JPS59202219A - Production of sulfonate group-containing polyester resin - Google Patents

Abstract

PURPOSE:To obtain the titled polyester resin suitable as a textile paste or the like, at low cost, by reacting an epoxy group-containing compound with an acid sulfite, and employing the produced sulfonate group-containing polyfunctional monomer as a component of the material. CONSTITUTION:A polyfunctional monomer containing both a sulfonate group and a hydroxyl group is produced by reacting an epoxy group-containing compound such as epichlorohydrin or ethylene glcyol monoglycidyl ether with an acid sulfite according to the reaction of the formula, wherein M is an alkali metal. The produced polyfunctional monomer is esterified and then condensed with a polyhydric alcohol, e.g., ethylene glycol or propylene glycol, and a polybasic acid, e.g., terephthalic or malonic acid, in the presence of an esterification catalyst and a condensation catalyst to obtain the purpose sulfonate group-containing polyester resin.

Description

[Detailed Description of the Invention] Attempt 1 of adding a sulfonic acid group in polyester) is expected to find new applications in binders with excellent dispersibility of pigments and magnetic materials, anionic functional resins, etc. At the same time, by introducing a relatively large amount of sulfonic acid groups, it is possible to make polyester TL/IJ resin water-soluble, and its application to fields such as textile pastes, paper processing, paints, and adhesives is further expanded. The most well-known method for decontaminating hesulfonic acid groups in polyester 43 fats is the condensation polymerization of sulfonate-containing compounds, which have been studied for a long time. Base-containing compounds, typically 5-sodium sulfoisulfuric acid and isophthalic acid! It condenses dicarboxylic acids such as i2 and polyhydric alcohols such as diethylene glycol. The polyester tJa produced by fG is useful for coating materials, textile pastes, sizing agents, etc. However, there is a problem that 5-sodiumsulfoiso7talic acid is an expensive compound, and it cannot be used in industrial methods. It goes without saying that the more sulfonic acid groups can be added to the polyester resin by using cheaper raw materials, the more advantageous it will be.

However, when producing 5-sodicumsulfoiphthalic acid, it is dangerous because strong acids such as concentrated sulfuric acid are used, and of course it is necessary to consider problems such as corrosion of production equipment, so it is relatively difficult to produce. It has the disadvantage of being subject to strict manufacturing constraints.

However, the inventors have worked hard to solve this problem.
As a result of repeated research, we found that using a polyfunctional monocontainer containing a sulfonic acid group obtained by reacting an acidic sulfite with a compound having an epoxy group as one component of polyester resin is inexpensive and solves the problems described above. The present inventors have discovered a more efficient method of introducing sulfonic acid groups than conventional methods, which enables the production of polyester resins containing sulfonic acid groups using a small amount of raw materials, and have completed the present invention.

Misfire 1) In 11, a sulfonic acid group-containing polyfunctional monomer obtained by reacting an epoxy group-containing compound with an acidic sulfite is used as a raw material for producing polyester resin.

Polyfunctionality as used in the present invention means that the molecule contains at least two or more carboxyl groups or hydroxyl groups in total, and the polyester resin can be produced due to the presence of these functional groups. The reaction of acidic sulfite with epoxy groups is conventionally known and is as follows.

As is clear from the above formula, one sulfonic acid group and one hydroxyl group are generated for each epoxy group, so trying to use the hydroxyl group in the kneading reaction of polynisder resin is a failure! This is the biggest feature of lJ. Therefore, if a compound having two or more epoxy groups is reacted with an acidic sulfite, a polyfunctional monomer having the same number of hydroxyl groups as the number of epoxy groups can be obtained. However, even if a compound has only one epoxy group, it may be difficult to find a compound that has one or more hydroxyl or carboxyl groups in the molecule, or a compound that has one or more hydroxyl or carboxyl groups in the molecule, or a compound that has one or more hydroxyl or carboxyl groups in the molecule, or a hydroxyl group due to hydrolysis etc. Alternatively, a compound having a group that can become a carboxyl group can be used as a raw material for polyester resin since it is possible to produce a polyfunctional monomer.

Compounds having such epoxy ends include epichlorohydrin, glycidol, ethylene glycol mono(or di)glycidyl ether, diethylene glycol mono(or di)glycidyl ether, triethylene glycol mono(or di)glycidyl ether, polyethylene glycol mono(or di)glycidyl ether, Glycidyl ether, propylene glycol mono (or di) glycidyl ether, polypropylene glycol mono (or di) glycidyl ether, gtylene gelicol mono (or di) glycidyl ether, polybutylene glycol mono (or di) glycidyl ether, neopentyl glycol mono ( or di)glycidyl ether, 1,6-hexanediol mono(or di)glycidyl ether, bisphenol A type mo/(
or di)glycidyl ether, bisphenol A type ethylene oxide adduct mono(or di)glycidyl ether, bisphenol A type propylene oxide adduct mono(or di)glycidyl ether water temperature bisphenol A type mono(or di)glycidyl ether, water & bisphenol A type Ethylene oxide adduct mono(or di)glycidyl ether, hydrogenated bisphenol A type propylene oxide adduct mono(or di)glycidyl ether, succinic acid mono(or! I:t di)glycidyl ester, mono(or di) succinic acid Glycidyl Nisdel, Cono monophosphate mono(or di)glycidyl ester, Gourmet/
1. /acid mono(or di)glycidyl ester, adipine mono(or di)glycidyl ester, pimelic acid mono(or di)glycidyl ester, mono(or di)glycidylnisder perate, azelaic acid mono(or di)glycidyl ester
Glycidyl ester, mono (or di) glycidyl ester, heptalic acid mono (or di) glycidyl ester, isophthalic acid mono (or di) glycidyl ester, terephthal mono (or di) glycidyl ester, Q, m, p-hydroxybenzoic acid glycidyl ether, o + ” + p-hydroxybenzoic acid glycidyl ester, o, m, p-hydroxybenzoic acid diglycidyl ester ether, 1,5-diglycidyl-5,5-dimethylhydantoin, etc. , cyclohexanediol mono(or di)glycidyl ether,
Alicyclic epoxy compounds such as cyclohexanedicarboxylic acid mono(or di)glycidyl ester, and polyhydric alcohols such as glycerin, penquerythritol, and trimethylolpropane in which at least one hydroxyl group is a glycidyl ether group. Typical examples include polybasic acids such as trimellitic acid and pyromellitic acid in which at least one of the carboxyl groups is a glycidyl ester group, glycidyl esters of isocyanic acid, and novolak-type glycidyl esters.

Examples of the acidic sulfite to be reacted with the compound having an epoxy group include t/i acidic sodium sulfite, acidic potassium sulfite, etc., but acidic sodium sulfite is more practical.

However, in the reaction between a compound having an epoxy group and an acidic sulfite, 1 to 4 moles of the latter are usually prepared per 1 mole of the former.
It is sufficient to carry out the reaction at a temperature of 20 to 200° C. in the presence or absence of a solvent. If necessary, it is also possible to use catalysts such as amines and imidazole. As the solvent, in addition to water, general-purpose solvents such as alcohol, ether, ester, benzene, toluene, xylene, acetone, and dioxane, and mixed solvents thereof can be used as appropriate.

As the polyester resin components other than the sulfonic acid group-containing polyfunctional monomer obtained by this method, any polyhydric alcohol or poly@basic acid used in the production of ordinary polyester resins can be used.

Polyhydric alcohols include ethylene glycol, diethylene glycol, phlopylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane dimetatool, pentaerythritol, and trimethylol. Examples include propane and glycerin.

Examples of polybasic acids include succinic acid, malonic acid, dimethylmalonic acid, succinic acid, glucuric acid, adipic acid,
Trimethyladipic acid, pimelic acid, 22-dimethylglucuric acid, acetate, fonic acid, Sebacin City, 1-cyclopenkune dicarboxylic acid, 1,6-cyclopenkune dicarboxylic acid, 1,4-Schiff To Kizandicarbon,
Fucururo father, Prephthal 1, isophthalic acid, 25-norbornanedicarboxylic acid, 2.14-naphthalic acid, siphenic acid, 4,4'-Ogishi Anzuki, own weight, diglycolic acid, thiodipropion, 44'-sulfonyl dicarboxylic acid Examples include benzoic acid, saturated carboxylic acids such as 2,5-knac dicarboxylic acid, and substituted alkyl esters thereof.

If necessary, maleic acid, maleic anhydride, fumaric acid,
Itaconic acid, citraconic acid, etc., without unsaturated carboxylic acids or their strong argyl esters, VC3-ptento-2-diol, 2-gutento-4-diol, 2.
Olefins such as 5-dimethyl-6-hexene-2,5-diol + g)-1-l, 1,5-hexadiene-6,
It is also possible to use unsaturated polyhydric alcohols such as 4-diol and 2-6-octazinine-4,5-diol.

A sulfonic acid group-containing polyester resin B is prepared by condensing a sulfonic acid group-containing polyfunctional monomer, a polyhydric alcohol, and a polybasic acid as described in (2) below. The amount of the sulfonic acid group-containing polyfunctional monomer may be adjusted arbitrarily depending on the purpose and use of the polyester resin to be obtained, but it is usually within the range of 40 mol% or less in the polyester resin. be done.

When performing a knitting reaction, use Jl'! Since the reaction is carried out under the same conditions as for ordinary polyester resin reactions, no special operations are required. That is, the above additive is dibutyltin oxide,
Antimony trioxide, f:'t'+' Fm After carrying out an esterification reaction at a temperature of 170 to 280°C in the presence of an esterification catalyst such as zinc, 0.5 to 1.0 in the presence of a condensation catalyst
The mixture is heated under vacuum at a temperature of 240 to 280°C. Examples of the condensation catalyst include t'v-glumanicum, antimony trioxide, tetocgutyl titanate, dibutyltin oxide, and the like.

Can the polyester resin obtained in this way be used for textiles? 11 agents, paper processing agents, fiber processing agents, adhesive agents, paints, coating agents for various films and their metallized films, water-soluble films, fibers, binders and anions that are excellent in handling pigments and magnetic materials. It is useful as a functional resin, etc.

Next, the method of the present invention will be explained in more detail by giving examples.

Example 1 0.5 mole of diethylene glycol diglycidyl ether and 1.5 mole of acidic subchloride, iL acid tricum, and water as a solvent>? , i' were reacted at 100° C. for 6 hours to obtain a sulfonic acid group-containing polyfunctional monomer (in this case, a dihydric alcohol).

On the other hand, in a 500-capacity reactor equipped with a distillation column, a rectification column, a nitrogen inlet pipe, and a vacuum device, 0.5 mole of terephcuric acid, 6 o.s. mole of isophthalic acid, 07 mole of ethylene glycol,
0.6 mol of neopentyl glycol, 0.1 mol of diethylene glycol, 0.2 mol of the above polyfunctional monomer containing a sulfonic acid group, and 0.1 part of digyltin oxide were charged and esterified at 140 to 220°C with stirring. After carrying out the above steps, a polyester resin having a phosphoric acid concentration of 0.05 and a limiting viscosity of 0.7 was produced. When the polyester resin 20y was added to 80 me warm water (80° C.) with stirring, a clear aqueous solution was obtained after 6 minutes.

Further, when the polynisder resin was analyzed by N'MR, the resin composition ratio was terephthalic acid: isophthalic acid: ethylene glycol: neopentyl glycol: diethylene glycol -〇, 5: 0.5: 0.2: 0.
5:0.5 (molar ratio), and elemental analysis confirmed that about 70 mol% of diethylene glycol contained sulfonic acid groups.

Example 2 0.5 mol of adipic acid diglycidyl ester and 1.5 mol of acidic sodium sulfite were mixed at a temperature of 1 using water as a solvent.
The mixture was reacted at 00"'C for 6 hours to obtain a sulfonic acid group-containing polyfunctional monomer (dihydric alcohol).

Hereinafter, in the same manner as in Example 1, 0.5 mol of terefucuric acid,
Isophthalic acid 0.5 mol, ethylene glycol 0.8 mol, neopentyl glycol 0.55 mol, diethylene glycol 0.1 mol, the above sulfonic acid f. 15 mol, 0.1 part digtyltin oxide and r1 Germanicum tatide Q
, Prepare 1st 11S and perform 10 steps. The obtained polyester material has an acid value of 0.25 and a water value of 1>2 and a base value of 5.
5. With standard viscosity & O, SS, 20p of the resin was stirred for 8 hours.
0mf! When 1d5 was added to hot water (80C), the same results as in Example 1 were obtained.
i Kit or Prephthal: 1: Isophthalic acid: Ethylene glycol: Neopentyl glycol: Thiethylene glycol: Polyfunctional mono-JIi compound with sulfonic acid base = 0.5: 0.5: 0.25: 0.45
: 0.15:0.15 (cell ratio) -1 Example Bisphenol A diglycidyl ether type epoxy resin (Tobu Kasei, tnyD-i2a: Epoxy UJ11
847 / eq ) O-5 mole and acidic sodium sulfite! 7 ml LO 5 mol τ of water and dioxane as solvents etc. 11
(Reaction was carried out at a temperature of 120° C. for 6 hours using a mixed solvent, to obtain a bisphenol A diglycidyl ether type sulfonic acid group-containing polyfunctional monomer (21-track alcohol).

Hereinafter, in the same manner as in Example 1, 0.5 mol of terephthal e, 940.5 mol of isophthal, 0.8 mol of ethylene glycol, 0.55 mol of neopentyl glycol, 0.1 mol of diethylene glycol, 1 sulfonic acid group-containing polyfunctional 0.15 mol of monomer, digyltin oxide 11
The composition of the resin was analyzed by elemental analysis, NMR, etc. Terephthalic acid: Isofucric acid: Ethylene glycol: Neopentyl glycol: Diethylene glycol: The above-mentioned sulfonic acid group-containing polyfunctional monomer = 0.5: 0.5: 0.55: 0.45
+0.05:0.15 (molar ratio).

Example 4 Trimethylolpropane triglycidyl ether/L10
．． 1 mol of acidic sodium ae and 0.65 mol of acidic sodium ae were reacted with water as a solvent at a temperature of TOO ℃ for 4 hours to obtain a trimethylolpropane triglycidyl ether type sulfonic acid group-containing polyfunctional single F, supernatant (filtration value). Alcohol) was invited.

Hereinafter, in the same manner as in Example 11, 0.5 mol of tele7curic acid, 5 mol of isophthalic acid, 0.4 mol of ethylene glycol, and 0.4 mol of neopentyl glycol were added. 0.26 mol of functional monomer,
0.1 part of digtyltin oxide and 0.1 part of germanicum oxide were charged and a reaction was carried out to obtain l'i', 21'jli
l 2, water 15 (a polyester resin with a base value of 61 and a vague limiting viscosity of 0.5).

When the 4'M fatty acid U-11 was analyzed by elemental analysis and NMR, it was found that terefucuric acid: isofucuric acid: ethylene glycol: neopentyl glycol: ethylene glycol i,
i body-〇, 5: 0.5: Hadaro 5: 0.4:
The molar ratio was 0.05:0.22. ′
Example 5 0.5 mol of pentaerythritol diglycidyl ether was reacted with 1.2 mol of acid sodium chloride and acid sodium as a condensing medium at a humidity of 100°C for 4 hours to form a sulfonic acid base of pen erythritol diglycidyl ether type. A synthesized polyfunctional monomer (dihydric alcohol) was obtained.

As in Example 1, 0.5 mol of terefucuric acid, 5 mol of isophthalic acid, 0.7 mol of ethylene glycol, 0.6 mol of neopentyl glycol, 0.1 mol of diethylene glycol, and the above-mentioned sulfonic acid group-containing polyester were added. 0.2 mol of functional monomer, 0 parts of digyltin oxide and 0.1 part of germanium oxide were charged and reacted to give an acid value of 2,
A polyester resin having a hydroxyl value of 8.2 and an intrinsic viscosity of 0.82 was obtained.

When the composition of Bm fat was analyzed by elemental analysis and NMR, it was found that terephthalic acid: iso-7thalic acid: ethylene glycol: neopentyl glycol: diethylene glycol
: 0.5 : O, Ro5 : 0.4 : 0.05
: 0.2 (molar ratio).

Example 6 0.5 mol of ethylene glycol monoglycidyl ether and acid salt! vk, rft 0.55 mol of sodium
．．・React for 2 hours at 100″C using water as 1 pear,
An ethylene glycol monoglycidyl ether-type sulfonic acid group-containing polyfunctional 1'↓mer (dihydric alcohol) was prepared as f-nia.

Thereafter, in the same manner as in Example 1, terephthal [iZo, 5 mol, isophthalic acid 0.5 mol, ethylene glycol 0.7
mol, neopentyl glycol 0.6 mol, diethylene glycol 1 mol, the above sulfone 1 Yukijo elbow, t-) 1
7Xh was carried out by charging 0.2 mol of a 2-monomer with 6 g, 0.1 part of dibutyltinio.
．． 6, hydroxyl group 1uli 5-0, degree of dryness 0.82
1 yuta of polynisdel, resin. When we analyzed the layer + J of this resin by original analysis and NMR, we found that pre-7curic acid: isophthalic acid: ethylene glycol: neopentyl glycol: jenalene glycol 2 The above-mentioned sulfonic acid base has a polyfunctional mono-11. Body-20,5: 0.5:
The molar ratio was 0.66:0.4:0.4:0.2.

Examples 7 to 10 Using 1,6-hexanesiol monoglycidyl ether instead of the ethylene glycol monoglycidyl ether used in Example B, the reaction was carried out at 100°C for 2 hours (practical example 7), and the reaction was carried out at 100°C using glycidol. (Example 8), reaction using succinic acid monoglycidyl ester at 100"C for 5 hours (Example 9), P-
A sulfonic acid base-combined multifunctional mono'iI'f body was obtained in the same manner as on the same side except that the reaction was carried out at 100°C for 4 hours using hydroxybenzoic acid, and the following procedure was carried out. A reaction similar to that described above was carried out to obtain polyester paulownia.

The physical properties of the obtained resin are as shown in Table 1, and the results of elemental analysis and 4'M resin composition by NMR are t/'i'fj
E The results were almost the same as those obtained in Example 6.

Table 1 Example 11 0.5 mole of epichlorohydrin, acidic IAf, and 0.55 mole of sodium acid were reacted in an aqueous solvent at 100°C for 1 hour, and then 0.7 mole of sodium bicarbonate was added. Hydrolysis was carried out at 100°C to obtain a sulfonic acid group-containing polyfunctional (dihydric alcohol). A polyester resin having an acid value of 0.5, a hydroxyl value of 6.8, and an intrinsic viscosity of 0.8 was obtained and analyzed by elemental analysis and NMR, and the resin composition was almost the same as in Example 6.

Example 12 0.5 mole of epichlorohydrin and 0.55 mole of acidic sodium sulfite were reacted at 100° C. for 2 hours in an aqueous solvent. Add 0.5 mol of potassium cyanide to this to make 1.5
After reacting for a period of time, hydrolysis was performed to obtain a sulfonic acid group-containing polyfunctional monogas (having one hydroxyl group and one carboxyl group in one monomer molecule).

Using this monomer, a reaction was carried out in the same manner as in Example 6, and 1111 polyester resin having an acid value of 0.5, a hydroxyl value of 6.7, and an intrinsic viscosity of 0.89 was obtained by elemental analysis, NM, and R. Analysis revealed that the resin composition was almost the same as Medical Example 6.

Claims (1)

[Claims] A method for producing a sulfonate group-containing polynisder resin, which comprises using a sulfonate group-containing polyfunctional monomer obtained by reacting a compound having an epoxy group with an acidic sulfite as one component of the polynisder resin.