JPH08301995A - Preparation of polyester from hydrous 2-butyl-2-ethyl-1,3-propanediol - Google Patents

Abstract

PURPOSE: To prepare a polyester possessing excellent handleability from hydrous 2-butyl-2-ethyl-1,3-propanediol. CONSTITUTION: Hydrous 2-butyl-2-ethyl-1,3-propanediol having a water content of more than 7.5 to 10.5wt.% and a process for preparing the same. The hydrous propanediol itself or a polyhydroxy compd. contg. the same is reacted with a polycarboxylic acid compd. composed mainly of at least one member selected among aliph., alicyclic and arom. dibasic acids, and esters thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to water-containing 2-butyl-2-
The present invention relates to a method for producing a polyester using ethyl-1,3-propanediol. More specifically, the present invention relates to a method for producing a polyester having improved workability and cost by using liquid hydrous 2-butyl-2-ethyl-1,3-propanediol having a uniform composition.

[Prior art]

[0002] Among the dimethylolalkanes represented by (Rm, Rn: aliphatic hydrocarbon group having 2 or more carbon atoms), 2-butyl-2-ethyl-1,3-propanediol is a plasticizer, a lubricant and an industrial intermediate. Further, it is used as a raw material for the above, or as a resin component or resin modifier represented by alkyd resin, polyester resin, unsaturated polyester resin, polyurethane resin, epoxy resin and melamine resin.

2-Butyl-2-ethyl-1,3-propanediol has attracted attention because its derivative has excellent physical properties, and its production scale has recently been expanding. As an application example of the specific derivative, polyester polyol for urethane resin having excellent hydrolysis resistance (Japanese Patent Publication No.
No. 86), modified polyester for heat-fusible composite fibers (JP-A-4-139212), vibration-damping adhesive composition (JP-A-4-261490, JP-A-6-220).
150) and a polyester plasticizer for a vinyl chloride resin-based sealant having excellent paintability and corrosion resistance (Japanese Patent Application No. 5-311366).

[0004]

However, 2-butyl-2-ethyl-1,3-propanediol has a solid form at around room temperature and is difficult to handle.
It was necessary to charge the mixture into a reaction vessel after pulverizing it into powder / flakes or heating it into a molten liquid. The powder / flakes or molten liquid is suitable for fine adjustment of the reaction or for large-scale charging. The crushing work of 2-butyl-2-ethyl-1,3-propanediol requires a lot of labor and time, and the work efficiency is poor. Investing in milling equipment has been a problem as it has resulted in increased costs. In addition, since 2-butyl-2-ethyl-1,3-propanediol has a melting point of 43 ° C., which is close to room temperature, this crushed product may easily cause blocking or the like near its own weight or a relatively warm room temperature. However, the powder obtained by crushing could not be maintained for a long time, and formed a lump again. The heating work of 2-butyl-2-ethyl-1,3-propanediol requires an extremely high-temperature heat source by a steam or electric furnace, a container excellent in closed heat retention and a heating and melting facility, which requires a large amount of equipment. Investment costs. Further, when 2-butyl-2-ethyl-1,3-propanediol is stored at high temperature for a long period of time, there is a fear of thermal decomposition depending on the storage environment. There is also a method of adding an anticoagulant such as ethylene glycol in order to prevent the solidification of 2-butyl-2-ethyl-1,3-propanediol, but 2-butyl-2-ethyl-
This may cause deterioration of the quality of the 1,3-propanediol derivative product.

Considering cost problems such as work efficiency, quality and capital investment when manufacturing polyester,
The presence of 2-butyl-2-ethyl-1,3-propanediol, which can maintain a liquid state even at a relatively low temperature near room temperature, is preferable, and a method for producing a polyester using this is desired. As a result of intensive studies by the present inventors, a liquid water-containing 2-butyl-2-ethyl-1,3 prepared from a specific ratio of water and 2-butyl-2-ethyl-1,3-propanediol.
It was found that the method for producing a polyester using propanediol has an excellent effect on the above problems, and the present invention has been completed.

[0006]

That is, the gist of the present invention is as follows. Water content exceeds 7.5% by weight 1
Water-containing 2-butyl-2-ethyl-containing 0.5% by weight or less
1,3-propanediol alone or a polyvalent hydroxy compound containing the same, an aliphatic dibasic acid, an alicyclic dibasic acid,
A method for producing a polyester, which is obtained by reacting a polyvalent carboxylic acid compound containing an aromatic dibasic acid or one or more of these esters as a main component.
The details of the present invention are described below. First, the water-containing 2- used in the method for producing a polyester using the water-containing 2-butyl-2-ethyl-1,3-propanediol of the present invention.
Raw materials and catalysts including butyl-2-ethyl-1,3-propanediol will be described.

The water-containing 2-butyl-2-ethyl-1,3-propanediol of the present invention maintains a uniform state without separating into two layers even when it is a liquid or when it is a solid by cooling. Therefore, the composition is not only easy to handle, but also has many advantages described later. The water used for the water-containing 2-butyl-2-ethyl-1,3-propanediol may be ordinary water, but distilled water and pure water obtained by ion exchange treatment are preferable.
Regarding pure water, the hydrogen ion concentration is 6.0 to 7.5, the electrical conductivity is 5 × 10 ⁻⁶ Ω ⁻¹ cm ⁻¹ or less at 25 ° C., sodium is 0.05 ppm or less, and chloride ion is 0.05 p.
It is desirable that the silica concentration is pm or less and the silica concentration is 0.05 ppm or less. The hydrogen ion concentration is preferably 6.9 to 7.
1. Sodium 0.01ppm or less, Chloride ion 0.01ppm or less, electrical conductivity is 3.5 × at 25 ℃
10 ^-6 Ω ^-1 cm ^-1 or less, the silica concentration is 0.02 ppm or less, and more preferably the hydrogen ion concentration is 6.95 to.
7.05, electric conductivity 0.5 × 10 ^-6 Ω ^-1 cm ^-1 or less, sodium 0.001 ppm or less, chloride ion 0.001 ppm or less, silica concentration 0.01 pp
It is preferably less than m.

If the hydrogen ion concentration is not around 7, 2-butyl-2-ethyl-1,3-propanediol (hereinafter referred to as D
(Abbreviated as MH) causes decomposition or reaction to reduce DMH purity. When the electric conductivity and the concentrations of sodium and chloride ions exceed the upper limits, there is a high possibility that sodium ions, chloride ions and various ions will hinder the reaction when the hydrous DMH reacts with an acid or the like. When the silica concentration exceeds the upper limit value, the reactivity of the water-containing DMH is hindered, and when the water-containing DMH is stored in the tank for a long period of time, sludge is generated, which may cause clogging of the conduit portion and pump failure. The DMH used for the water-containing DMH may be a commercial product.

The water-containing DMH is prepared by preparing DMH in an inert gas atmosphere at 43 ° C. or more and 90 ° C. or less and completely dissolving it, and then adding the above water to DMH in an amount of more than 7.5% by weight and 10.5% by weight. % By weight or less, preferably 7.8% by weight or more 1
It is performed by pouring 0.0 wt% or less and stirring. Alternatively, water-containing DMH may be prepared by preparing water and DMH and then heating both at the same time according to the above method, or by adding DMH or melted DMH to water or heated water and applying the above method. Water-containing DMH may be prepared according to the above. Further, the water-containing DMH of the present invention is further stirred and, if necessary, subjected to ultrasonic treatment and bubbling treatment to become a more transparent and uniform liquid. The freezing point of the water-containing DMH used in the present invention, which is a ratio of more than 7.5% by weight of water to 10.5% by weight of DMH, is JIS-K00.
When measured according to No. 65, it was in an extremely narrow temperature range of 25.0 ° C. or less and exceeding 22.0 ° C. When the water content with respect to DMH is 7.5% by weight or less, the freezing point becomes close to room temperature and the fluidity decreases, and when it exceeds 10.5% by weight, the water content D
MH does not separate into an oil layer and an aqueous layer to form a liquid having a uniform composition.

When the heating temperature during the production of water-containing DMH is less than 43 ° C., DMH is not completely dissolved and remains a solid and does not become a liquid with a uniform composition. Not only becomes difficult to control, but there is concern about thermal decomposition of DMH. It is desirable that the stirring is performed with a blade shape having a good stirring efficiency and rotation of 50 min ⁻¹ or more, and that the stirring time is 10 minutes or more. After completion of stirring, it is preferable to perform ultrasonic treatment and bubbling treatment. The frequency of ultrasonic waves is within a reasonable range where a uniform liquid is obtained when the frequency is 15 Hz or more and 220 MHz or less. It is desirable that the bubbling ejects an inert gas through a large number of extremely small holes below. Ultrasonic waves and bubbling of an inert gas may be used together with the stirring treatment. As the inert gas, there are nitrogen, helium and argon, and nitrogen is industrially preferable from the economical point of view.

The thus-prepared hydrous DMH of the present invention is stored in a container at a temperature higher than 25 ° C. and having fluidity according to its water content, and if necessary, for example, during initial mass production or final production. The necessary amount is added at the time of the minute adjustment preparation at the stage. During storage in a container, an inert gas atmosphere or an atmosphere having an inert gas concentration of 50 vol% or more is preferable, and the equipment of the container preferably has a stirring equipment or a circulation pump equipment. When not in use, even if the temperature in the container falls below the freezing point, water and DMH
Does not separate and maintains homogeneity, and by reheating, a uniform solution can be obtained again.

If the temperature is lower than 25 ° C., the water-containing DMH is likely to be solidified and there is a risk that the pipe may be blocked during transportation. If the temperature exceeds 90 ° C., the stored DMH is likely to be thermally decomposed. More preferably 40
It is to keep the temperature in the range of -60 ° C. Since the freezing point is low in the water concentration range of the water-containing DMH used in the present invention, the liquid state can be maintained within the above container storage temperature range, and the DMH
There is no thermal decomposition. For this reason, the water-containing DMH can be stored in good quality for a long time, and the necessary amount can be immediately transported to the target device as a liquid. The reason why the water-containing DMH used in the present invention can maintain an excellent liquid state is not always clear, but water molecules enter between molten DMH molecules to form a gradual hydrogen bond, and statistically per DMH molecule. Can form one molecule of water next to each other, and has a uniform composition of water-containing DMH
It is expected that the liquid can be maintained even at around room temperature while keeping the maximum concentration of 10.5% by weight of water therein.

Next, a method for producing a polyester using the water-containing DMH of the present invention will be described. First, the raw materials and catalysts other than the hydrous DMH used in the production will be described.
In the polyester production method of the present invention, DMH of the water-containing DMH is preferably 30% of the total polyvalent hydroxy compound.
Although it is used in an amount of not less than 50% by weight, more preferably not less than 50% by weight, the following polyhydric hydroxy compounds may be used together. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,2-diethyl-1,3-propanediol, 2-pentyl-2-propyl-1,3-propane Diol, 1,5-pentanediol, 3-methylpentanediol, 2-ethyl-1,3-hexanediol,
2,2,4-trimethyl-1,3-pentanediol,
Divalent aliphatic compounds such as 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, dipropylene glycol and polypropylene glycol And alicyclic diols are preferably used, and examples of the trivalent or higher-valent hydroxy compound include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. Among these, ethylene glycol, 1,4-butanediol,
1,3-butanediol, 2,2-diethyl-1,3-
Propanediol, 2-pentyl-2-propyl-1,
3-propanediol, 3-methylpentanediol,
1,6-hexanediol, neopentyl glycol,
1,4-cyclohexanedimethanol and dipropylene glycol are preferable, and further 2,2-diethyl-1,3
-Propanediol, 2-pentyl-2-propyl-
1,3-propanediol is particularly preferred. The kind of these polyhydric hydroxy compounds and the ratio to the water-containing DMH can be changed depending on the purpose.

Regarding the polyvalent carboxylic acid compound used in the polyester production method of the present invention, the aliphatic dibasic acid may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid or azelaic acid. , Sebacic acid, the alicyclic dibasic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, further aromatic dibasic acid Terephthalic acid,
Isophthalic acid, orthophthalic acid, phthalic anhydride, 2,6
-Naphthalenedicarboxylic acid and the like are particularly preferred. Aromatic dicarboxylic acids such as 5-methylisophthalic acid, and 1,2-
Dicarboxylic acids such as bis (4-carboxyphenyl) ethane, bis (4-carboxyphenyl) sulfone, bisphenyldicarboxylic acid and bis (4-carboxyphenyl) oxide, and polyvalent compounds such as trimellitic anhydride and pyromellitic anhydride Carboxylic acid and the like can also be used. As required, dimethyl terephthalate, diethyl terephthalate,
Aromatic dicarboxylic acid esters such as dimethyl isophthalate and diethyl isophthalate are also preferably used. Among these, malonic acid, adipic acid, sebacic acid, 1,4
-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, diethyl terephthalate,
Dimethyl isophthalate and diethyl isophthalate are preferable, and further adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate and the like are particularly preferable. The combination of these polyvalent carboxylic acid compounds can be arbitrarily selected, and the ratio can be changed according to the purpose.

The catalyst is not particularly limited, but monobutyltin oxide, dibutyltin oxide, dibutyltin laurate, dibutyltin acetate, tributyltin hydroxide, tin compounds such as stannous oxide, tetramethylgermanium, tetra Phenyl germanium, trimethyl germanium chloride, germanium compounds such as germanium oxide, lead stearate, lead ethyl compounds such as tetraethyl lead, tetraphenyl lead, lead oxide, manganese acetate, calcium acetate, zinc acetate, antimony acetate, magnesium acetate, aluminum acetate, Cobalt acetate, cesium acetate, and antimony trioxide can be exemplified, but if necessary, monobutyltin trichloride, dibutyltin dichloride,
Other examples include dibutyl titanium oxide, titanium tetrabutoxide, sulfuric acid, paratoluene sulfonic acid, and the like. Other known ones may be used.

Next, a method for producing a polyester using the water-containing DMH of the present invention will be described. As a production method, a one-step reaction and a two-step reaction are preferably used. The one-step reaction is a method of terminating the esterification reaction or transesterification reaction and the polymerization reaction at the same time, and the two-step reaction is a method of separately carrying out the ester reaction or the transesterification reaction and the reduced pressure polymerization reaction. As a result of the study conducted by the present inventors, considering the shortening of the reaction time and the easiness of producing the high molecular weight polyester, the reaction of the present invention is more preferably a two-step reaction.

That is, in the two-step reaction, the polyvalent carboxylic acid compound (hereinafter abbreviated as an acid compound) is added in a theoretical amount to the polyvalent hydroxy compound (hereinafter abbreviated as a hydroxy compound) contained in excess in the first step. 80% or more, preferably 85
% Or more, more preferably 90% or more to obtain an ester oligomer, and the polyester can be obtained by polymerizing the ester oligomer while removing the excess hydroxy compound in the second step. 1.05 to 4 total hydroxy compound components containing hydrous DMH per 1 mol of total acid compound components of an acid compound containing an aliphatic dibasic acid, alicyclic dibasic acid or aromatic dibasic acid or a mixture thereof. In moles, preferably the total hydroxy compound components are reacted in a ratio of 1.2 to 2 moles. If the concentration of total hydroxy compounds exceeds the upper limit, the reaction vessel becomes unnecessarily large, and if it is less than the lower limit, unreacted hydroxy compounds and acid compounds flow out together with by-products of water or alcohol to balance the hydroxy compounds and acid compounds. The target molecular weight is not achieved and the reaction rate decreases.

The catalyst is used in the usual way. Preferably, the reaction temperature is 80 ° C. or higher and lower than 290 ° C., preferably 130 ° C.
The reaction is carried out at a temperature of 230 ° C. If the temperature is lower than 80 ° C, the catalytic activity cannot be substantially exhibited, and if the temperature exceeds 290 ° C, not only DMH is decomposed and the coloring tends to occur, but also thermal decomposition of the catalyst itself occurs depending on the catalyst species. In the present invention, the catalyst may be added at any of the initial raw material charging step, the heating and heating step, and the reaction step, but it is preferable that the catalyst is charged before the temperature at which the esterification reaction or transesterification reaction starts. More preferably, it is better to charge the catalyst before the esterification reaction or transesterification reaction after the water of water-containing DMH is removed by heating. The catalyst may be charged all at once or successively in small amounts. In the method for producing a polyester using water-containing DMH of the present invention, the acid compound and the hydroxy compound containing water-containing DMH may be charged in any order. The acid compound and the hydroxy compound may be charged all at once or added little by little. The charging time may be any step before heating before the esterification reaction or transesterification reaction starts, or during heating during heating.

The esterification reaction or transesterification reaction of the present invention is preferably carried out in an inert gas atmosphere of nitrogen, argon and helium, and from an economical viewpoint, nitrogen gas is particularly preferable industrially. The reaction in the air is not preferable because DMH is thermally decomposed and colored, and other materials are also thermally decomposed. The first step is carried out at atmospheric pressure for 0.5 to 50 hours, and then the second step is carried out in a reduced pressure environment to carry out the reaction at a final pressure of 30 Pa or less for 0.5 to 10 hours. The reaction in each of these stages may be carried out continuously or discontinuously. Furthermore, if necessary, a heat stabilizer can be added. As a heat stabilizer, phosphoric acid compounds such as trimethyl phosphate and triphenyl phosphate, Irganox 1
Hindered phenol compounds such as 010 can be mentioned.

The polyester production method using the hydrous DMH of the present invention may be a one-step reaction instead of the two-step reaction. In the one-step reaction, an acid compound and a hydroxy compound containing water-containing DMH are sequentially reacted, and 90% or more of the theoretical amount, preferably 95
A polyester is obtained by reacting at least 100%. The amount of the hydroxy compound charged is 1.01 mol times or more and less than 1.2 mol times the set amount of the acid compound, preferably 1.
It is preferably from 05 mole times to less than 1.1 mole times. 1.01
If it is less than the molar ratio, there is a high possibility that a large amount of unreacted hydroxy compound will flow out during the reaction to disturb the set amount balance.
If it is more than the molar amount, the unreacted hydroxy compound will be decomposed by heating for a long time, or the balance with the acid compound will be lost and the target molecular weight will not be obtained. The reaction conditions for the one-step reaction are similar to those for the two-step reaction, but the reaction temperature is 150 ° C to 290 ° C, preferably 180 ° C to 230 ° C, and the reaction time is 1 hour to
90 hours is reasonable. 1 to 3 at 300 Pa or less
It is preferable to remove the low-boiling impurities by decompressing for a period of time.

Although the reason why the water-containing DMH of the present invention has not been used in the method for producing polyester up to the present day is not exactly understood, it is presumed as follows. The acid compound and the hydroxy compound are synthesized into an ester through an ester reaction or transesterification reaction, but by-products such as water and alcohol must be removed to the outside of the reaction system in order to proceed the reaction. It is believed that hydrous DMH was not used in the production of the polyester because the presence of water hinders the reaction and requires extra energy. In addition, it is considered that hydrolysis was likely to occur in the presence of a large amount of water, making it difficult to obtain high-quality polyester. However, the production method of the present invention not only improves workability, but also can easily remove water during the reaction, and the quality of the produced polyester shows the same appearance, composition and molecular weight as the conventional products. .

[0022]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Water content D shown in Examples and Comparative Examples in the text
The measurement of the physical properties of the polyester using MH and hydrous DMH and the preparation of the experimental equipment were performed as follows.

1. Physical property measurement (1) Acid value measurement The acid value of the polyester was measured according to JIS-K0070. (2) Hydroxyl value measurement The hydroxyl value of polyester was measured according to JIS-K0070. (3) Molecular weight measurement Tetrahydrofuran 1.0m using GPC (gel permeation chromatography) manufactured by JASCO Corporation
The molecular weight of the polyester was measured at a flow rate of 1 / min, and the molecular weight was converted with a polystyrene standard solution. (4) Moisture content measurement Kyoto Electronics Manufacturing Co., Ltd. Karl Fitzshire moisture meter MK
Hydrous D according to JIS-K0068 using A-3P
The water content of MH was measured. (5) Freezing point measurement A constant temperature water bath, a standard thermometer, a double test tube, etc. that can be controlled at 0 ° C to 100 ° C were prepared, and the freezing point of hydrous DMH was measured according to JIS-K0065. (6) Measurement of melting point and glass transition point Differential scanning thermal analyzer (DS
C) was used to measure the melting point and glass transition point of the polyester according to JIS-K7121. (7) Molar ratio analysis of polyester component The molar ratio of the acid compound and the hydroxy compound of the polyester was calculated from the proton intensity curve in the nuclear magnetic resonance spectrum measurement.

2. Synthesis Experimental Apparatus An apparatus diagram relating to the production method of the present invention is shown in FIG. This device is a typical example used in synthetic experiments, and the present invention is not limited thereto. The heating / warming container is connected to the reaction container via a pipe section having a circulation pump. A flow meter and a thermometer can be attached to the pipe section to measure the flow rate and temperature of DMH and water-containing DMH. DMH is put in a heating and heat-retaining container as it is in a lump form, and stored in the form of molten DMH or hydrous DMH. The powdery / flake or liquid acid compound, the hydroxy compound, the catalyst and the like are charged into the reaction vessel from a hopper attached to the reaction vessel.

3. Production Preparation and Polymerization Experiment Example The following polymerization experiment was conducted after observing and measuring the method for producing hydrous DMH and the transfer of the polyester raw material to the reaction vessel.

(Example 1) Solid bulk DMH 90.0 kg
On the other hand, 10.0 kg of water was placed in a heating and heat-retaining container under a nitrogen atmosphere, and the mixture was stirred at 70 ° C. for 30 minutes to obtain a water-containing DM of uniform composition
100.0 kg H was produced and stored. The water content of the stored water-containing DMH was measured to be a uniform composition of 9.9% by weight. While circulating this water-containing DMH with a circulation pump, the water-containing DMH was gradually cooled to 25 ° C. and the state of the circulation was observed. The state of this observation is shown in Table 1. Hydrous D in Table 1
When the MH flows, it is marked with O, and when it clogs, it is marked with X. Next, the hydrous DMH was changed from 25 ° C to 50 ° C. 32.05 kg of water-containing DMH kept at 50 ° C. was fed to the reaction vessel at a flow rate of 1000 kg / h for 1.92 minutes by using a circulation pump while being kept at 50 ° C. On the other hand, 312.60 kg of dimethyl terephthalate (hereinafter abbreviated as DMT) powder was charged from the hopper of the reaction vessel, 0.2 kg of zinc acetate and 0.1 kg of antimony trioxide were further added as a catalyst, and then the reaction vessel was placed in a nitrogen atmosphere. did. These reactions are 200 ~
Heated at 205 ° C for 2 hours and added methanol and water in total 13.
After removing 75 kg, ethylene glycol (hereinafter referred to as E
182.61 kg was injected and reacted for 5 hours to remove 91.76 kg of methanol and water. Furthermore, after heating at 250 to 260 ° C. for 0.5 hour, the pressure in the reaction vessel is reduced to a final pressure of 35 Pa, and the reaction is performed for 4 hours to polymerize while distilling 97.58 kg of excess hydroxy compound to yield 323.87 kg of polyester. Obtained. Table 2 shows the results of measuring the hydroxyl value, molecular weight measurement, component molar ratio, glass transition point and melting point of the obtained polyester.

Example 2 Solid bulk DMH 92.0.0
8.0 kg of water per kg is put into a heating and heat-retaining container having a nitrogen atmosphere, and the mixture is stirred at 70 ° C. for 30 minutes to obtain a water-containing D of uniform composition.
100.0 kg of MH was prepared and stored. The water content of the stored water-containing DMH was measured to be 8.0% by weight as a homogeneous composition. While circulating this water-containing DMH with a circulation pump, the water-containing DMH was gradually cooled to 25 ° C. and the state of the circulation was observed. The state of the observation is shown in Table 1. Next, hydrous DMH4
Keep 8.31kg at 50 ℃
It was fed into the reaction vessel at a flow rate of 00 kg / h for 2.90 minutes. On the other hand, 29.22 kg of adipic acid (hereinafter abbreviated as AA) powder was charged from the hopper of the reaction vessel, and 0.05 kg of antimony trioxide was further added as a catalyst, and then the reaction vessel was placed in a nitrogen atmosphere. In order to obtain a polyester with a target molecular weight of 2000, 190 under normal pressure in a nitrogen atmosphere
The esterification reaction is carried out at 5 ° C to 200 ° C for 5 hours, and water 1
A polyester was obtained by removing 6.91 kg and 1.88 kg of DMH. The acid value, hydroxyl value and molecular weight of 58.71 kg of the obtained polyester were measured and shown in Table 3.

Example 3 Water-containing DMH prepared in the same manner as in Example 1 was observed and the results are shown in Table 1. Further water-containing DM
After cooling the temperature of H to 7 ° C, make it flowable 5
It was set to 0 ° C. The water content of water-containing DMH was measured to be 9.8% by weight. 543.56 kg of water-containing DMH was fed into the reaction vessel at a flow rate of 1000 kg / h for 32.62 minutes using a circulation pump. On the other hand, 332.28 terephthalic acid (hereinafter abbreviated as TPA) powder was fed from the hopper of the reaction vessel.
Then, 0.60 kg of dibutyltin oxide was added as a catalyst, and the reaction vessel was also filled with a nitrogen atmosphere.
To obtain a polyester with a target molecular weight of 5000, 20
After heating at 0 ° C. to 205 ° C. for 5 hours to remove 126.36 kg of water, the reaction vessel was depressurized at the same temperature to obtain a final pressure of 35 Pa.
For 4 hours to remove excess DMH from 149.75k
Polyester was polymerized while distilling off to give polyester. The acid value, hydroxyl value and molecular weight of 599.55 kg of the obtained polyester were measured and shown in Table 3.

Comparative Example 1 Solid mass DMH 100.0k
Add g to a heating / heat-retaining container in a nitrogen atmosphere and hold at 70 ° C for 3
It was heated for 0 minutes, completely melted and stored. DMH stored
The water content was measured to be 0.08% by weight. While circulating this DMH with a circulation pump,
It was gradually cooled to and the state of its circulation was observed. The state of the observation is shown in Table 1. Next, the temperature was adjusted to 50 ° C. so that DMH had fluidity. 28.85 kg of DMH kept at 50 ° C
Using a circulation pump at a flow rate of 1000 kg / h.
It was sent to the reaction vessel in 74 minutes. On the other hand, 312.64 kg of DMT powder was charged from the hopper of the reaction vessel, 0.2 kg of zinc acetate and 0.1 kg of antimony trioxide were further added as catalysts, and then the reaction vessel was placed in a nitrogen atmosphere.
These reactions were heated at 200-205 ° C for 2 hours to remove 10.88 kg of methanol and then EG.
Inject 61 kg and react at the same temperature for 5 hours to reach 91.52
kg of methanol was removed. Furthermore, 250-260
After heating at 0 ° C for 0.5 hours, depressurize the reaction vessel to final 3
The reaction is carried out at 5 Pa for 4 hours to remove excess hydroxy compound from 9
While distilling off 7.61 kg, the polyester is polymerized to 3
23.99 kg was obtained. Table 2 shows the results of measuring the hydroxyl value, molecular weight measurement, component molar ratio, glass transition point and melting point of the obtained polyester.

(Comparative Example 2) Solid lump DMH 85.0 kg
On the other hand, 15.0 kg of water was placed in a heating and heat-retaining container in a nitrogen atmosphere, and the mixture was stirred at 70 ° C. for 30 minutes to obtain a water-containing DM of uniform composition
100.0 kg H was produced and stored. The water content of the stored water-containing DMH was 9.1 to 17.8% by weight in five measurements.
Was measured. While circulating this water-containing DMH with a circulation pump, the water-containing DMH was gradually cooled to 25 ° C. and the state of the circulation was observed. The state of the observation is shown in Table 1. Hydrous D
Although MH was liquid at any temperature, suspension was observed in the liquid during transportation and DMH alone could not be measured. When it was taken out as a liquid sample and allowed to stand, the liquid separated into an oil layer and an aqueous layer, so the reaction of the polyester was abandoned.

(Comparative Example 3) The results of observation of molten DMH prepared in the same manner as in Comparative Example 1 are shown in Table 1. Furthermore, after cooling the temperature of DMH to 7 ° C, 50 ° C so that it has fluidity.
And The water content of DMH was 0.01% by weight. 5
DMH (38.61 kg) kept at 0 ° C. was fed into the reaction vessel at a flow rate of 1000 kg / h for 2.32 minutes using a circulation pump. On the other hand, 29.22 kg of AA powder was charged from the hopper of the reaction container in minutes, and 0.05 kg of antimony trioxide was further added as a catalyst, and then the reaction container was also placed in a nitrogen atmosphere. In order to obtain a polyester having a target molecular weight of 5000, an esterification reaction was carried out at 190 ° C. to 200 ° C. for 5 hours under atmospheric pressure in a nitrogen atmosphere to obtain 7.20 kg of water and DM.
1.78 kg of H was removed to obtain polyester. The measurement results of acid value, hydroxyl value and molecular weight of 58.84 kg of the obtained polyester are shown in Table 3.

Comparative Example 4 489.2 kg of DMH was pulverized by two workers for 60 minutes and charged into the reaction vessel from the hopper in 5 minutes. In addition, 332.28 kg of TPA,
After adding 0.60 kg of dibutyltin oxide as a catalyst, the reaction vessel was also filled with a nitrogen atmosphere. Target molecular weight 5000
To obtain polyester of 5
After heating for 71 hours to remove 71.86 kg of water, the reaction vessel was evacuated to a final pressure of 35 Pa and reacted for 4 hours to distill excess DMH of 149.68 kg and polymerize it to obtain a polyester. The acid value, hydroxyl value and molecular weight of 599.48 kg of the obtained polyester were measured and shown in Table 3.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

The water-containing DMH used in the present invention has a low freezing point because it contains an appropriate amount of water, and therefore can be handled as a liquid in a wide temperature range. Further, once solidified, water and DMH do not separate, and by reheating, a uniform liquid is obtained again, and handling such as transportation and removal is easy. In the production method of the present invention using DMH of the present invention, it can be automatically fed into the reaction container through a pipe without blocking from the heating / heat-retaining container near room temperature, and the working efficiency at the time of preparation is improved. Therefore, the manufacturing cost by the manufacturing method of the present invention is smaller than that of the conventional method, and it is possible to inexpensively supply the polyester equivalent to the conventional one. Further, the polyester produced by the production method of the present invention has the same appearance, composition ratio, molecular weight and thermal properties as those of the polyester produced by the conventional production method and maintains good quality. Further, as a result of keeping the water content low with the water-containing DMH of the present invention, industrial wastewater is relatively small, and deactivation of the catalyst is hardly seen, so that many catalysts are not required. In the above meaning, the water-containing DMH of the present invention and the method for producing polyester using the same have great industrial significance.

[Brief description of drawings]

FIG. 1 is a polyester manufacturing apparatus. The heating / heat-retaining container is connected to the reaction container via a pipe section having a circulation pump, and has a slender cylindrical shape. A flow meter and a thermometer are attached to the piping section DMH and water-containing DMH
The flow rate and temperature of can be measured. DMH is put into a heat insulation container as a lump and melted or hydrous DMH.
Saved as the shape of. The powdery / flake or liquid acid compound, the hydroxy compound, the catalyst and the like are charged into the reaction vessel from a hopper attached to the reaction vessel.

Claims (1)

[Claims] 1. A water content of more than 7.5% by weight.
Water-containing 2-butyl-2-ethyl-1, which is 5% by weight or less,
3-Propanediol alone or a polyvalent hydroxy compound containing the same and a polyvalent carboxylic acid compound containing an aliphatic dibasic acid, an alicyclic dibasic acid, an aromatic dibasic acid or one or more of these esters as main components A method for producing a polyester, which is obtained by reacting