JP3107316B2 - Novel bisphenol-based condensate and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a concrete water reducing agent,
The present invention relates to industrial dispersants such as dispersants for disperse dyes, carbon fine powder slurry dispersants, and dispersants for water-soluble paints, condensates useful as ion exchange resins, and methods for producing the same.

[0002]

2. Description of the Related Art As shown in the reaction formulas (II) and (III), a method for producing a condensate from a phenol, an aldehyde and a sulfite, and a method for producing a condensate from a phenol and an aldehyde A method for producing a condensate from amides and amino acids is known and used as a dispersant such as a dye dispersant (Japanese Patent Application No. 60-141767). However, the condensate obtained by this production method has a problem that a low-molecular portion having poor dispersibility tends to remain. Therefore, in these fields, there has been a demand for a condensate having a low molecular weight portion and a higher performance.

[0003]

[0004]

[0005]

As a result of various studies, the present inventors have found that bisphenols, which are solid and hardly soluble in water, retain high reactivity even in a solid-liquid reaction under aqueous conditions. . And a novel condensate obtained by reacting bisphenols, aldehydes, and sulfites, or sulfonates of amino acids or melamines under solid-liquid conditions,
And a method for producing the same.

That is, under aqueous conditions, (A) a compound of the formula (I) or a salt thereof, (B) an aldehyde, (C) a sulfite, an amino acid, or a sulfonated product of a melamine are reacted. It is intended to provide a condensate obtained by the reaction and a method for producing the condensate. [Where X is Wherein n is an integer of 1 to 5, R ₁ ,
R ₃ each independently represent hydrogen or an alkyl group, R ₂ represents an alkyl group, and R ₄ represents an alkylene group)]

The compound represented by the general formula (I) used in the present invention is 2,2-bis (4-hydroxyphenyl)
Propane, 4,4'-dihydroxydiphenylmethane,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-ethylidene-bisphenol, 4,4-bis (4-hydroxyphenyl) valeric acid, 4,4-bis (4-hydroxyphenyl) butyric acid, and the like Isomers are preferably used, and these can be used in combination.

[0008] As the sulfite, sodium sulfite, ammonium sulfite, sodium hydrogen sulfite, sodium pyrosulfite, potassium bisulfite, ammonium bisulfite and the like can be used.

The amino acids include glutamic acid, glycine, iminodiacetic acid, alanine, aspartic acid, serine, aminobutyric acid, glutathione, aminocaproic acid,
Valine, phenylalanine, methionine, leucine and the like can be used.

As sulphonated melamines, sulphonated melamine, acetoguanamine and benzoguanamine can be used. In addition, the condensate of the present invention can be produced following the sulfonation of melamine, acetoguanamine and benzoguanamine.

As aldehydes, formaldehyde polymerization and condensation products such as formaldehyde, paraformaldehyde and hexamethylenetetramine, acetaldehyde and the like are useful, and particularly preferred are formaldehyde and its derivatives.

The proportion of the compound represented by the general formula (I) is the same as that of the compound represented by the general formula (I) and sulfite or sodium glutamate.
Um or molar ratio of the sulfone product of melamines, 1: is preferably 0.2 to 3.0. If the molar ratio is out of this range, the polymer is excessively polymerized or, conversely, does not polymerize. A particularly preferred reaction molar ratio is 1: 0.5 to 2.5.
The aldehyde is preferably used in an amount of 1.2 to 6.0 mol per 1 mol of the compound represented by the formula (I). In the production method of the present invention, the pH of the aqueous solution of the condensate is 6
It is preferably from 14 to 14, and an alkali is added and reacted as needed. In this case, as the alkali, sodium hydroxide, ammonia and hydroxide of an ammonium group can be used. At these use rates, under aqueous conditions, at normal pressure or under pressure, at a temperature of 30 to 140 ° C., usually for 2 to 50 hours,
By reacting, a condensate can be obtained. Note that, as the tendency, in the general formula (I), the stronger the electron-withdrawing property of X,
It is preferable to increase the reaction temperature and lengthen the condensation time.

It is preferable that the aldehyde is added dropwise within 1 to 2 hours after the start of the reaction, and the reaction concentration is usually 20 to 60% by weight.
Do with.

[0014]

The condensate of the present invention has the following characteristics as compared with the condensate composed of phenols, aldehydes and sulfites or amino acids.・ It is easy to control the molecular weight distribution of the condensate and there are few low molecular parts. -Good reactivity with sulfites or amino acids. This is thought to be due to the difference in steric hindrance between bisphenols and phenols.

This will be described in more detail. How to control the molecular weight distribution of the condensate is a very important issue, and the properties of the condensate are greatly influenced by the molecular weight distribution. In the case of a condensate composed of phenols and aldehydes and sulfites or amino acids, the phenols have high reactivity and the condensation of phenols with sulfites or amino acids progresses and the condensation of phenols simultaneously. It is easy to proceed and a random reaction occurs, and it is difficult to polymerize. Therefore, a low molecular weight portion tends to remain and the molecular weight distribution tends to be widened. On the other hand, bisphenols in the production method of the present invention have much greater steric hindrance during condensation than phenols, and the formation of bisphenol homopolymer is suppressed. For this reason, the condensation of the sulfonate of bisphenols and sulfites or amino acids or melamines first proceeds reliably and becomes water-soluble. And it gradually polymerizes. For this reason, compared with the condensate consisting of phenols, aldehydes and sulfites, or amino acids, the reaction proceeds more rapidly because it is polymerized more uniformly, and the molecular weight distribution becomes narrower because the number of low molecular parts is reduced.

Therefore, the condensate of the present invention is a good water reducing agent which is excellent in water reduction, for example, when used as a concrete water reducing agent, as compared with a condensate comprising phenols, aldehydes and sulfites or amino acids. be able to.

Further, in the production method of the present invention, bisphenols having various structures can be introduced, whereby the balance between the hydrophilicity and the hydrophobicity of the condensate and the polarity can be increased and decreased. Can be.

[0018]

The following examples illustrate the bispheno of the present invention .
The details of the polyester-based condensate and the method for producing the same will be described, but the parts in the examples are parts by weight. Example 4
Is an example of a method for producing a condensate.

Example (1) 228.3 parts (1 mol) of 2,2-bis (4-hydroxyphenyl) propane and 126.3 parts of sodium sulfite were placed in a reactor equipped with a stirrer, a reflux unit, a thermometer and a formaldehyde aqueous solution dropping unit. (1 mol) and 826 parts of water. This solid-liquid was added to a 37% formaldehyde aqueous solution at a temperature of 100 ° C.
(3 moles of formaldehyde) was added dropwise over 1 hour, and the mixture was further reacted at that temperature for 14 hours to obtain an aqueous solution of the condensate of the present invention. FIG. 1 shows the infrared absorption spectrum of the obtained condensate.
And the number average molecular weight is shown in Table 1. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Example (2) 250.3 parts (1 mol) of 4,4'-dihydroxydiphenyl sulfone and sodium sulfite were placed in a reactor equipped with a stirrer, a reflux unit, a thermometer, and a formaldehyde aqueous solution dropping unit.
Charge 126.3 parts (1 mol), 34 parts of 47% sodium hydroxide (0.4 mol of sodium hydroxide) and 860 parts of water. 243.3 parts of a 37% formaldehyde aqueous solution (formaldehyde 3 mol) was added dropwise to the solid-liquid at a temperature of 100 ° C. over 1 hour, and further reacted at the temperature for 20 hours to obtain an aqueous solution of the condensate of the present invention. Table 1 shows the number average molecular weight of the obtained condensate.
The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Example (3) 228.3 parts (1 mol) of 2,2-bis (4-hydroxyphenyl) propane and 187.2 parts of sodium glutamate were placed in a reactor equipped with a stirring device, a reflux device, a thermometer, and a dropping device for formaldehyde aqueous solution. (1 mol), sodium hydroxide 40
Parts (1 mole) and 845 parts of water. The solid-liquid temperature is 100
At 27 ° C., 202.7 parts of a 37% aqueous formaldehyde solution (2.5 mol of formaldehyde) were added dropwise over 1 hour, and the mixture was further reacted at that temperature for 3 hours to obtain an aqueous solution of the condensate of the present invention. FIG. 2 shows the infrared absorption spectrum of the obtained condensate, and Table 1 shows the number average molecular weight. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Example (4) 200.0 parts (1 mol) of 4,4'-dihydroxydiphenylmethane and 133.1 of iminodiacetic acid were placed in a reactor equipped with a stirrer, a refluxing device, a thermometer, and a dropping device for formaldehyde aqueous solution.
Parts (1 mol), sodium hydroxide 80 parts (2 mol), water 8
Prepare 54 parts. 202.7 parts of a 37% formaldehyde aqueous solution at a temperature of 100 ° C (formaldehyde 2.5 mol)
Was added dropwise over 1 hour and further reacted at that temperature for 2 hours to obtain an aqueous solution of the condensate of the present invention. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Example (5) 250.3 parts (1 mol) of 4,4'-dihydroxydiphenylsulfone and 187.2 parts (1 mol) of sodium glutamate were placed in a reactor equipped with a stirrer, a reflux unit, a thermometer, and a dropping device for formaldehyde aqueous solution. , 40 parts of sodium hydroxide (1
Mol) and 870 parts of water. At a temperature of 100 ° C
202.7 parts of a 37% aqueous formaldehyde solution (2.5 mol of formaldehyde) were added dropwise over 1 hour, and the mixture was further reacted at that temperature for 2 hours to obtain an aqueous solution of the condensate of the present invention. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Example (6) 126.1 parts (1 mol) of melamine and 243.3 parts (3 mol of formaldehyde) of a melamine aqueous solution were charged into a reactor equipped with a stirrer, a reflux device, a thermometer, and a dropping device for formaldehyde aqueous solution. Incubate at 70 ° C for 1 hour. Thereafter, 208 parts (2 mol) of sodium hydrogen sulfite and 400 parts of water were added to the reaction solution, the pH was adjusted to 11 with an aqueous sodium hydroxide solution, and the mixture was reacted at a temperature of 60 ° C. for 2 hours to obtain an aqueous solution of sulfonated melamine. To this aqueous solution, 114.2 parts of 2,2-bis (4-hydroxyphenyl) propane (0.5
), And 162.2 parts of a 37% aqueous formaldehyde solution (2 mol of formaldehyde) were added dropwise over 1 hour at a temperature of 100 ° C, and further reacted at that temperature for 10 hours to obtain an aqueous solution of the condensate of the present invention. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Comparative Example (1) 2,2-bis (4-hydroxyphenyl) of Example (1)
The reaction was carried out under the same conditions as in Example (1) except that 228.3 parts (1 mol, 2 mol as phenol nucleus) of propane were changed to 188.0 parts (2 mol) of phenol to obtain an aqueous solution of a condensate. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Comparative Example (2) 243.3 parts (37 mol of formaldehyde) of 37% aqueous formaldehyde solution of Comparative Example (1) were changed to 364.9 parts (4.5 mol of formaldehyde) of 37% aqueous formaldehyde solution.
The reaction was carried out under the same conditions as in Comparative Example (1) except that the reaction time of 14 hours was changed to 20 hours, to obtain an aqueous solution of a condensate. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight is
The condensate was measured by gel permeation chromatography and converted to polyethylene glycol standard.

Comparative Example (3) 2,2-bis (4-hydroxyphenyl) of Example (3)
The reaction was carried out under the same conditions as in Example (1) except that 228.3 parts (1 mol, 2 mol as phenol nucleus) of propane were changed to 188.0 parts (2 mol) of phenol to obtain an aqueous solution of a condensate. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight was obtained by measuring the condensate by gel permeation chromatography and converting the condensate using polyethylene glycol standards.

Comparative Example (4) 202.7 parts (2.5 mol of formaldehyde) of 37% aqueous formaldehyde solution of Comparative Example (3) were changed to 364.9 parts (4.5 mol of formaldehyde) of 37% aqueous solution, and the reaction time of 3 hours was reduced to 10 hours. Except for the change, the reaction was carried out under the same conditions as in Comparative Example (3) to obtain an aqueous solution of a condensate. Table 1 shows the number average molecular weight of the obtained condensate. The number average molecular weight is
The condensate was measured by gel permeation chromatography and converted to polyethylene glycol standard.

[0029]

[Table 1]

Table 1 shows that the number average molecular weight of the example is higher than that of the comparative example. Further, in the comparative example, it can be seen that even if the amount of formaldehyde is increased and the reaction time is lengthened, it is difficult to polymerize.

Use Example The consistency of the concrete to which the condensate of the present invention was added was compared with the consistency of the concrete to which the condensate of the comparative example was added. The composition is shown in Table 2.

[0032]

[Table 2] 1) C cement: ordinary Portland cement W water: tap water S fine aggregate: Shimane river sand Specific gravity 2.59 M.
2.60 G Coarse aggregate: crushed stone from Yamaguchi Specific gravity 2.71 F. M.
6.86

The concrete is mixed with water containing cement, aggregate, and condensate by a 90-liter portable tilting mixer.
After kneading for 2 seconds, the slump and the amount of air were measured. The slump and the amount of air were performed according to JIS. Table 3 shows the measurement results.

[0034]

[Table 3]

Table 3 shows that the condensate of the present invention is more excellent in water reduction than the condensate of the comparative example. From these results, it is clear that the condensate of the present invention has an excellent effect.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a condensate obtained in Example (1) of the present invention.

FIG. 2 is a diagram showing an infrared absorption spectrum of a condensate obtained in Example (3) of the present invention.

Continued on the front page (72) Inventor Takatoshi Morimoto 2-1-1, Iida-cho, Iwakuni-shi, Yamaguchi Pref. Sanyo Kokusaku Pulp Co., Ltd. Production Engineering Laboratory (72) Inventor Susumu Mihara 2--8, Iida-cho, Iwakuni-shi, Yamaguchi No. 1 Sanyo Kokusaku Pulp Co., Ltd. Production Technology Laboratory (56) References JP-A-59-157062 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 8/28 C08G 14/06

Claims (4)

(57) [Claims] 1. A method according to claim 1, wherein (A) a compound represented by the general formula (I) or a salt thereof, (B) an aldehyde, (C) a sulfite, an amino acid, or a melamine sulfonate, at pH 6 to 14 under aqueous conditions. At 30 ° C
(A) :( B) :( C) = 1: 1.2-6.0:
A method for producing a condensate having a number average molecular weight of 1 × 10 ³ to 10 × 10 ³ , wherein the reaction is carried out at a molar ratio of 0.2 to 3.0. [Where X is (Where n is an integer of 1 to 5, R ₁ ,
R ₃ each independently represent hydrogen or an alkyl group, R ₂ represents an alkyl group, and R ₄ represents an alkylene group)] 2. The process according to claim 1, wherein the component (A) is 2,2-bis (4-hydroxyphenyl) propane, the component (B) is formaldehyde, and the component (C) is sodium sulfite. 3. The method according to claim 1, wherein the component (A) is 2,2-bis (4-hydroxyphenyl) propane, the component (B) is formaldehyde, and the component (C) is sodium glutamate. 4. The process according to claim 1, wherein component (A) is 2-bis (4-hydroxyphenyl) propane, component (B) is formaldehyde, and component (C) is sulphonated melamine.