JPH03161452A - Propanediol and production thereof - Google Patents

Abstract

NEW MATERIAL:2-Pentyl-2-propyl-1,3-propanediol. USE:Synthetic raw material for polyurethane resin, polyester resin, plasticizers, cosmetics, etc., thermal medium, reaction solvent, vehicle for forming conductive film, etc. PREPARATION:The subject novel substance can be produced by reacting 2- propylheptanal with formaldehyde or paraformaldehyde at a molar ratio of 1:(2.1-3.0) at 30-90 deg.C in the presence of an aqueous solution of an alkali metal or alkaline-earth metal hydroxide. The amount of the alkali metal or alkaline- earth metal hydroxide is 1.1-1.2mol per 1mol or 2-propylheptanal.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention can be used with high performance as a synthetic raw material for polyurethane resins, polyester resins, plasticizers, cosmetics, etc., as a heat medium, as a reaction solvent, as a vehicle for forming conductive films, etc. 2-pentyl-2-propyl-1, which is easy to handle because it is ready and liquid.
．． This invention relates to 3-propanediol and its manufacturing method.

(Prior art) In general, polyester resins synthesized from glycols that do not have a hydrogen atom on the β-carbon atom, such as neobentyl glycol, have heat resistance, water resistance, alkali resistance,
It is already known that it has excellent acid resistance. In particular, neopentyl glycol esters are stable against alkalis and acids, and are difficult to be hydrolyzed because the two methyl groups on the β-carbon atom of neopentyl glycol block attacks by hydroxide ions and hydrogen ions. It is believed that this is because It is also thought that the heat resistance is due to the fact that it does not have a hydrogen atom at the β-position carbon atom, so it cannot form a six-membered ring as a transition state during the thermal decomposition process. However, in recent years, demands for higher functionality in various uses have been increasing, and raw material diols with even higher functionality are being sought.

2. Examples of 2-dialkyl-substituted-1,3-propanediol include those in which the dialkyl group is dimethyl (neopentyl glycol, hereinafter sometimes abbreviated as NPC), and diethyl (2-diethyl-1,3-propanediol, hereinafter referred to as DMP). (sometimes abbreviated), ethyl, butyl (sometimes abbreviated)
2-butyl-2-ethyl-1,3-propanediol,
(hereinafter sometimes abbreviated as DMH) is well known. Also 1~
Japanese Patent Publication No. 3B-1545 is known as a diol having an alkyl group of 8 carbon atoms. Similar descriptions include Japanese Patent Publication No. 41-8769, Japanese Patent Application Laid-open No. 10223-1982, Japanese Patent Publication No. 18928-1982, and Japanese Patent Application Publication No. 57-53.
There is a publication No. 421.

(Problems to be Solved by the Invention) Diols having an alkyl group of 1 to 6 carbon atoms are known in Japanese Patent Publication No. 39-1545, but the compound closest to the detailed explanation is 2.2. -') Propyl-■,3-propanediol, 2-methyl-2-dodecyl-L 3-propanediol, and 2,2-diisobutyl-1,3-propanediol are described. But 2
-pentyl-2-propyl-1. There is no detailed description of 3-propanediol.

Furthermore, conventionally known 2. All of the 2-dialkyl-substituted 1,3-propanediol is solid in chamber 774, which not only complicates transportation and reaction preparation handling, but also evaporates during transesterification in polyester synthesis with polybasic acids. Problems such as the diol component solidifying inside the outlet pipe caused blockage.

Conventionally, as a countermeasure to this problem, the piping was forcibly heated from the outside or an anti-caking agent such as ethylene glycol was added, but heating the piping requires installation costs and is disadvantageous in terms of utility. Furthermore, the addition of anti-caking agents has been a factor in deteriorating product quality.

Recently, there has been an increasing demand for higher functionality in the fields of polyurethane resins, polyester resins, plasticizers, cosmetics, etc., but to date, no raw material diol has been known that can meet these various demands for higher functionality.

The present invention provides raw material diols that can be used to improve functionality in the fields of polyurethane resins, polyester resins, plasticizers, cosmetics, etc., easy-to-handle diols, and methods for producing the same.

(Means for Solving the Problems) As a result of intensive studies in view of the recent demand for higher functionality, the present inventors found that 2-pentynolyte 2, a new diol,
-7'ropinole-1. It has been found that 3-propanediol has extremely excellent performance when used as a raw material for various purposes.

The present invention provides a method of combining 2-pentyl-2-propyl-1,3-propanediol and 2-propylheptanal with formaldehyde or paraformaldehyde in the presence of an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide. 2-pentyl-2-propyl-1 to react with
．． This is a method for producing 3-7"ropanediol.

That is, the nool of the present invention has 1. It is 3-prohaneshiol, and like neopentylglyfur, it does not have a hydrogen atom at the β-position carbon atom, and has an extremely large branched alkyl group compared to neopentyl glycol.

It is noteworthy that the diol of the present invention and the compounds made from this diol have not been known to date, and that the 2-betinole 2-propynoley 1.3-7' lobanol of the present invention is a novel diol. .

The method for producing 2-pentyl-2-propyl-1.2-pentyl-2-propyl-1.
3-propanediol can be easily obtained.

The 2-probylheptanal used in the method of the present invention is obtained by subjecting valeraldehyde to conventional aldol condensation followed by partial hydrogenation.

The reason why the 2-pentyl-2-propyl-1.3-propanedionole of the present invention has not been known until now is that valeraldehyde, the raw material, is not easily available. In other words, current petrochemistry has developed based on ethylene and propylene, and the aldehydes produced by the oxo process are limited to butyraldehyde, and the production of valeraldehyde by the oxo reaction of butene has not yet been produced on a commercial level. do not have. On the other hand, the recent trend toward fine chemicals requires new products, and the development of butene-1 derivatives, such as valeraldehyde, as well as its derivatives, will continue to be widely sought after in many fields.

As the formaldehyde used in the method of the present invention, an industrially available 5 to 50 wt% formaldehyde aqueous solution can be used as it is, but 70 to 95 wt%
t% of paraformaldehyde is used to obtain the desired product, 2-pentyl-2-propyl-1. This is advantageous in terms of reducing the dissolution loss of 3-propanediol and the amount of waste water treated. The formaldehyde used is generally used in a stoichiometric amount to an excess amount relative to 1 mole of 2-probylheptanal. That is, the amount used is preferably 2.0 to 4.0 mol, particularly 2.1 to 3.0 mol.

The alkali metal hydroxide or alkaline earth metal hydroxide used as a catalyst is used as an aqueous solution, and the agricultural degree is 1.
% to saturation, but like formaldehyde, it is recommended to reduce the dissolution loss of the target product 2-pentyl-2-propyl-1,3-propanediol and the amount of wastewater treated. Higher concentrations are more advantageous;
It is also possible to increase the solubility by heating and use it at a higher concentration. The alkali metal hydroxide or alkaline earth metal hydroxide used is generally used in a stoichiometric amount to an excess amount relative to 1 mole of 2-probylheptanal. That is, i. The amount used is preferably o-1.5 mol, especially 1.1 to 1.2 mol. Specific examples of alkali metal hydroxides or alkaline earth metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, carunium hydroxide, barium hydroxide, etc. Considering the price, sodium hydroxide is particularly preferred. The reaction temperature is selected to be in the range from about 5 to 100°C, particularly preferably from 30 to 90°C.

Specific methods for carrying out the methylolation and cross-Cannizzaro reaction from 2-propylheptanal and formaldehyde include a) a method in which 2-propylheptanal, formaldehyde and an aqueous alkali solution are simultaneously added dropwise to react; - A method of reacting while adding formaldehyde to a stirring mixture of proylheptanal and an aqueous alkaline solution, c) Adding an alkaline aqueous solution to a stirring mixture of 2-probylheptanal and formaldehyde. There are three methods that can be considered: a method of reacting while adding, but according to the studies of the present inventors, method c) is the most preferable in terms of yield, economical efficiency of the apparatus, and operability. understood.

After the Kanisotuaro reaction is completed, the aqueous layer containing a large amount of formate is removed, and the organic layer is washed with water to remove alkaline content. It is preferable to wash with water until the pH of the washing water becomes 7 to 7.5. If I)H is 7.5 or more, decomposition occurs during distillation, and the production of =I+ organisms becomes significant, resulting in a decrease in yield.

The water, which has been removed from the reaction stage, may be subjected to simple distillation or, if necessary, to rectification using a packed column or plate column.

(Example) The present invention will be described in more detail below with reference to Examples and Comparative Examples.

Example 1 2-propylheptanal 624.24. ○g and 300.0 g of rose formaldehyde (92 ± 1%), and under a nitrogen blanket, add 48%-Na while stirring from the dropping funnel.
26.6 g of OH aqueous solution was added dropwise over 5 minutes. The temperature of the reaction solution rose to 55°C. Thereafter, the mixture was stirred and aged at 55°C for 2 hours. After that, the temperature was increased and when the reaction solution reached 65°C, 48%-N a OH 7k 356. Og was added dropwise over 65 minutes. The reaction temperature during the dropwise addition was maintained at 75°C or lower. After the reaction is complete, oil and water are separated and the organic layer is separated into 2
It was washed three times with 00 cc of water. After that, the organic layer was distilled under reduced pressure to remove water and low-boiling components, and the pot temperature was 175°C, 3mm.
A main fraction of Hg1 136-145°C was obtained.

The structure of this product was confirmed by instrumental analysis such as NMR, IR, and GC-MS. Table 1 shows the measurement results along with other characteristic values.

Example 2 148.0 g of adivic acid, 2- obtained in Example 1
Pentyl-2-propyl-1. 233.0 g of 3-propanediol 0.15 g of antimony trioxide as an esterification catalyst was charged into a flask with an internal volume of LL equipped with a thermometer, nitrogen inlet tube, stirrer, water separator, and reflux condenser, and the mixture was heated in a nitrogen stream. , ■ Esterification was carried out for 6 hours at 95-220''C.During the reaction, produced water was distilled off, and 35.7g of produced water was distilled out after 6 hours of reaction.Then, at the same temperature, 22.9 g of excess diol in the reaction system was distilled out under reduced pressure, and the number average molecule ffi 2 0 0
285 g of polyester polyol of 0.0 was obtained. During the reaction, no clogging of the tube due to solid precipitation occurred.

Next, after cooling the reaction solution to room temperature, 480 g of cyclohexanone and 35 g of 4.4''-diphenylmethane diisocyanate were added, and the mixture was reacted at 80''C for 2 hours, solid content 40%, viscosity 9400cl)s (25°C), A urethane resin composition having a number average molecular weight of 25,000 was obtained.

Comparative Example 1 225 g of polyester polyol with number average molecular weight M2000 was prepared in the same manner as in Example 3 using 146.0 g of adipic acid, 129.0 g of neopentyl glycol, and 0.15 g of antimony trioxide as an esterification catalyst.
I got it. During the reaction under reduced pressure, a large amount of neopentyl glycol precipitated in the cooling tube, so the cooling water was turned off and forced heating was applied to dissolve it.

Next, after cooling the reaction solution to room temperature, 400 g of cyclohexanone and 35 g of 4.4"-diphenylmethane diisocyanate were added and reacted at 80°C for 2 hours to form a urethane resin composition with a solid content of 40% and a number average molecular weight of 21,000. I got it.

Comparative Example 2 Adipic acid 146.0g1 2-Butyl-2-ethyl-L 3-propanediol 198g. O g, antimony trioxide as esterification catalyst 0. ■By the same method as in Example 3 using 5g, the number average molecule! 285 g of 2000 polyester polyol was obtained. During the reaction, the diol precipitated in the cooling tube and blocked the tube, so the cooling water was stopped and warm water at 60° C. was passed through to dissolve it.

Next, after cooling the reaction solution to room temperature, 400 g of cyclohexanone and 35 g of 4.4'-diphenylmethane diisocyanate were added and reacted at 80°C for 2 hours to form a urethane resin with a solid content of 40% and a number average molecular weight of 2SO○0. I got something.

Test Example 1 The urethane resin composition shown in Example 2, Comparative Example 1, and Comparative Example 2 was applied onto a 0.8 mm thick 1 300 mm x 50 mm cold-rolled steel plate using a spray gun, and the composition was kept at room temperature for one day.
After the painted surface was dried, it was further dried for 2 hours in a heat dryer at 100°C. The coating thickness when completely dry is 0.4m.
I made it m.

The obtained test pieces were evaluated by the method shown below.

Loss Coefficient (η) Two ends of the obtained test piece (rectangular shape) were fixed, vibration of 500 Hz was applied to the test piece, and the damping performance was evaluated by determining the loss coefficient from the resonance performance.

When the water resistance test pieces were immersed in running water (room temperature) for two weeks, those with no change in the state of the paint film compared to before immersion were marked O, and those with some changes were marked Δ. , those that have changed significantly are marked with an x.

The heat resistance test piece was placed in a vertical position at a temperature of 200"C.
When left standing for a period of time, the condition of the coating film shows no change at all compared to before heating, marked with O, marked with Δ when partially changed, and marked with X when markedly changed. It was shown in

The weather resistance test piece was kept in a Sanya Inn Weather Meter for 1200 hours, and the one with no change in the coating film shape compared to the blank was marked O, and the one with a change was marked Δ.
Those that have changed markedly are marked with an x mark.

The impact resistance test piece was placed horizontally, and a striking core of 500 g was dropped on a 1/2 inch spherical surface from a predetermined height to determine the height at which no significant change was observed.

The above test results are shown in Table 2.

Example 3 Adipic acid 205.5 g, 2-pentynolyl 2-probyl-1. 3-Prono Kunzionore 284. Og,
83.2 g of 2-ethylhexanol was heated to 30°C.
Four flasks each having an internal volume of 1 liter were equipped with a nitrogen inlet tube, a stirrer, a water separator, and a reflux condenser, and the mixture was heated while stirring in a nitrogen stream until the temperature of the reaction solution reached 140°C. At this point, 0.1 gm of tetraisobuvir tanate was added as a catalyst, and while the produced water was continuously removed from the system through the water separator, the overnight acid value of the reaction was approximately 20 mg KO.
The reaction was controlled at a temperature of 200°C until H/g+. Reaction time was 2.5 hours. Then, this reaction system was heated to 2-3 mmHg(7)il;! pressure, 2 2
The transesterification reaction was carried out for 2.5 hours at 0.5"C to obtain a desired polyester plasticizer. No precipitation of solid was observed during the transesterification reaction.

Comparative Example 3 314.5 g of adipic acid, 267.4 g of neobentyl glycol, and 108.6 g of 2-ethylhexanol were placed in a flask with an internal volume of LL equipped with a thermometer, nitrogen inlet tube, stirrer, water separator, and reflux condenser. and heated while stirring in a nitrogen stream until the reaction temperature reached 140°C.
When the temperature reached 0.1g, 0.1g of tetraisopropyl titanate was added as a catalyst, and the produced water was continuously removed from the system using a water separator until the acid value of the reaction solution reached approximately 20mgK.
The reaction was carried out at a temperature of 200'C until OH/g. Reaction time was 2.5 hours. This reaction system was then subjected to transesterification at 220 DEG C. for 2.5 hours under a reduced pressure of 2 to 3 mmHg to obtain a desired polyester plasticizer. During the transesterification reaction, neobentyl glycol was so precipitated that it clogged the cooling tube, so the cooling water was stopped and the diol was dissolved by forced ripening.

Comparative Example 4 205.5 g of adivic acid, 2-butyl-2-ethyl
241.5 g of 1,3-propanediol and 83.2 g of 2-ethylhexanol were placed in a flask with an internal volume of IL equipped with a thermometer, nitrogen inlet tube, stirrer, water separator, and reflux condenser, and a nitrogen stream was added. Heating was carried out while stirring in the reactor, and when the temperature of the reaction solution reached 140"C, as a catalyst,
Add 0.1 g of Tetraisobyl titanate and heat at 200 ml until the acid value of the reaction solution reaches approximately 20 mg KOH/g while continuously removing produced water from the system using a water separator.
The reaction was controlled at °C. Reaction time was 2.5 hours. This reaction system was then subjected to transesterification at 220° C. for 2.5 hours under a reduced pressure of 2 to 3 mmHg to obtain a desired polyester plasticizer. During the transesterification reaction, the precipitation of 2-butyl-2-x+L-3-propanediol caused a blockage in the cooling tube, so the cooling water was stopped and the diol was dissolved by passing warm water at EO'C.

Test Example 2 Summary of various properties of the polyester plasticizer made from 2-pentyl-2-propyl-1,3-propanediol of the present invention shown in Example 3 and the polyester plasticizers of Comparative Examples 3 and 4. The results are shown in Table 3. In addition, in order to examine water resistance, compatibility (bleeding), and migration, 90 parts by weight of the polyester plasticizer synthesized in Example 3 was added to 100 parts by weight of polyvinyl chloride resin (nivolit SM homopolymer with a degree of polymerization of 1300), and a stabilizer. 4 parts by weight of dibasic lead sulfate and 1 part by weight of lead stearate were combined in a cell mixer and kneaded for 7 minutes with 8-inch rolls at a roll temperature of 180'C. The obtained sheet was press-molded using a press molding machine at 170゛C under the conditions of applying a pressure of 150 kg/cm2 for 3 minutes and cooling for 3 minutes. Specified test pieces were prepared from the obtained press sheet and subjected to various tests. I tried it. In addition to the tests for water resistance, IJ-F properties, and migration properties, general properties such as a tensile test, thermal stability, and hardness were also measured.

For comparison, in addition to the polyester plasticizers synthesized in Comparative Examples 3 and 4, two types of commercially available adipate polyester plasticizers were selected and various similar tests were conducted.

Various tests were conducted using the following methods.

A water resistance test specimen (JIS K7113 Type 2 specimen) is immersed in a stainless steel container containing boiling water that has been preheated to 90°C or higher, and the container is sealed. This is 100'C
The test piece was placed in an oven for 48 hours, then taken out, and after wiping off the stickiness on the surface of the test piece, it was dried in an oven at 100'C for 2 hours. After drying, measure the weight of the test piece,
The rate of weight change from the weight of the test piece before the test is determined.

Bleedability test Length 60mm1 Width 30m ITh Thickness 1mm
The test piece is kept under constant temperature and humidity conditions at a temperature of 70° C1 and a relative humidity of 80 oA, and the surface condition of the test piece is observed over time to determine the presence and extent of bleeding.

Migration test Length 50mms Width 50m ffh Thickness 1m
A test piece of m is sandwiched between ABS resin plates or AS resin plates,
After applying a load of 1 kg and leaving the test piece at a temperature of 70°C for 168 hours, the transferability is calculated from the weight change before and after the test.

Regarding the transfer to an acrylic-coated board, the test piece was sandwiched between the acrylic-coated boards and left at a load of 1 kg, a temperature of 70°C, and a relative humidity of 80% for 240 hours, and the transferability was determined from the weight change of the test piece before and after the test. calculate.

Track stability test Length 30 mrrb Width 25 m mt Thickness 1 m
A test piece of m was placed in a gear oven at 180°C, and
Observe and compare the colored state of the test piece every 0 minutes.

Tensile test Compliant with JIS Kf3723.

Hardness JISK6301 (according to spring type hardness test type A)
Compliant with.

These results are summarized in Table 4.

From the above results, when the 2-pentyl-2-propynole-1,3-propanediol of the present invention is used as a raw material for urethane paints, it has extremely superior water resistance compared to, for example, products made from neobentyl glycol. properties, heat resistance,
It was recognized that it has properties such as weather resistance, impact resistance, and vibration damping properties.

Similarly, when used as a raw material for a polyester plasticizer, superior water resistance, compatibility, and non-migration properties were observed compared to commercially available polyester plasticizers or those made from neopentyl glycol. Furthermore, a significant improvement in performance was observed compared to 2-butyl-2-ethyl-1,3-propanol shown in the comparative example.

(Effect of the invention) 2-pethyl-2-propyl-1 of the present invention. 3-Propanediol was liquid at room temperature. Currently known various 2,2-dialkyl groups 1-negative 1,3-
This is a noteworthy property considering that all frobandiol, including inobentyl glycol, are solid at room temperature. Whether the raw materials used for the reaction are solid or liquid at room temperature does not make a huge difference in terms of production, not only in terms of raw material transfer but also in terms of ease of charging into the reactor. It's self-evident.

Since the 2-pentyl-2-probyl-L-3-brobanediol of the present invention is liquid at room temperature, when extracting excess glycol under reduced pressure when producing polyester polyols and polyester plasticizers, it is necessary to Since blockage does not occur, there is no need for special expensive heating and insulation equipment.

Furthermore, the 2-pe-chi-2-pro-1,3- of the present invention
Propanediol is liquid at room temperature, so in addition to this,
It can be used for a variety of purposes, including as a heating medium, reaction solvent, and vehicle for forming conductive films.

Naturally, the 2-pentyl-2-propyl-1,3-propanediol of the present invention, like neopentyl glycol, has an extremely reactive alcoholic primary hydroxyl group at the terminal, so it is difficult to synthesize It can be used for reaction purposes, for example, after forming polyester polyol with dibasic acid such as anovic acid, it was converted into urethane with diisonanate such as diphenylmethane diisocyanate, and the physical properties of the coating film were evaluated. Compared to neopentyl glycol, It was found to have excellent properties such as water resistance, heat resistance, weather resistance, impact resistance, and vibration damping properties.

Also, for example, the 2-propylene chloride #-1 of the present invention.
When 3-propanediol was used as a polyester plasticizer, particularly excellent performance was found in terms of water resistance, compatibility, and non-migration. Also, 2-buteru-2-ethyl-1.
Significant improvement in performance was also observed compared to 3-propanediol.

In this way, the 2-pentyl-2-propyl-1,
3-Propanediol has the advantage of being liquid at room temperature, making it easy to handle and useful as a heat medium, reaction solvent, and vehicle for forming conductive films.It is also used as a polyurethane resin, which has recently been required to have higher functionality. It is useful as a raw material diol for polyester resins, plasticizers, cosmetics, etc.

Table I Table 2 Table 3 DMN: 2-inch 2-inch A-1.3-7
'II Functional NPG: tOhesylgelicoll DMH: 2-Futility 2-! Thiru 1.3-Phantanesiol 1.3-BD: 1,3-Phantanesiol 1.4-BD: 1,4-Phantanesiol Table 4 Example 3 Comparative Example 3 Comparative Example 4 Commercial Product A Commercial Product B :gf/m厘2) P(%) ;Moguraz''/as2) !.70 445 0.51 l.78 449 0.51 l.77 443 0.52 1.92 428 0.62 1.71 471 0.48 Unitization rate (X) -0.95 -3.96 -1.81 -8.88 -6.91 sliI (IO × Δ ×× ×× 3 resin (%) sealant (x) Painted board (X) -0.03 -0.02 -Q.OI -0.19 -0.19 -0.65 -0.07 -0.06 -0.01 -0.63 -0.84 - 1.32 -0.71 -1.64 -1.40 l 68 68 69 67 65 Procedural amendment (voluntary)

Claims (2)

[Claims] (1) 2-pentyl-2-propyl-1,3-propanediol (2) 2-pentyl-2-propyl-1,3-propanediol is produced by reacting 2-propylheptanal with formaldehyde or paraformaldehyde in the presence of an aqueous solution of an alkali metal hydroxide or alkaline earth metal hydroxide. Manufacturing method.