No. 142.184 (Dietze et al.), the reaction product A traditional TMP preparation method by Giru is mentioned to obtain a Shodoru sole containing about 3% of: This bottom is treated with methanol and strengthened to liberate additional TMP. Passed through acid resin.

In Yoromba Patent No. 289.921, Marget et al. 1m, the trialkylation of n-butyraldehyde and aqueous formaldehyde The hydrogenated effluent of the min-catalyzed reaction is being treated.

In the first method, they remove water by distillation at 100-200'C. and remove excess trialkylamine. solid as its formate salt The trialkylamine determined is the free trialkylamine and the polyol form. reacts with trimethylolalkane under distillation conditions to give the mate ester. Ru. Next, they use methanol and alkali or alkaline earth metal alcohols. to produce trimethylolalkane, which is recovered by distillation. collect. A second method is to remove excess water by distillation followed by the addition of methanol to the bottom of the distillation. and the removal of free trialkylamines. This mixture is then evaporated under pressure to 1 heated to 00-200 °C and trialkylamine and methyl formate is removed by distillation. In this case, the water concentration is very limited and 5~ Not more than 15%, the product is finally recovered by distillation, but the purity is not mentioned. The method of the present invention does not require any special treatment prior to the addition of alcohol. and leads to a product of very high purity.

In Example 1 of East German Patent No. 273,434, Raνe et al. Ca (O H) Describe a method for recovering formaldehyde from v-catalyzed reactions . The treatment first consisted of neutralization of the reaction effluent, followed by addition of methanol and 50 min under vacuum. Light stripping at °C, treatment with acetonitrile, removal of calcium salts stripping, addition of additional methanol and stripping to 90°C, formaldehyde Includes removal of light substances including hydride. Product recovery is not mentioned. main application The inventive method is simple and different, and leads to high purity TMP.

Summary of the invention The method of the present invention involves aldol reaction of n-butyraldehyde and formaldehyde. followed by the formula R'R2CHO1+ (where R1 and RZ are independently hydrogen, or an alkyl group having from 1 to about 5 carbon atoms, but - lower alcohols (having no more than 6 carbon atoms) directly accompanied by a hydrogenation step carried out in the presence of at least about 20% by weight. to hydrogenation stage In this case, the catalyst, preferably copper chromite, is heated to a temperature of about 100°C to about 200°C. For use in the pressure range of 500 to about 3000 ps+, and relatively low pressures, i.e. 0 The present invention is very advanced, as will become clear in the following sections. It will give a good yield of the desired product with high purity.

To produce the hydrogenation feed, n-butyraldehyde and formaldehyde are , about 0.5=about 10, preferably O,S:S and most preferably about 1:about 2. Should be used in a molar ratio of 5.

In the present invention, 20 to 90% alcohol, preferably 30 to 60% alcohol Alcohol and most preferably a hydrogenation feed containing 50% alcohol is used. The preferred alcohol is methanol. Alcohol is added after hydrogenation However, most preferably the alcohol is added before hydrogenation. , which is a preferred embodiment of the present invention.

Detailed description of the invention The invention will be described in particular embodiments by the following examples.

Paraformaldehyde ±, -ro　Special properties using cubic paraformaldehyde A specific reaction is described as follows: The reaction consists of 1.00 equivalents of NBAL, 2.50 equivalents of paraformaldehyde and about 0.01-0.05 equivalents of triethylamine is carried out in a reflux apparatus placed under an inert atmosphere. overhead With constant stirring, the reaction mixture was first heated in a water bath at 50 °C; The temperature is gradually increased to 80°C over a period of 30 minutes. The reaction continued for another hour and stopped. The clear molten liquid is alcohol, preferably methanol distilled at about 160°C and 1000 psiHz, Hydrogenation is carried out by passing the reaction solution over a copper romate catalyst. High purity (99 % or more of the TMP product is recovered by distillation.

Another method using formaldehyde is water-injecting formaldehyde. The specific reaction of can be described as follows: The reaction consists of 1.00 equivalents of NBAL, 2 ．． 50 equivalents of aqueous formaldehyde and about 0.04-0.08 equivalents of triethyl It is carried out in a reflux apparatus in which the amine is placed under an inert atmosphere. preferred Alternatively, NBAL is added to a stirred mixture of aqueous formaldehyde and triethylamine. It is added dropwise over a period of 0°25 to 1 hour. Mix the reaction with overhead stirring. Heat the mixture in a water bath at 60'C for 2 hours. The clear liquid is alcohol, which is preferable. preferably diluted with methanol and heated at about 160°C and about 1000 psi. The reaction solution is hydrogenated by passing the reaction solution over a conventional copper chromite catalyst. . High purity (>99%) TMP product is recovered by distillation.

Hill method using formaldehyde More typically, about 2 to about 10 equivalents of formaldehyde are used along with 1 equivalent of NBAL. and about 0.001 to about 1.0 (preferably about 0.05 to about 0.5) equivalents of a third An amine catalyst is placed in a reaction vessel. Most of the NBAL Stir at 60-80°C until consumed. Alcohol, the resulting solution Preferably diluted with methanol and hydrogenated using a hydrogenation catalyst. high A pure TMP product is obtained in good yield by distillation.

up in flames A series of Hantz Aldol reactions were carried out in glassware as follows: A, n-butyraldehyde (1069.3 g, 14.89 mol), baraform Aldehyde (1223.4g, 37.07mol), water (132.4g, 7. 35 mol) and triethylamine (75.0 g, 0.74 mol) in over Three neck round bottom flask equipped with head stirrer, inert atmosphere purge and reflux condenser was filled. The device was placed in a water bath at 50"C. The bath was placed in a water bath for 2 hours. and heated to a temperature of 80'C, at which point more than 99% of the n-butyraldehyde has reacted. I was made to respond. The reaction mixture was diluted in methanol and the methanol solution was A 50-layer aldol was produced. Continuous hydrogenation at 160°C 10,5/hour Copper chromite at a liquid hourly space velocity (LH5V) of by passing the methanolic aldol effluent upward through the stationary phase. I did it. The resulting hydrogenated product was buffered using an 8 inch long packed column. high purity trimethylolpropane product was recovered (99.18% purity, 7363% recovery).

B, n-butyraldehyde (643.7 g, 8.93 mol), aqueous formua aldehyde (1811.2 g, 22.32 mol), and triethylamine (45, 2 g, 0.45 mol) with an overhead stirrer, inert atmosphere purge and reflux. A three neck round bottom flask equipped with a condenser was charged. Place the device in a water bath at 40°C. Placed. Heat the bath to a temperature of 60°C for 1 hour and then The reaction continued for a period of time, at which point more than 97% of the n-butyraldehyde had reacted. So Dilute the reaction mixture in methanol and add 5% 1% aldo in methanol solution. produced a roll.

Continuous hydrogenation at 160°C, 0.5/hr LH5V and 1001000 psi , the methanolic aldol effluent upwardly through the copper chromite stationary phase. This was done by passing it through. The resulting hydrogenated product was placed in an 8-inch long packed cup. A high purity trimethylolpropane product was recovered by batch distillation using ram. (99.07% purity, 68.4% recovery).

C0 example 1. A. Repeated. However, if the aldol reaction mixture is Rather, it is diluted with n-butyl alcohol, and in n-butyl alcohol solution, 0% by weight of aldol was produced. Obtain high purity trimethylolpropane product (99.15% purity, 72.3% recovery).

D. A "control" experiment was performed by repeating Example 1.B, except that hydrogen 9 Recovered trimethylolpropane product with addition of methanol solvent after oxidation was of low purity (98.33% purity, 73.0% recovery).

The data for these four experiments are summarized in Table I. The result is hydrogenation made possible by the addition of a suitable alcohol solvent to the aldol reaction product before represents a surprising improvement in trimethylolpropane purity.

Table ■ Example IA, IB, IC, ID, (“control”) Solvent level 50% 50% 50% 5% (wt%) (included) TMP recovery rate 73% 68% 72% 73%■1 Two Hutchialdol reactions were carried out in glassware as follows: A, n-butyraldehyde (772.4 g, 10.71 mol), aqueous formua aldehyde (2173.4 g, 26.78 mol), and triethylamine (54 , 2 g, 0.54 mol) in an overhead stirrer, an inert atmosphere, and The mixture was charged into a three neck round bottom flask equipped with a reflux condenser. The device was heated at 40°C. Placed in a water bath. Heat the bath to a temperature of 60"C for 2 hours and at this point More than 99% of n-butyraldehyde was reacted. The reaction mixture is Diluted in tanol to produce 90% by weight aldol in methanol solution . Continuous hydrogenation was carried out at 160'C, 0.5/hr Ll (SV and 1000ps ig the methanol on three sides through a copper chromite stationary phase stabilized with Hg. This was done by passing the aldol effluent. The obtained hydrogenated product was Batch-distilled using an inch-long packed column to produce high-purity trimethylol The bread product was recovered (99.02% purity, 66% recovery).

B, n-butyraldehyde (943.4 g, 13.08 mol), paraforma Rudehyde (1079.3g, 33.71 mol), water (116.8g, 6.4 8 mol) and triethylamine (66.2 g, 0.65 mol) were added to the overhead in a three-neck round-bottom flask equipped with a head stirrer, an inert atmosphere purge, and a reflux condenser. Filled. The device was placed in a water bath at 50°C. I stayed in that bathtub for an hour. heated to a temperature of 80°C and continued for a further 1 hour, at which point more than 99% n -Butyraldehyde was reacted. Dilute the reaction mixture in methanol , produced 20% by weight aldol in methanol solution. Continuous hydrogenation, Stabilized at 160°C 10,5/hr LIISV and 10001000psi The methanolic aldol effluent is passed upwardly through the copper chromite stationary phase. This was done by passing. The resulting hydrogenated product was packed into an 8-inch length. Batch distillation is performed using a column to recover a highly pure trimethylolpropane product. (99.01% purity, 91% recovery).

When compared to Example IA and Example IB, the data for those two experiments are: Good results using high (90 wt%) and low (20 wt%) methanol levels. These results show similar TMP distillation purity (greater than 99%) with reasonable recoveries. Shown in Table I+.

Table I+ Examples: IA, IB, 2A, 2B.

solvent level (wt%) 50% 50% 90% 20% TMP recovery rate 73% 68% 6 A 6% to 91% patch aldol reaction was performed in glassware as follows. It was: n-Butyraldehyde (600.0g, 8.32mol), Balaforma J Rede Hyde (686.4g, 20.80mol), water (74.31g, 4.12mol) ) and triethylamine (42.1 g, 0.42 mol) with overhead stirring. Fill a three-neck round-bottom flask equipped with a stirrer, inert atmosphere purge, and reflux condenser. Ta. The device was placed in a water bath at 50°C. 80 in that bathtub for 2 hours °C, at which point 99% of the n-butyraldehyde has reacted. Ta. The reaction mixture was diluted in 2-methyl-1-butanol solution and the methanol solution was 511% aldol was produced in the liquid. Continuous hydrogenation at 160°C, 0.5 / Time IJIsV and 1000ps igHg, stabilized copper chromite by passing the methanolic aldol effluent upward through the stationary phase. I did it. The resulting hydrogenated product was passed through an 8 inch long packed column for 1, s. A high purity trimethylolpropane product was recovered (99. 49% purity, 72% recovery).

When compared to Example IA, the results obtained from this experiment show that alcohols of different compositions 1 (IJ distillation) using an alcoholic solvent, i.e. 2-methyl-1-butanol. The obtained TMP purity and recovery rate are shown.

Table III TMP recovery rate 73% 72% Group↓ The Hantschialdol reaction was carried out in glassware as follows; n-Butyraldehyde (772.4 g, 10.71 mol), aqueous formaldehyde Dehyde (2173.4 g, 26.78 mol) and triethylamine (54. 2g.

0.54 mol) with an overhead stirrer, inert atmosphere purge and reflux condenser. It was filled into a three-neck round-bottom flask equipped with a The device was placed in a water bath at 40°C. . The bath was heated to a temperature of 60°C for 2 hours, at which point more than 99% n-Butyraldehyde was reacted. Continuous hydrogenation at 160°C, 0.5 /hour (7) LHSV and 1000 psigHg, stabilized copper chromite Passing the undiluted aldol effluent upward through the stationary phase of So I did it. The obtained hydrogenated product was diluted in methanol and methanol 50% by weight aldol was produced in solution. The obtained hydrogenated product was Batch distillation using inch-long packed columns to produce trimethylolpropane The product was recovered (98.92% purity, 68% recovery).

Example 10 (a “control” experiment using an alcoholic solvent was added before hydrogenation or distillation) results obtained from this experiment when compared to a similar experiment Shows improved distilled TMP purity in yield.

However, the product purity is limited by hydrogenation, which is the most preferred embodiment of the invention. If an alcoholic solvent is added to the aldol effluent before (e.g. Example I The results are summarized in Table IV. shown.

Table IV Example IA, ID, (“Control”) 3. 4゜T) IP recovery rate 73% 73 % 72% 68% patch aldol reaction in glassware as follows. Did: n-butyraldehyde (960.0 g, 13.31 mol), paraformalde Hyde (1098.3g, 33.28mol), water (111.3g, 6.17mol) ) and triethylamine (67.4 g, 0.67 mol) overhead. Fill a three-necked round-bottom flask equipped with a stirrer, inert atmosphere purge, and reflux condenser. did. The device was placed in a water bath at 50°C. 8 in that bathtub for an hour Heating to a temperature of 0°C and continuing for a further 1 hour, at which point 98% n-butyl Aldehydes were reacted. The reaction mixture was mixed with isopropyl alcohol (I PA) to produce 50% by weight aldol in methanol solution.

Continuous hydrogenation at 160°C, 0.5/hr LH3V and 1001000 psi, The methanolic aldo This was done by passing the effluent through the tube. The resulting hydrogenated product was cut into an 8-inch long Batch distillation using a packed column to produce high purity trimethylolpropane product was recovered (99.29% purity, 70% recovery).

The data for this experiment, when compared to Example IA and Example IB, are as follows: Using secondary alcohol, TMP distillation purity (99%) with good recovery was obtained. % or more).

Table■ Continuation of front page (72) Inventor Pugachi, Joseph Eagles, Monroeville, Pennsylvania 15146, United States Strain 1000, Apartment #1035 (72) Inventor Area Carol L., Pennsylvania, United States 15068° Newke 240 Rampart Blvd., Rampart Blvd. (72) Inventor Karow, Leonard Nee.

United States, Pennsylvania 15601゜Greensburg, Maple Terrace, Maple Drive 315

Claims (15)

[Claims] 1. Reacts n-butyraldehyde and formaldehyde under aldol reaction conditions. and the formula R1R2CHOH, where R1 and R2 are hydrogen, and from 1 to about independently selected from alkyl groups having 5 carbon atoms, but together alcohols having no more than 6 carbon atoms) in the presence of about 20% by weight (based on the mixture of alcohol and said reaction products). hydrogenating the reaction product to obtain high purity trimethylolpropane. Method for manufacturing. 2. Claim 1, wherein the hydrogenation is carried out in the presence of a copper chromite catalyst. the method of. 3. Claims wherein said hydrogenation is conducted at a pressure in the range of about 500 to about 3000 psig. The method described in item 1. 4. 2. The method of claim 1, wherein said alcohol includes methanol. 5. The aldol reaction step has the formula RlR2R3N, where R1 and R2 and R3 is independently selected from alkyl and aryl groups having 1 to 5 carbon atoms and R1 and R2 are substituted or unsubstituted atoms having about 5 to about 10 carbon atoms. in the presence of a catalyst comprising an amine (capable of forming a substituted cyclic group) The method according to claim 1. 6. Claim wherein the aldol reaction step is carried out in the presence of a triethylamine catalyst. The method described in item 5. 7. Claim No. 1, wherein said formaldehyde is present in the form of paraformaldehyde. The method described in Section 1. 8. Claim No. 1, wherein said formaldehyde is present in the form of aqueous formaldehyde. The method described in Section 1. Claims that trimethylolproban with a purity of 9.99% or more is recovered by distillation. The method described in Scope 1. 10. Claims wherein said hydrogenation step is conducted at a temperature of about 100<0>C to about 200<0>C. The method described in paragraph 1. 11. n-butyraldehyde in the aldol reaction: formaldehyde 2. The method of claim 1, wherein the molar ratio is from about 1:2 to about 1:5. 12. Claims wherein said methanol is present in an amount of about 30% to about 60% of the hydrogenation feed. The method described in item 4. 13. React n-butyraldehyde and formaldehyde under aldol conditions. and the reaction product is hydrogenated to give the formula R1R2CHOH, where R1 and R2 are independently selected from hydrogen and alkyl groups having from 1 to about 5 carbon atoms; , but together they have no more than 6 carbon atoms) At least about 20% by weight of cole is added to the reaction product and the resulting distilling the mixture to obtain high purity trimethylolproban. Method for producing limethylolproban. 14. The alcohol comprises from about 20% to about 90% by weight of the mixture after such addition. Claim 13 added to the hydrogenated reaction product in an amount of % by weight. How to put it on. 15. 14. The method of claim 13, wherein the alcohol is methanol.