JPS5958026A - Manufacture of polyester containing sulfonate group - Google Patents

Abstract

PURPOSE:To obtain titled polyester suitable for dispersants, etc., either by adding an acid sulfite to an unsaturated polyhydric alcohol followed by polycondensation with a polybasic acid, or by adding an acid sulfite to a polyester from an unsaturated polyhydric alcohol and polybasic acid. CONSTITUTION:(A) An unsaturated polyhydric alcohol such as 2-butene-1, 4-diol and (B) sodium bisulfite are made to react, for example in the presence of an iron oxide by heating to 70 deg.C to prepare a sulfonated polyhydric alcohol, which is then subjected to polycondensation with a polybasic acid such as oxalic acid to obtain the objective polyester. Alternatively, a polyester formed from said unsaturated polyhydric alcohol and polybasic acid is dissolved in, e.g., benzene followed by incorporating, in the presence of an iron oxide, 10-200mol% based on the unsaturated group, of sodium bisulfite in the system and carrying out a reaction at a temperature between 60 deg.C and the boiling point to obtain the objective polyester. USE:For pastes for use in fibers, paper processing agent, adhesives, coatings, water-soluble films, etc.

Description

Detailed Description of the Invention The attempt to introduce sulfonic acid groups into polyester is expected to find new applications in binders with excellent dispersibility for pigments and magnetic materials, anionic functional resins, etc. By introducing a relatively large amount of water, it is possible to make polyester resin water-soluble, and its application to fields such as textile pastes, paper pastes, paints, and adhesives has been expanded since ancient times. It is being done.

Conventionally, the most well-known method for introducing sulfone [-1) base into polyester is the method of finely mixing the sulfonate base, for example, with a sulfonate group-containing compound. 15-Sodicumsulfoisophthalic acid is condensed with a dicarboxylic acid such as iso-7curic acid or a polyhydric alcohol such as diethylene glycol. The resulting water-soluble polyester is useful as fiber A, (sizing agent for silk, silk sizing agent, etc.).

However, there is a problem that 5-sodicumsulboisophthalic acid is an expensive compound, and the more sulfonic acid groups can be introduced into polyester by using cheaper raw materials than t:1 in industrial methods, the more advantageous it becomes. I can't even tell you what happened.

However, as a result of intensive research to solve this problem, the inventors of the present invention found that either a sulfonated polyhydric alcohol in which an acidic sulfite is added to the unsaturated bonds of an unsaturated polyhydric alcohol is reacted with a polybasic acid, or an unsaturated polyhydric alcohol has a polybasic acid. When acidic sulfite is added to the unsaturated bonds of an unsaturated polyester obtained by reacting a saturated polyalcohol and a polybasic acid, the introduction of sulfonic acid groups is carried out at a high rate, and the water-soluble polyester is easily converted into 1
91J was discovered and the present invention was completed.

Since the acidic sulfite used in Fudanri is an inexpensive compound that can be easily obtained industrially, the method from scratch 1 of introducing hesulfonic acid groups into polyester using such raw materials is extremely useful industrially. be.

In the present invention, an unsaturated polyhydric alcohol is reacted with an acidic sulfite, and a polybasic acid is polycondensed with a sulfonated polyhydric alcohol in which the acidic sulfite is added to the unsaturated bonds in the alcohol. Although it is possible to carry out either method of reacting an acidic sulfite with an unsaturated polyester obtained by polycondensation of a saturated polyhydric alcohol and a polybasic acid and adding the acidic sulfite to the unsaturated bond, the former method is suitable for polyester. In the former method, an unsaturated polyhydric alcohol and an acidic sulfite are first subjected to an addition reaction to prepare a sulfonated polyhydric alcohol. The reaction between the two is, for example, 2-butene-1,4-
This is done by heating IJ cum to about 70°C in the presence of iron oxide.

Next, the sulfonated polyhydric alcohol and polybasic acid are condensed to obtain a polyester. This reaction is carried out under the same conditions as for ordinary polyester reactions, so no special operations are required. That is, after esterifying a polyhydric alcohol and a polybasic acid at a temperature of 170 to 280°C in the presence of an esterification catalyst such as dibutyltin oxide, antimony trioxide, or zinc acetate, 0.5 ~1.0 m
The condensation reaction is carried out under the vacuum of HH at a temperature of 240 to 280°. Examples of the condensation catalyst include germanicum oxide, antimony trioxide, tetrabutyl titanate, dibutyltin oxide, and the like.

In the latter method, first, to prepare an unsaturated polyester, unsaturated polyhydric alcohol and saturated alcohol are mixed in a ratio of about 1.5 to 2 moles per mole of polybasic acid, together with a catalyst and a stabilizer, using a stirrer, The temperature is 230 to 270° when charged into a reaction vessel equipped with a finer, a partial condenser, and a torque meter.
Carry out the lees U reaction.

Next, the unsaturated polynisder and acidic sulfite are reacted to add acidic nitrite and acid salt to the unsaturated bonds in the polyester.

Reaction: Dissolve the unsaturated polyester in benzene and add acidic sulfite in the presence of iron oxide.
They are mixed in a proportion of mol % to 200 mol % and heated at 60° C. to the boiling point. After about 60 minutes to 6 hours, excess acidic sulfur and acid sodium are neutralized with sodium hydroxide to complete the reaction.

In any of the above methods, it is essential to require an unsaturated poly-1111 alcohol as a component constituting the unsaturated bonds in the polyester, and if an unsaturated polybasic acid is used instead, gelation occurs during polymerization. There is a risk of

The unsaturated polyhydric alcohols used in the present invention include 6-ptento-2-diol, 2-ptento-4-diol,
Olefinic glycols such as 2,5-dimethyl-6-hexene-2,5-diol, 1,5-hexene-
Examples include diolefin thread glycols such as 6,4-diol 2,6-octazine-4,5-diol.

Examples of alcohols used in combination with other than the above include ethylene glycol, diethylene glycol, fluoropylene glycol, dipropylene glycol, neopentyl glycol,
Examples include cyclohexane dimetatool and pentaerythritol.

Examples of polybasic acids include succinic acid, malonic acid, dimethylmalonic acid, succinic acid, geltal acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylgeltaric acid, azelaic acid, sebacic acid, 1,6 -Cyclohexanedicarboxylic acid, 1,6-cyclopencunedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 2,5-
Norbornane dicarboxylic acid, 1,4-naphthalic acid, siphenic acid, 4,4'-ogishibenzoic acid, diglycolic acid, thiodipropion, 4,4'-sulfonyl dibenzoic acid, 2,5-naphthalene dicarboxylic acid Examples include saturated carboxylic acids such as.

If necessary, an unsaturated carboxylic acid such as maleic acid, hydromaleic acid, fumaric acid, itaconic acid, or citraconic acid may be used in combination.

The above carboxylic acid may be in the form of lower alkyl ester, silicic acid chloride, or the like.

As the acidic average monoacid, acidic nitrite, acidic nitrite, acidic potassium sulfite, etc. are practically used.

The thus obtained polyester-1 fiber paste, paper processing agent, fiber processing agent, adhesive, paint, water-soluble film, fiber, pigment and magnetic substance dispersibility, anionic functional resin, etc. It is for t, te].

Next, I will explain E'lJ's method in more detail using an example.

Example 1 5j equipped with a stirrer, rectification, nitrogen sakai inlet tube, and vacuum device
l Ome Yong I! , terephthalic acid 0.5 mol, isophthalic acid 0.4 mol, adipic acid 0.1 mol, ethylene glycol 0.45 mol, diethylene glycol 1.
0 mol, 2-radiosulfo-1,4-butanediol 0
．． After charging 15 mol and 0.1 part of dibutyltin oxide and carrying out esterification at 14.0 to 220°C with stirring, 0.05 part of phosphoric acid and 0.1 part of antimony trioxide were added. ~l, under vacuum of Om+++IIg25
A polyester having an intrinsic viscosity of 0.58 was produced by performing polyfoaming at 0°C. K 80 while stirring 20 kg of the polyester
When K was added to warm water (80'C), an aqueous solution that was 100% permeable was obtained after 6 minutes.

As a control example, a similar test was conducted on a polyester obtained in the same manner as in Example 1, except that the use of 2-radiosulfo-1,4-butanediol was omitted, and no swelling occurred.

Example 2 50 equipped with a stirrer, refinement tower, nitrogen introduction pipe, and vacuum device
0 me volume reacted with Te1/phthalic acid, 42 mol, isophthalic acid 0.46 mol, adipic acid 0.15 mol, ethylene glycol 0.76 mol, neobenzal glycol 0.75 mol, 2-radio Sulfo-14-butanediol O, [ ] 22 mol and digityltin ochizoid 0.
After charging 1 part and carrying out Nisdel treatment at 140 to 220°C with stirring, 0.05 part of phosphoric acid, antimony trioxide [1,1
A polyester having an intrinsic viscosity of 0.68 was produced by adding 5 to 1 parts of the polyester and performing grading under a vacuum of 0 rn = tIIK.

The polyester 20y was heated with 80 me warm water (80 me) while stirring.
When the solution was added at 0° C., an aqueous solution of #[transparency E]1 was obtained after 60 minutes.

In addition, Example 2 except that the use of 2-radiosulfo-1,4-butanediol in Control Example and 17 was omitted in 11+ and 14.
When the same test was conducted on polyester obtained by the same method as above, no zeta-swelling shift occurred.

Example 6 The same method as in Example 1 was carried out except that 3-sodiosulfo-1,2-butanediol was used instead of 2-sodiosulfo-1,4-butanediol.
The same results as for the side were obtained.

Patent Applicant: Nippon Gosei Kagaku Kosou Co., Ltd. Procedural Amendment Group (Hakuhaku) 1981 4!12 JI1 1, Director General of the Y License Office Wakasugi Sodaidono 1, Displaying 1 Patent Application No. 169085 J゛2 , Name of the invention: Process for producing polyester containing sulfonic acid groups 3, Relationship with the person making the amendment (111 cases) Patent applicant: 9-6-4, Nozaki-cho, Kita-ku, Hiaka-shi, Patent specification subject to amendment Issue 1-11. -Detailed H of J (1 Ming no Kana 5, Contents January Specification, Page 10, Add the following sentence after Example B) -.

[Example 4] Stirrer, rectification column, chamber infiltration tube, vacuum device c7 (4 [7
500 me etc. reaction can 1/(teL/71 acid f1
．． 5 mol, isophthalic acid 11.4 mol, adipic acid t
], 17 cells, enalenocricol (1,75 cells, neopentyl glycol 0.75 cells, 2-7 ten-1.4
- 0.015 mole of diol and 0.1 part of dibutyltin oxide were charged and stirred (after esterification was carried out at 140 to 220°C, 1.05 part of phosphorus 14N and 0.1 part of antisulfate trioxide were added to Shirika L0.5~□ 1.01111
+I The limiting viscosity is 0.8 by tightening the nails under a vacuum of ITg.
7σ) Polyester is prepared by mixing the obtained unsaturated polynisdel with benzene ((: bath f +
4 A solution with an L-C concentration of 30 wt 1i% and 17, and further added to this solution 5y of iron oxide, 1141 acid submers, 1 acid 15
] was added, the temperature was maintained at 611-8 noC and stirred for 6 hours, and acidic sodium sulfite was added to the unsaturated bonds in 2-butene-1,4-dial. Ta. After the reaction is completed, neutralize with sodium sulfite as a filter material, and P.
[separately] After separation, benzene was removed by distillation, and maleic anhydride was added in place of 2-zonal-1,4-diol to prepare a polyamide ester, but the product was 1:1. Inside 1
1" It was extremely viscous, and it was not possible to obtain a sulfonic acid group-containing poly(L) stellate. ) Humanities

Claims (1)

[Claims] Adding acidic sulfite to the unsaturated bonds of unsaturated polyhydric alcohol (
(It is characterized by adding an acidic sulfite to the unsaturated bonds of an unsaturated polyester obtained by reacting an added sulfonated polyhydric alcohol and a polybasic acid, or by reacting an unsaturated polyhydric alcohol and a polybasic acid.) IjA method for producing polyester containing sulfonic acid groups.