JPH0639514B2 - Process for producing new condensate of bisphenol and aromatic aminosulfonic acid and its condensate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a condensate of a novel bisphenol and an aromatic aminosulfonic acid, and a condensate thereof.

[Conventional technology]

Recently, as a water-reducing agent that improves the consistency of cement compositions and reduces fluidity changes such as slump loss over time, a condensate having a high molecular weight of aromatic aminosulfonic acid and phenols has been developed. (Japanese Patent Laid-Open No. 1-113419).

However, in this reaction, a large amount of unreacted aromatic amino sulfonic acid that does not exhibit water-reducing property (dispersibility) remains.
It is considered that this is because phenols easily form homopolymers. Further, due to the properties of these phenols, the stability under acidic conditions is not good.

[Means for Solving the Problems]

An object of the present invention is a condensate containing an aromatic aminosulfonic acid as a component, which reduces unreacted aromatic aminosulfonic acid which is an ineffective component as much as possible, and also has a polar skeleton, a heat-resistant structure, and a steric property in the hydrophobic skeleton. By giving, the conventional aromatic amino sulfonic acid-based condensate has excellent performance,
Another object is to provide a condensate useful in a wider range of fields.

That is, the present invention is represented by the general formula (I) [Where X is (Wherein R ₁ , R ₂ , and R ₃ represent hydrogen or an alkyl group, and R ₄ represents an alkenyl group)], or a salt thereof, a compound represented by the general formula (II) A method for producing a novel condensate obtained by condensing an aromatic aminosulfonic acid represented by the formula (wherein Y represents hydrogen or an alkyl group) or a salt thereof with formaldehyde under an alkali catalyst. Is.

The compound represented by the general formula (I) is 2,2-bis (4-hydroxyphenyl) propane represented by the formula (III) or a salt thereof. Wherein the compound represented by the general formula (II) is 4-aminobenzenesulfonic acid represented by the formula (IV) or a salt thereof. , The resulting novel condensate has the following general formula (V)
It is presumed to be a 4-aminobenzenesulfonic acid · 2,2-bis (4-hydroxyphenyl) propane · formaldehyde condensate represented by

(In the formula, n is an integer of 1 to 20) In the present invention, the condensation reaction is represented by the general formula (I) with respect to 100 parts by weight of the aromatic aminosulfonic acid represented by the general formula (II) or a salt thereof. It is carried out at a ratio of 20 to 150 parts by weight of bisphenol or a salt thereof and 20 to 65 parts by weight of formaldehyde, preferably one compound of the compound of the general formula (I) or a salt thereof, or a total molar ratio of two or more compounds. The molar ratio of the compound of formula (II) or salt thereof to formaldehyde is 0.3 to 1.0: 1.0: 1.5 to 3.0.

Further, the alkali catalyst used is a metal hydroxide such as sodium hydroxide, calcium hydroxide or potassium hydroxide, and a hydroxide of an ammonium group, and the like, and the aromatic aminosulfonic acid represented by the general formula (II) is used. 0.5 for 1 mol
To 2.0 molar equivalents are preferably used.

If these molar ratios deviate from the molar equivalent ratio range, the amount of unreacted aromatic aminosulfonic acid tends to increase. Such condensation reaction can be carried out in a suitable solvent that does not cause condensation, but is preferably a bisphenol represented by the general formula (I) and an aromatic aminosulfonic acid represented by the general formula (II), and It is carried out by mixing an alkali with water and performing a solid-liquid reaction. In this case, the bisphenols represented by the general formula (II) are sparingly soluble in water (except under strong alkaline conditions), but are dissolved as the reaction progresses.

Alternatively, the salt of aromatic aminosulfonic acid may be dissolved in water, and bisphenols may be added thereto for reaction. In this case, it is preferable to adjust the pH of the aqueous solution of the aromatic aminosulfonate to 7 to 12 with an alkali catalyst. If the amount is out of this range, the amount of unreacted aromatic aminosulfonic acid tends to increase.

The reaction temperature is 60 to 110 ° C., and the reaction time is not particularly limited, but is preferably 4 to 20 hours. Also, after reacting for several hours, adjusting to a strong alkaline condition (pH 10 to 13) and allowing the reaction to proceed again, the condensation proceeds rapidly.

Formaldehyde is preferably added dropwise in 1 to 3 hours, and the reaction concentration is usually 20 to 50 wt%.

[Action]

The condensate of the present invention composed of bisphenols and aromatic aminosulfonic acid can extremely reduce the residual ratio of unreacted aromatic aminosulfonic acid as compared with the condensate composed of phenols and aromatic aminosulfonic acid. Is.
This is thought to be due to the difference in the ease with which bisphenols and homopolymers of phenols are formed. Bisphenols have a larger steric hindrance than phenols,
It is considered that this is because the degree of freedom of the reaction point is greatly limited, so that it is difficult for the homopolymer to be produced by itself and the reaction with the aromatic aminosulfonic acid is almost complete.

As a result, almost all of the used aromatic aminosulfonic acid can be used as the active ingredient.

Further, since the condensate itself does not easily undergo recondensation, the stability of the condensate is good even under acidic conditions.

Furthermore, useful polar groups, hydrophilic groups, or heat resistant structures can be introduced into the hydrophobic skeleton.

Further, the hydrophobic skeleton can be made to have three-dimensionality so that it is difficult to be adsorbed by the dispersion medium.

From these, the condensate of bisphenols and aromatic aminosulfonic acid can exhibit its usefulness in a wide range of fields.

〔Example〕

 Hereinafter, the present invention will be described in detail with reference to examples.

Example 1 A reactor equipped with a stirrer, a reflux device, a thermometer, and a formaldehyde aqueous solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 2,2-bis (4-hydroxyphenyl) propane 114.15 g (0.5 mol) ・ NaOH aqueous solution To this solid liquid, 171.43 g (formaldehyde, 2 mol) of 35% aqueous formaldehyde solution was charged at 90 ° C. in 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzene sulfonic acid) amount is 31,568 and 2.5 respectively
% (Vs. solid content).

The weight average molecular weight was measured by gel permeation chromatography and converted by pullulan standard. The residual monomer was obtained from the area ratio of the gel permeation chromatography using a differential refractometer.

The gel permeation chromatography of the obtained condensate is shown in FIG. 1, its infrared spectrum is shown in FIGS. 2 and 3, and the nuclear magnetic resonance spectrum is shown in FIG.

2,2-bis (4-hydroxyphenyl) at 44ppm in Figure 4.
There is a peak derived from the methyl group of 2,2-bis (4-hydroxyphenyl) propane at 33 ppm, which is a peak derived from the quaternary carbon of propane, and is a condensation product of 2,2-bis (4-hydroxyphenyl) propane. I understand.

Example 2 A reactor equipped with a stirrer, a reflux device, a thermometer and a formaldehyde aqueous solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 4,4'-dihydrodiphenylmethane 100.12 g (0.5 mol) ・ NaOH aqueous solution To this solid liquid, 171.43 g of a 35% aqueous solution of formaldehyde (formal aldehyde, 2 mol) was charged at a temperature of 90 ° C. for 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzenesulfonic acid) amount is 31,290 and 3.8 respectively
% (Vs. solid content).

Example 3 A reactor equipped with a stirring device, a reflux device, a thermometer, and a formaldehyde aqueous solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 4,4'-dihydroxybiphenyl 93.10 g (0.5 mol) ・ NaOH aqueous solution To this solid liquid, 171.43 g (formaldehyde, 2 mol) of 35% aqueous formaldehyde solution was charged at 90 ° C. in 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzene sulfonic acid) amount is 26,361 and 2.7 respectively
% (Vs. solid content).

Example 4 A reactor equipped with a stirrer, a reflux device, a thermometer and a formaldehyde aqueous solution dropping device was charged with a predetermined amount of the following substances.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 4,4'-dihydroxydiphenyl sulfone 125.15 g (0.5 mol) ・ NaOH aqueous solution To this solid liquid, 171.43 g of 35% aqueous formaldehyde solution (formaldehyde, 2 mol) was charged at a temperature of 90 ° C. in 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzenesulfonic acid) amount is 38,210 and 1.8 respectively
% (Vs. solid content).

Example 5 A reactor equipped with a stirrer, a reflux device, a thermometer, and a formaldehyde solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 4,4'-dihydroxydiphenyl ether 101.00 g (0.5 mol) ・ NaOH aqueous solution To this solid liquid, 171.43 g of a 35% aqueous formaldehyde solution (formaldehyde, 2 ml) was charged at a temperature of 90 ° C. for 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzene sulfonic acid) amount is 26,981 and 3.1 respectively
% (Vs. solid content).

Example 6 A reactor equipped with a stirrer, a reflux device, a thermometer and a formaldehyde aqueous solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 4,4-bis (4-hydroxyphenyl) valeric acid 143.17 g (0.5 mol) ・ NaOH aqueous solution 171.43 g of 35% aqueous formaldehyde solution (formaldehyde, 2 mol) was charged to this solid liquid at a temperature of 93 ° C. for 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzenesulfonic acid) amount is 28,238 and 4.1, respectively.
% (Vs. solid content).

Example 7 A reactor equipped with a stirrer, a reflux device, a thermometer, and a formaldehyde solution dropping device was charged with the following substances in predetermined amounts.

・ 4-aminobenzenesulfonic acid 173.20 g (1 mol) ・ 2,2-bis (4-hydroxyphenyl) propane 91.32 g (0.4 mol) ・ 4,4-bis (4-hydroxyphenyl) valeric acid 28.63 g (0.1 mol ) ・ NaOH aqueous solution To this solid liquid, 171.43 g of 35% aqueous formaldehyde solution (formaldehyde, 2 mol) was charged at a temperature of 92 ° C. for 1 hour.

Then, the mixture was refluxed at a temperature of 100 ° C. for 9 hours to obtain an aqueous solution of a condensate.

The weight average molecular weight (Mw) of the obtained condensate and the residual monomer (4-
Aminobenzenesulfonic acid) amount is 32,450 and 3.1 respectively
% (Vs. solid content).

〔The invention's effect〕

The condensate of the present invention is useful as an industrial dispersant and a curing agent for epoxy resins.

When the present invention is used as a water reducing agent for cement compositions such as cement paste, mortar and concrete, the water reducing property is particularly high, and the fluidity is less likely to decrease with time, and the workability is low.
Workability is improved.

In addition, when used as a dispersant for dyes, it does not show stains on the cloth and has good high temperature dispersion stability. Furthermore, it exhibits excellent dispersibility in coal / water slurry, gypsum, calcium carbonate and the like.

[Brief description of drawings]

FIG. 1 shows gel permeation chromatography of the condensate of Example 1, FIGS. 2 and 3 show its infrared absorption spectrum, and FIG. 4 shows its nuclear magnetic resonance spectrum.

Claims (5)

[Claims] 1. A general formula (I) [Where X is (Wherein R ₁ , R ₂ , and R ₃ are each independently hydrogen, or an alkyl group, and R ₄ is an alkenyl group)], or a salt thereof with general formula (II) A novel method for producing an aromatic aminosulfonic acid / bisphenol / formaldehyde-based condensate, which comprises reacting a compound represented by the formula (wherein Y represents hydrogen or an alkyl group) or a salt thereof with formaldehyde. . 2. A compound represented by general formula (I) or a salt thereof, and two or more compounds reacted with a compound represented by general formula (II) or a salt thereof and formaldehyde.
A method for producing the novel condensate described. 3. The number of moles of the compound of the general formula (I) or the total number of moles of two or more compounds of the general formula (I) and the general formula (II).
The number of moles of the compound, the number of moles of formaldehyde, and the molar equivalent of alkali are: A: the number of moles of compound (I), or the total number of moles of two or more types of compound (I) B: compound (II) 3. The number of moles of C: the number of moles of formaldehyde D: the molar equivalent of alkali A: B: C: D = 0.3 to 1.0: 1.0: 1.5 to 3.0: 0.5 to 2.0. Of the novel condensate of. 4. Formula (III) 2,2-bis (4-hydroxyphenyl) propane or a salt thereof represented by the formula (IV) Of 4-aminobenzenesulfonic acid / 2,2-bis (4-hydroxyphenyl) propane / formaldehyde condensate characterized by reacting 4-aminobenzenesulfonic acid or salt thereof with formaldehyde represented by Method. 5. A condensate of 4-aminobenzenesulfonic acid or a salt thereof and 2,2-bis (4-hydroxyphenyl) propane or a salt thereof and formaldehyde, which has the following general formula:
(V) (In the formula, n is an integer of 1 to 20) A novel 4-aminobenzenesulfonic acid-2,2-bis (4-hydroxyphenyl) propane-formaldehyde condensate.