JPS58157761A - Preparation of glycol solution of 5-metal sulfoisophthalic acid compound - Google Patents

Abstract

PURPOSE:To obtain the titled highly concentrated low-viscosity solution having improved handleability, by heating a 5-metal sulfoisophthalic acid and/or its dialkyl ester and a glycol in the presence of an ester exchange catalyst under whole reflux. CONSTITUTION:A 5-metal sulfoisophtalic acid (e.g., 5-sodium sulfoisophthalic acid) and/or its dialkyl ester, especially 1-4C lower alkyl ester and a glycol (e.g., ethylene glycol) are heated in the presence of an ester exchange catalyst (e.g., calcium acetate) under whole reflux (preferably in a range of 80-180 deg.C), to prepare highly concentrated glycol solution of 5-metal sulfoisophthalic acid compound. The concentration of the glycol solution of the 5-metal sulfoisophthalic acid compound is preferably 7-50wt% based on solution, the solution having improved handleability is obtained easily by this process, and the productivity of polyester can be raised.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 5-metal sulfoisophthalic acid compound glyco1
1. Concerning the method for preparing a polyester solution, more specifically, the production of a modified polyester copolymerized with a 5-metal sulfoisophthalic acid component; solution! 1M
1 Regarding the manufacturing method.

Polyethylene
A method of copolymerizing 5-metal sulfoisophthalic acid and/or 5-metal sulfoisophthalic acid components to improve the dyeability and water absorption is known. A method widely used in the T industry is to make the dialkyl ester into a Glyfur solution, remove foreign substances by filtration, etc., and then add it to the polyester synthesis reaction system for co-integration.1 However, Konera's 5
- Metal sulfo-d-ynophthalic acid compounds have low solubility in glycol; for example, dimethyl 5-sodium sulfo-iso-7talate dissolves at most 7% by weight in ethylene glycol at room temperature. Therefore, there is no problem if the amount of copolymerization is small, but if the 5-metal sulfoisophthalic acid component is added in multiple layers to achieve a sufficient effect, excess glycol will be added to the polyenpur synthesis reaction system. As a result, the amount of free glycol in the system increases, and the amount of by-products of mnemethylene glycol increases, lowering the softening point of the polymer, and causing droplets of 7/mers to exit the system. The number of companions will increase. Furthermore, additional heat treatment and time are required to remove excess glycol, which is disadvantageous in terms of energy and production costs.

The present inventor dissolved 5-sodium sulfoisophthalic acid dimethinochloride in ethylene glycol at a high concentration (
We tried various studies on how to set the standard. One of them is that when heating and dissolving 1-, solidification and precipitation occur and fluidity is lost when the liquid temperature drops, making it less practical. This process is difficult due to quality problems such as deterioration due to deterioration and equipment problems, and furthermore, it is difficult to add VC before starting the transesterification reaction.
), the internal temperature of the reaction mixture increases due to the addition of a high-temperature solution, and as a result, when a transesterification reaction catalyst is added, the transesterification reaction proceeds rapidly and causes operational problems, such as bumping. The present inventor further attempted to prepare a glycol ester of 5-sodium sulfoisophthalate by previously reacting dimethyl 5-sodium sulfoisophthalate with 1 cJ of ethylene glycol. Specifically, di-isophthalic acid is added to ethylene glycol, heated in the presence of a catalyst, and the methanol produced is distilled off to cause a transesterification reaction. However, in this case, the reaction takes a long time of 5 to 6 hours, and the viscosity of the resulting reaction product increases significantly.
In addition, this reaction requires a separate transesterification reactor, which is impossible due to cost considerations. , ivy. .

The inventor of the present invention has made a surprising discovery as a result of extensive research into creating a highly concentrated glycol-free solution of dimethyl 5-sodium sulfoisophthalate that can be easily produced in an extremely short time and has excellent binding properties. In particular, dimethyl 5-sodium sulfoisophthalate was introduced into ethylene glycol and the M
By simply treating the solution for 1 to 2 hours without distilling off the metal and -C, a clear solution can be obtained in which the temperature is lowered to room temperature and no precipitation and assimilation of -C occurs. - It was discovered that a clear liquid of about 40% by weight of dimethyl sodium sulfoisophthalate at a temperature of 4111 degrees can be obtained in a state of low viscosity with good entring properties.Based on this knowledge, further extensive studies were carried out, and the present invention was developed. Accordingly, the present invention provides a method for preparing a highly concentrated glycol solution of 5-metal sulfoisophthalic acid and/or its dialkyl ester. A method for preparing a glycol solution of a 5-metal sulfoisophthalic acid compound is used, which comprises heating an ester and a glycol under total reflux in the presence of a transesterification catalyst.

The metals of 5-metal sulfur 4, isophthalic acid and its dialkyl esters used in the present invention do not need to be particularly limited.
However, alkali metals or full earth metals are preferred, and alkali metals are particularly preferred. Further, as the dialkyl ester, one in which the furkyl group is a lower alkyl group having 1 to 4 carbon atoms is preferable. A particularly preferred example of such a 5-metal sulfoisophthalic acid compound is 5-sodium sulfoisophthalic acid.

5-potassium sulfoisophthalate, 5-lithium sulfoisophthalate, 5-sodium dimethyl sulfoisophthalate, 5-potassium dimethyl sulfoisophthalate, 5-
Examples include lithium, dimethyl lewisophthalate, and the like.

As the glycol used in the present invention, any glycol can be used, but preferably one having 2 to 6 carbon atoms.
at least one glycol selected from fullylene glycol/l, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and particularly preferably from 1,000 range glycol and tetramethylene glycol. 1. In actual application, 5.
It is particularly preferred to select the same glycol as the glycol component constituting the base polyester to be copolymerized with the metal sulfoisophthalic acid component.

The ratio of the above-mentioned 5-metal sulfoisophthalic acid compound to glycol can be selected arbitrarily, but if the amount of 5-metal sulfoisophthalic acid compound used is too large, the viscosity of the final solution will increase. Since the ndling property is deteriorated, the concentration of the 5-metal sulfoisophthalic acid compound in the glycol solution is preferably 7 to 50% by weight based on the solution.

In the present invention, in order to dissolve the above-mentioned 5-metal sulfoisophthalic acid compound in glycol, K requires the presence of a transesterification catalyst.

Any transesterification catalyst can be used as the transesterification catalyst. In particular, calcium, mag-halfium, spuntium, and lithium.

Natori tsim, potassium! lljLead, manganese, lead.

Elemental metals such as titanium, cobalt, tin, cerium, hydrides, carbonates, borates, p-gulfides, oxides, hydroxides, aliphatic and aromatic monohydrochlorides and dibasic acid pots. , organic complex compounds, furfurate, etc. are used. The labor involved
Particularly preferred specific examples of chill exchange catalysts include tosium acetate, magsium acetate, cobalt acetate, and lidium acetate.

Examples include sodium acetate, potassium acetate, zinc acetate, manganese acetate, tisine acetate, cerium acetate, zinc benzoate, titanium te-1-lysoproboxide, and the like.

If the amount of the star exchange reaction catalyst used is too small, it will be difficult to dissolve the 5-metal sulfoisophthalic acid compound in glycol beyond its solubility;
On the other hand, if the amount is too large, a catalytic metal salt of 5-metal sulfoiophthalic acid tends to form. Therefore, the amount is preferably in the range of 0.1 to 10 mol% based on the 5-metal sulfinoataric acid compound. 5-metal sulfoisophthalic acid components together
When the combined polyester is produced by a transesterification method, a glycol solution of the above-mentioned 5-metal sulfoisophthalic acid compound is added to the Justeno 1-exchange reaction sequence of the copolymerization, and the above-mentioned transesterification catalyst present in the solution is added. may also be used as a catalyst for the transesterification reaction in the production of copolymerized polyester.

In the method of the present invention, in order to dissolve the above-mentioned 5-metal sulfur isophthalic acid compound in glycol beyond its solubility, it is sufficient to provide the above-mentioned transesterification catalyst and heat it under total reflux. Boiling point components are distilled out of the system L2 to proceed with esterification reaction and Gostyl exchange reaction,
There is no need to change the 5-metal sulfoisophthalic acid compound to 5-metal nurphoinphthalic acid di(β-human p-xyethyl) ester9. This is rather inappropriate since it will increase the viscosity. Heating conditions are solution 1
! Although it varies depending on the degree etc., the temperature is usually 80 to 180
The temperature range is preferably from 100 to 140°C, particularly preferably from 100 to 140°C.

The time can be in the range of 30 minutes to 3 hours.

By doing this, a high concentration of 5-metal sulfoinphthalic acid compound in glycol solution 9- can be easily obtained at room temperature and in a state with good undling properties.
- It becomes possible to produce a polyester copolymerized with a large amount of a metal sulfoisophthalic acid component with high quality and good green brittleness.

Further explanation will be given below with reference to Examples. In Examples, parts and % indicate parts by weight and % by weight, respectively.
parts, 20 parts of dimethyl 5-sodium sulfoisophthalate and 0.092% of sodium acetate trihydrate (based on dimethyl 5-sodium sulfoisophthalate], 0 mol%)
was added, the temperature was raised to 120° C. over 30 minutes under normal pressure, and the temperature was further maintained at this temperature for 60 minutes while stirring. Then, it was cooled to room temperature to obtain a colorless and transparent solution. After using this solution for one year, he did not notice any precipitation.

100 parts of dimethyl terephthalate, 5- above.

--10-- 75 parts of a solution of sodium dimethyl sulfoisophthalate in 20-ethylene glycol (molar ratio of dimethyl glycol to terephthalic acid: 1.88°; 9.8 moles of 5-sodium dimethyl sulfoisophthalate to dimethyl terephthalate) ), +t [0.03 part of manganese tetrahydrate (0.024 molti relative to dimethyl terephthalate) was charged into a transesterification tank, and 14
The transesterification reaction was carried out while raising the temperature from 0°C to 230°C and distilling the generated methanol out of the system. Subsequently, 0.027 part of a solution of 561 orthophosphoric acid (0.030 mol % based on dimethyl terephthalate) and 0.04 part of antimony trioxide were added to the obtained product, and the mixture was transferred to a polymerization vessel. Then, over 1 hour, 76[1wnH)' to 1
The pressure was reduced to W H and at the same time the temperature was raised from 230°C to 285°C over 3 () minutes. I mx He
Under the following reduced pressure, continue at a combined temperature of 285℃ [30 minutes total 2
After time polymerization, the intrinsic viscosity is 0°415. A copolymer with a softening point of 245°C was obtained.Example 2 Manganese acetate tetrahydrate was used in place of the sodium acetate trihydrate used in preparing the ethylene 11-col solution of dimethyl 5-sodium sulfoinphthalate in Example 1. jJK 0.
The procedure of Example 1 was repeated except that 0.079 parts (0.48 mol % based on dimethyl 5-sodium sulfoiphthalate) was used to obtain a pale yellow, transparent solution. No precipitation was observed in this solution even after one year had passed.

100 parts of dimethyl terephthalate, 3 parts of ethylene glycol
0 parts, 38 parts of a 20% ethylene glycol solution of the above dimethyl 5-sodium sulfoisophthalate (5.0 mole 5-sodium dimethyl sulfoisophthalate to methyl terephthalate, 0.024 mole manganese acetate 4 water to 0.024 mole terephthalate) dimethyl terephthalate) was charged into the transesterification vessel (total charge molar ratio of ethylene glycol to dimethyl terephthalate +, 8S). A transesterification reaction and polycondensation & reaction were carried out in the same manner as in Example 1 without adding a separate transesterification reaction catalyst.

The copolymer had an intrinsic viscosity of 0.4.50 and a softening point of 253.5°C.

Comparative Example In the ethylene glycol solution MN of dimethyl 5-sodium sulfoisophthalate in Example 1, the same procedure as in Example 1 was repeated except that sodium acetate trihydrate was used.
There was one. A transparent solution was obtained at 120°C, but precipitation occurred during cooling. As a result of conducting similar dissolution tests with different t values of dimethyl 5-sodium sulfoisophthalate and 5-sodium sulfoisophthalate, it was found that a clear solution was obtained at room temperature without precipitation, and the peak height was 7 cm. .

Using this 7tiglycol solution, Example 1 and open cleavage elC were carried out.
A polyester was produced by copolymerizing a 5-sodium sulfoisophthalic acid component. That is, instead of 75 parts of the 20% glycol solution used in Example 1, 213.6 parts of 7-thiethylene glycol (mW) of 5-sodium dimethyl sulfoinphthalate (ethylene glycol to dimethyl terephthalate) was used. The same procedure as in Example 1 was carried out except that 9.8 moles of 6.2.5-sodium dimethyl sulfoinphthalate to dimethyl terephthalate were used. The resulting copolymer 1 (the intrinsic viscosity of the remer is n, 4) 3. The softening point was 204°C.

In this comparative example, the softening point of the obtained copolymer and the abrasive K were also lowered, so at the start of the transesterification reaction (acetic acid was used as a ethyl bond formation inhibitor)
11.1169 parts of i was added, and the rest was carried out in the same manner as in the above comparative example. The intrinsic viscosity of the obtained copolymer was 0.
4+3. The softening point was 231°C.

Patent Applicant Teijin Ltd. 14- Procedural Amendment April 10, 1980 To the Commissioner of the Japan Patent Office 1 Indication of Case Patent Application No. 1987 39365 2 Title of Invention 5 - Method for Preparing Glycol Solution of Metal Sulfoisophthalic Acid Compound 3 Relationship with the case of the person filing the amendment Patented applicant: 1-11 Minamihonmachi, Higashi-ku, Osaka (300) Teijin Ltd. Representative Tomoo Tokusue 5 "Claims" column of the amended specification and ``Column 6 of Detailed Description of the Invention 1, Contents of Amendment 1 - Attachment (1) The scope of claims of feature #'f of the description is corrected as shown in the attached sheet.

(21, 5Jj, line 14, 900, line 7, and 10th tributary, line 9, Kr reflux) has been corrected to ``reflux''.

(3) Page 9, line 11 K [di(β-hydroxyethyl)] is corrected to [di(hydroxyalkyl)].

(4) On page 14, line 4, 1cr uses j is corrected to ``use.''

Top 2-2, Claim 5 - In preparing a highly concentrated glycol solution of metal sulpoinphthalic acid and/or its dialkyl ester,
1. A method for preparing a glycol solution of a 5-metal sulfoisophthalic acid compound, which comprises heating 5-metal sulfoisophthalic acid and/or its dialkyl ester and glycol under total reflux in the presence of a transesterification catalyst.

Claims (1)

[Claims] In preparing a highly concentrated glycol solution of 5-metal sulfoisophthalic acid and/or its dialkyl ester,
5-metal sulfoisophthalic acid and/or its sialic 4-
1. A method for preparing a glycol solution of a 5-metal sulfoisophthalic acid compound, which comprises heating a glycol ester and a glycol under total reflux in the presence of a transesterification catalyst.