JPH0693067A - Water-soluble bisphenol condensate - Google Patents

Abstract

PURPOSE:To provide a novel condensate which has a specific molecular weight and a negative charge, readily makes an aqueous slurry of carbonaceous fine particles increased concentration and shows not only excellent productivity, transportability, operability but also extremely high dispersibility. CONSTITUTION:The product is obtained by reaction of (A) a bisphenol, preferably 4,4-dihydroxydiphenylsulfone, (B) aminobenzenesulfonic acid and (C) formaldehyde and has a weight-average molecular weight of 1X10<4> and a negative charge of -1.7X10<3>mev per 100 molecular weight. The condensate is obtained by charging components A and B and alkali at a molar ratio of 0.48:1:1.05 to 0.52:1:1.2, adding water so that each component makes a solution of 25 to 35wt.%, then 1 to 1.2 mole of component C is added dropwise at 100 deg.C to effect the reactions, then 0.7 to 0.9 mole of component C is added dropwise at 80 to 85 deg.C to complete the condensation reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel water-soluble bisphenol-based condensate, particularly a water reducing agent for cement, a dye,
The present invention relates to a water-soluble bisphenol-based condensate suitable as a dispersant for organic substances such as water-soluble paints, slurry of coal and water, or inorganic substances such as gypsum and calcium carbonate.

[0002]

2. Description of the Related Art Conventionally, formaldehyde condensates of bisphenols and aminobenzenesulfonic acid (referred to as bisphenol-based condensates) have been used as water-reducing agents for cement (JP-A-3-187960) and as dispersing agents for dyes (see (Kaihei 3-199270) or as an additive for an aqueous slurry of carbonaceous fine powder represented by a slurry composed of coal and water (Japanese Patent Laid-Open No. 3-263494) (Japanese Patent Laid-Open No. 3-140317). Gazette).

However, the above-mentioned bisphenol-based condensate has the drawback that it is difficult to increase the concentration of the slurry and is insufficient in terms of productivity, transportability and workability. There is a drawback that the effect as an agent cannot be fully exerted.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, when a bisphenol-based condensate having a specific molecular weight and a negative charge was used, good results were obtained. The present inventors have reached the present invention by finding that the results can be obtained. Therefore, an object of the present invention is not only excellent in productivity, transportability and workability, since it is easy to increase the concentration of an aqueous slurry of carbonaceous fine powder, and bisphenol excellent in dispersibility than ever before. To provide a system condensate.

[0005]

The above objects of the present invention are as follows.
A condensate obtained by reacting bisphenols, aminobenzenesulfonic acid, and formaldehyde, having a weight average molecular weight of 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ , and having a negative charge amount per 100 of molecular weight of −. 1.7 x 1
Achieved by a water-soluble bisphenol-based condensate characterized by being below 0 ³ meV.

As the bisphenols used in the present invention, it is preferable to use the bisphenols represented by the following chemical formula 2.

[Chemical 2] In the above formula, X is _{-SO 2 -, - CO -,} - S -, - O-,
_{-CH 2 -, - C (CH} 3) 2 - is or a covalent bond.

As specific examples of these, for example, 4,
4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4 '-(perfluoroisopropylidene) diphenol, 4,4'-dihydroxydiphenylmethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybiphenyl and isomers thereof, and the like are used in combination. You may.

Specific examples of the aminobenzenesulfonic acid used in the present invention include 4-aminobenzenesulfonic acid,
2-amino-5-methylbenzenesulfonic acid and isomers thereof can be mentioned. The form of the formaldehyde used in the present invention is not particularly limited, and an aqueous formaldehyde solution can be generally used.

The bisphenol-based condensate of the present invention can be easily obtained by reacting bisphenols, aminobenzenesulfonic acid and formaldehyde as described above. In the above reaction, it is preferable to use an alkali from the viewpoint of promoting the reaction.

Preferred alkalis include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like. The bisphenol condensate of the present invention has a weight average molecular weight of 1.0 × 10 ⁴ to
It is preferably in the range of 2.0 × 10 ⁴ .
When it is 2.0 × 10 ⁴ or more, the cohesiveness becomes strong and the dispersibility when used as a dispersant is deteriorated, and when it is 1.0 × 10 ⁴ or less, the adsorptivity to the dispersoid is lowered. Also, the dispersibility deteriorates.

The bisphenol condensate having the above weight average molecular weight can be easily obtained by the following reaction. That is, the above reaction was carried out using bisphenols (number of moles:
A), aminobenzenesulfonic acid (number of moles: B) and alkali (molar equivalent: C), A: B: C = 0.45:
1.00: 0.95 to 0.55: 1.00: 1.30 ratio range, preferably A: B: C = 0.48: 1.0
The reaction vessel was charged so that the ratio was in the range of 0: 1.05 to 0.52: 1.00: 1.20, and water was added so that the concentration of all these substances was 25 to 35% by weight. The reaction is carried out in the following two steps after the aqueous conditions have been set.

In the first stage reaction, the reaction system is maintained at 100 ° C. or higher, preferably 100 ° C., and formaldehyde 1.
After dripping 0 to 1.2 mol over 0.5 hours, bisphenols and aminobenzenesulfonic acid were condensed for 3 to 4 hours to condense 1 bisphenol and 2 aminobenzenesulfonic acids. It is a reaction that produces a structural unit.

In this reaction, only the formaldehyde necessary for producing the above structural units is added dropwise and the temperature of the reaction system is kept at 100 ° C. or higher. Therefore, only the condensation reaction of bisphenols and aminobenzenesulfonic acid is carried out. It can be done mainly. In this case, if excessive formaldehyde is added or the reaction temperature is set to less than 100 ° C., the product becomes polymerized, and it becomes difficult to control the molecular weight in the subsequent reaction.

The reaction in the second step is carried out at 80 to 85 ° C.
And 0.7 to 0.9 mol of formaldehyde was added dropwise to the product obtained in the first step over 0.5 hours to give 5-2.
By reacting for 0 hour, the weight average molecular weight was 1.
It is a reaction for obtaining a bisphenol-based condensate in the range of 0 × 10 ^{4 to} 2.0 × 10 ⁴ . In this case, the amount of formaldehyde added dropwise is preferably adjusted so that the total amount of the formaldehyde used in the first step is 1.95 mol or less, and particularly 1.85 mol or less.

This reaction is a polymerizing reaction in which the constituent units obtained in the first step are condensed with each other at the bisphenol moiety. In this case, since the reaction system is maintained at 80 to 85 ° C., the weight average molecular weight of the obtained bisphenol-based condensate is in the range of 1.0 × 10 ^{4 to} 2.0 × 10 ⁴ . The weight average molecular weight can be easily determined by gel permeation chromatography (GPC).

As described above, the bisphenol-based condensate of the present invention has a negative charge amount of −1./100 per molecular weight from the viewpoint of improving the dispersibility when used as a dispersant.
It is preferably 7 × 10 ³ meV or less. Here, the amount of negative charge per 100 of the molecular weight means the molecular weight of 100 of the condensate constituent unit calculated by the semi-empirical molecular orbital method.
The most stable structure per unit is calculated, and the amount of negative charges obtained at that time is shown per 100 of molecular weight.

The calculation by the above semiempirical molecular orbital method is
PM3 method (J. Comput. Chm., 10, 20
9,221,1989: Stewart
Can be easily performed by using MOPAC version 5.0, which is a computer program based on the calculation method developed in 1989).

The reason why the water-soluble bisphenol condensate of the present invention has good dispersibility as a dispersant is not clear, but since the condensate has a weight average molecular weight in a specific range, it is agglomerated. It is presumed that this is because the dispersoid is dispersed due to the repulsive force with the negative charge of the dispersion medium because it has a low property and has a high adsorptivity to the dispersoid and has a high negative charge. Since the water-soluble bisphenol-based condensate of the present invention has a weight average molecular weight in a specific range and also has a high negative charge, it is easy to increase the concentration of an aqueous slurry of carbon fine powder.

[0019]

As described above in detail, the water-soluble bisphenol-based condensate of the present invention is not only excellent in productivity, transportability, workability and quality, but also an inorganic substance such as cement, gypsum and calcium carbonate or coal. It is a condensate having extremely high dispersibility when used as a dispersant for organic substances such as dyes and water-soluble paints.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.
In addition, "part" which shows a compounding quantity shows a weight part.

Example 1. The following substances were charged into a reaction vessel equipped with a stirrer, a reflux device, a formaldehyde aqueous solution dropping device, and a temperature control device. 4,4'-Dihydroxydiphenyl sulfone 0.5 mol [125.2 parts] 4-aminobenzenesulfonic acid 1.00 mol [173.2 parts] Sodium hydroxide 1.10 mol [44.0 parts] Water [745 .0]

The resulting mixed solution was heated to 100 ° C., and 1.00 mol of formaldehyde (37% by weight aqueous solution 81.1) was added.
(Part) was added dropwise over 0.5 hour and then reacted at 100 ° C. for 3 hours (first step reaction). Then, the reaction system is set to 80
After cooling to ℃, formaldehyde 0.70 mol (37
A 5% by weight aqueous solution of formaldehyde (56.8 parts) was added dropwise over 0.5 hour, and the mixture was further reacted at 80 to 85 ° C. for 16 hours to obtain an aqueous solution of a condensate (second step reaction).

The weight average molecular weight of the obtained condensate measured by GPC was 1.5 × 10 ⁴ . The negative charge amount per 100 molecular weight calculated by the semi-empirical molecular orbital method using MOPAC version 5.0 of the obtained condensate was -1.9 × 10 ³ meV. The above results are summarized in Table 2.

The weight average molecular weight was measured by GPC according to the following conditions. Column: KB-80M + KB-803 + KB-
802.5 (manufactured by Showa Denko KK) Column temperature: 55 ° C Eluent: 0.05 molar solution of sodium nitrate aqueous solution and acetonitrile at a volume ratio of 8: 2 Flow rate: 1.0 ml / min Molecular weight standard sample: Polyethylene glycol detection Instrument: Differential refractometer

Mortar Test Using the obtained condensate, a mortar flow test according to JIS was carried out as follows. Ordinary Portland cement 480 parts, Kawasago (Shimane prefecture) 1,200 parts, and the obtained condensate 1.5 parts (solid content conversion) dissolved in 220 parts water were charged into a mortar mixer and kneaded for 3 minutes. Then, mortar was obtained.

The obtained mortar was packed in a flow cone on a flow table, pierced with a stick 15 times, the surface of the flow cone was made uniform with a cement knife, and the flow cone was gently removed vertically upward. A cone-shaped mortar was obtained. The obtained cone-shaped mortar was dropped on the flow table 15 times for 15 seconds, and the diameter of the expanded lowermost end surface in the maximum expansion direction and the diameter in the direction perpendicular to the diameter were measured using a flow measuring scale. The average value of these measured values was used as the flow value. The results are as shown in Table 7.

Examples 2-5. 4, used in Example 1
The substances shown in Table 1 were used instead of 4'-dihydroxydiphenylsulfone and 4-aminobenzenesulfonic acid, and 4,4'-dihydroxydiphenylsulfone, 4-aminobenzenesulfonic acid and water used in Example 1 were used. Except that the number of moles of sodium oxide was changed to the number of moles shown in Table 1 and the number of moles of formaldehyde used in the reactions of the first step and the second step was changed to the number of moles shown in Table 1, respectively. A condensate was prepared in exactly the same manner as in Example 1. The weight average molecular weight and negative charge of the obtained condensate are
The results of measurement and calculation performed in exactly the same manner as in Example 1 are shown in Table 2.
As shown in.

[0028]

[Table 1]

[0029]

[Table 2] Further, using the obtained condensate, the same mortar test as in Example 1 was performed. The results are as shown in Table 7.

Comparative Example 1. Into the same reaction vessel as used in Example 1, the following substances were charged. 4,4'-Dihydroxydiphenyl sulfone 0.5 mol [125.2 parts] 4-aminobenzenesulfonic acid 1.00 mol [173.2 parts] Sodium hydroxide 0.90 mol [36.0 parts] Water [745 0.0 parts] The obtained mixed liquid was heated to 100 ° C., 2.00 mol of formaldehyde (37% by weight aqueous solution: 162.2 parts) was added dropwise over 1 hour, and then the mixture was reacted at 100 ° C. for 18 hours to obtain a condensate. An aqueous solution of

The weight average molecular weight and the amount of negative charge of the obtained condensate were measured and calculated in exactly the same manner as in Example 1 and found to be 2.8 × 10 ⁴ and -1.9 × 10 ³ , respectively. It was The results are summarized in Table 6. A mortar test was conducted using the obtained condensate in exactly the same manner as in Example 1. The results are as shown in Table 7.

Comparative Examples 2-5. 4 used in Comparative Example 1
4,4′-dihydroxydiphenyl sulfone, 4-aminobenzenesulfonic acid and water used in Comparative Example 1 using the substances shown in Table 3 instead of 4′-dihydroxydiphenylsulfone and 4-aminobenzenesulfonic acid, respectively. A condensate was prepared in exactly the same manner as in Comparative Example 1 except that the number of moles of sodium oxide was changed to the number of moles shown in Table 3.

The weight average molecular weight and negative charge of the obtained condensate were measured and calculated in exactly the same manner as in Example 1.
The results are as shown in Table 6. A mortar test was conducted using the obtained condensate in exactly the same manner as in Example 1. The results are as shown in Table 7.

[0034]

[Table 3]

Comparative Examples 6 to 16. 4, used in Example 1
4,4′-dihydroxydiphenylsulfone and 4-aminobenzenesulfonic acid used in Example 1 were replaced with the substances shown in Tables 4 to 5 instead of 4′-dihydroxydiphenylsulfone and 4-aminobenzenesulfonic acid. And the number of moles of sodium hydroxide is changed to the number of moles shown in Table 3, or the number of moles of formaldehyde used in the reaction in the first step and the second step is changed to the number of moles shown in Tables 4 to 5, respectively. A condensate was prepared in exactly the same manner as in Example 1 except that the above conditions were changed. The weight average molecular weight and negative charge of the obtained condensate were measured and calculated in exactly the same manner as in Example 1. The results are as shown in Table 6.

[0036]

[Table 4]

[0037]

[Table 5] The results of a mortar test using the obtained condensate in exactly the same manner as in Example 1 are as shown in Table 7. The results in Table 7 demonstrate that the dispersibility is extremely good when the water-soluble bisphenol condensate of the present invention is used as a dispersant.

[0038]

[Table 6]

[0039]

[Table 7]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 11, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

However, the above cements, dyes, charcoal
In the industrial field of water-based slurry of fine powder, quality,
In order to improve productivity, transportability and workability,
To further reduce the concentration (increasing the concentration of dispersoids)
There is an increasing demand for conventional bispheno to meet this demand.
The polyol-based condensate had a drawback that its dispersion performance was insufficient .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, when a bisphenol-based condensate having a specific molecular weight and a negative charge was used, good results were obtained. The present inventors have reached the present invention by finding that the results can be obtained. Therefore, the object of the present invention is to
Has even better dispersion performance than bisphenol condensates
This enables higher concentration of dispersoids than ever before.
However, it is another object of the present invention to provide a bisphenol condensate capable of improving quality, productivity, transportability and workability.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

[0019]

As described in detail above, the water-soluble bisphenol condensate of the present invention is a condensate having extremely high dispersibility.
Ri, cement, inorganic substances such as gypsum and calcium carbonate,
Or, when used as a dispersant for organic substances such as coal, dyes and water-soluble paints , make the dispersoid more concentrated than before.
And improve quality, productivity, transportability, and workability.
You can

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taro Abe 2-8-1 Iida-cho, Iwakuni-shi, Yamaguchi Sanyo-Kokusaku Pulp Co., Ltd.

Claims (2)

[Claims] 1. A condensate obtained by reacting bisphenols, aminobenzenesulfonic acid and formaldehyde, having a weight average molecular weight of 1.0 × 10 ^{4 to} 2.0 ×.
With 10 a ^4, a water-soluble bisphenol condensate, wherein the negative charge amount per molecular weight 100 is -1.7 × 10 ³ meV or less. 2. The water-soluble bisphenol-based condensate according to claim 1, wherein the bisphenol is a bisphenol represented by the following chemical formula 1. Reduction in one formula, X is _{-SO 2 -, - CO -,} - S -, - O
_{-, - CH 2 -, -} C (CH 3) 2 - is or a covalent bond.