JPH041005B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to condensation products of substituted phenolsulfonic acids and formaldehyde. Condensation products of aromatic sulfonic acids and formaldehyde are widely used as dispersants in many applications such as cement, concrete, etc. US Pat. No. 2,141,569 (Tucker et al) describes the use of condensation products of certain aromatic sulfonic acids and formaldehyde as dispersants in cement and concrete. U.S. Pat. No. 2,905,565 (Dietz et al) describes naphtholsulfonic acids and their cresol-
The use of condensates with formaldehyde resins to reduce moisture in green mix slurries in the production of Portland cement by wet methods is described. US Pat. No. 3,277,162 (Johnson) describes the production of condensation products of naphthalene sulfonic acid and formaldehyde for use in oil well cements. US Pat. No. 3,333,983 describes the production of aralkyl phenols, such as styrenated phenols, by alkylating phenols with styrene. According to the invention, (a) a substituted phenolsulfonic acid having 1 to 8 sulfonic acid groups selected from the group consisting of arylphenolsulfonic acids and aralkylphenolsulfonic acids; a condensation product with 0.5 to about 4 moles of formaldehyde, and (b) a substituted phenolsulfonic acid having 1 to 8 sulfonic acid groups selected from the group consisting of (i) arylphenolsulfonic acids and aralkylphenolsulfonic acids; and (ii) a condensation product of an arylsulfonic acid with about 0.5 to about 4 moles of formaldehyde per mole of substituted phenolsulfonic acid and arylsulfonic acid, where the weight ratio of substituted phenolsulfonic acid to arylsulfonic acid is about A condensation product is provided that is from 0.95:0.05 to about 0.05:0.95. If desired, the condensation product can be used directly or reacted with a salt-forming cation to obtain a salt. The condensation products are useful in numerous applications such as hydraulic cement, concrete, etc. Useful condensation products include 1 mole of one or more aryl phenols or aralkyl phenols mixed with about 1.0 to about 8.0 moles of sulfuric acid to about 20 to about 1 mole of sulfuric acid.
sulfonation at 100°C to form a substituted phenolsulfonic acid, and then condensing 1 mole of the substituted phenolsulfonic acid with about 0.5 to about 4 moles of formaldehyde at about 60 to about 120°C to form the condensation product of the free acid. It can be manufactured by generating. Similarly, arylphenolsulfonic acids or aralkylphenolsulfonic acids and arylsulfonic acids can be condensed with about 0.5 to about 4 moles of formaldehyde per mole of arylphenolsulfonic acids, aralkylphenolsulfonic acids, and arylsulfonic acids; The weight ratio of arylphenolsulfonic acid and aralkylphenolsulfonic acid to arylsulfonic acid is from about 0.95:0.05 to about 0.05:0.95. formula where R is an aryl group, such as phenyl, diphenyl, naphthyl, hydroxymethylphenyl, etc., and R ₁ is hydrogen or an alkyl group having about 1 to about 5 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, etc., _R2 is hydrogen or an alkyl group having about 1 to about 5 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, etc., and n is 1 to 3; Substituted phenols are useful, including arylphenols and aralkylphenols, where b is 0-1. Examples of useful arylphenols include 4-phenylphenol, 2-phenylphenol, 2,4
-diphenylphenol, 2,6-diphenylphenol, 4-naphthylphenol, 2-naphthylphenol, 4-biphenylphenol, 2-
Biphenylphenol and the like. Useful aralkyl phenols include alpha methyl benzyl paraphenol and benzyl phenols prepared by alkylation of phenols with styrene. Dibenzylated phenols and tribenzylated phenols prepared by alkylating phenols with styrene can also be used. Aralkyl phenols such as isopropylidene diphenol can also be used. Sulfonation of arylphenols and aralkylphenols can also be carried out using other sulfonating agents such as sulfuric acid, sulfur trioxide, etc. to yield the desired substituted phenolsulfonic acids. Useful arylsulfonic acids include the following aryl hydrocarbon sulfonic acids: benzene, methylbenzene, propylbenzene, isopropylbenzene, butylbenzene, dimethylbenzene, diethylbenzene, diisopropylbenzene, dibutylbenzene, naphthalene, methylnaphthalene,
Ethylnaphthalene, propylnaphthalene, butylnaphthalene, dimethylnaphthalene, diethylnaphthalene, dibutylnaphthalene, biphenyl, methylbiphenyl, ethyldiphenyl, diisobutylbiphenyl, diphenylmethane, diphenylethane, diphenylpropane, diphenylbutane, etc. Formaldehyde used in the condensation of arylphenolsulfone, aralkylphenolsulfone and arylsulfone is used in the form of 10-40% aqueous solution, 30-55% alcohol, such as methanol, ethanol, i-propanol, n-butanol, etc. can. Compositions that liberate formaldehyde can be used, such as paraformaldehyde, trioxane, and the like. Compositions such as acetals that can generate formaldehyde can also be used. Salts of the condensation products can be prepared by neutralizing the condensation products of the free acids with salt-forming bases, such as alkali metal hydroxides, alkaline earth metal hydroxides, or organic amine bases. Useful bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, zinc hydroxide, aluminum hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, and the like. Useful organic bases are methylamine, diethylamine,
Includes triethanolamine, isopropanolamine, etc. The condensation product of arylphenolsulfonic acid or aralkylphenolsulfonic acid and formaldehyde is prepared by combining (a) 1 mole of a substituted phenol, e.g., arylphenol or aralkylphenol, with about 1 to about 8 moles of a sulfonating agent and about 20 to about 120 moles of a sulfonating agent; ℃
(b) condensing the substituted phenolsulfonic acid with about 0.5 to about 4 moles of formaldehyde at about 60 to about 120°C to produce a free acid condensation product; and then optionally (c) neutralizing the condensation product of the free acid with a base to form a salt of the condensation product. The condensation product of arylphenolsulfonic acid or aralkylphenolsulfonic acid with arylsulfonic acid and formaldehyde is prepared by: (a) sulfonating 1 mole of substituted phenol with about 1 to about 8 moles of sulfonating agent at about 20 to about 120°C; to produce a substituted phenolsulfonic acid,
and (b) adding the arylsulfonic acid to the substituted phenolsulfonic acid to form a mixture of substituted phenolsulfonic acids and arylsulfonic acids, wherein the weight ratio of substituted phenolsulfonic acids to arylsulfonic acids is from about 0.95:0.05 to about 0.05:0.95,
and (c) a mixture of a substituted phenolsulfonic acid and an arylsulfonic acid at a rate of about 0.5 per mole of the mixture.
~about 4 moles of formaldehyde and about 60 to about 120
C. to form a condensation product of the free acid, and then optionally (d) neutralizing the condensation product of the free acid with a base to form a salt of the condensation product. , can be manufactured. Condensation products and salts of substituted phenolsulfonic and arylsulfonic acids with formaldehyde from about 0.10 to about 10% based on the weight of the cement
It is useful as a dispersant in cement and concrete when used at concentrations of . They are particularly useful in reducing the viscosity of high brine cement slurries when used at concentrations of about 0.10% to about 10% based on the weight of the cement. These condensation products also act as wear reducers in cement slurries and as superplasticizers in concrete mixtures. They are particularly useful as viscosity reducers in cement slurries made in brine solutions. When these condensation products are added to concrete, they increase the compressive strength of the hardened concrete. Concrete is made by mixing cement, sand, gravel and water. It is a hard and strong building material. The water in the mixture hardens the cement, binding the entire mixture together into a hard mass. In concrete technology, it is well known that strength - compressive strength, usually measured by ASTM test C39-72, is a reliable standard of general quality. For this reason, all concrete technologies are developed around obtaining significant and practical strength while minimizing cost and maximizing convenience of use. Despite extensive research, most of the concrete currently in use is a simple mixture of sand and coarse stone containing a small proportion of Portland cement, and adding enough water to mold the mixture. be fluid enough to be placed inside. As is well known in the art, the less water used in concrete, the higher the strength. Considerable research has been devoted to finding mixtures of sand and stone of different particle sizes that form flowable concrete with minimal water content. Addition of these condensation products to concrete mixtures can reduce the moisture content. The following examples illustrate the nature and advantages of the invention. All amounts, proportions, and percentages are by weight and all temperatures are in degrees Celsius, unless otherwise specified. Example 1 This example describes the preparation of a condensation product of benzylphenolsulfonic acid and formaldehyde. Production of benzylphenolsulfonic acid

[Table] B Procedure Styrenated phenol was placed in a flask equipped with a stirrer, thermometer and ice bath. Then sulfuric acid (20%
SO ₃ ) was added dropwise. After adding all of the sulfuric acid,
The reaction mixture was stirred for an additional 2 hours at 25-35°C. At the end of 2 hours, the reaction mixture was
Heated to 80°C for about 1 hour. Then a total of 12.71g
of water was added to the reaction product at 75-85°C, while the temperature was controlled by external cooling. Condensation A of benzylphenolsulfonic acid with formaldehyde Composition of the condensation mixture Benzylphenolsulfonic acid from 36.47 g parts 6.20 g formaldehyde (37%) * (mol.
0.0765) 36.52g formaldehyde 20.81g ammonium hydroxide (28%
NH ₄ OH) 10000 g of condensation product mixture *Molecular weight of 37% CH ₂ O=81 The flask containing the benzylphenolsulfonic acid from part B was heated to reflux. Formaldehyde and water were then added and the condensation mixture was heated to 95±2° C. for 24 hours. At the end of this period, the condensation was stopped and the acid number of the free acid condensation product of benzylphenolsulfonic acid and formaldehyde was determined. Determine the condensation product using phenolphthalein as an indicator.
By titration with 0.5N sodium hydroxide, an acid value (AV) of 3.0 mgKOH/g was obtained.
The condensation product of the free acid was then neutralized with ammonium hydroxide until the pH of a 10% solution of the ammonium salt of the condensation product was 7.0±0.5. Examples 2-14 The procedure of Example 1 was repeated except that 1 mole of styrenated phenol was replaced with 3 moles of fuming sulfuric acid (20%
SO ₃ ) to produce benzylphenolsulfonic acid, the benzylphenolsulfonic acid is condensed with 0.6 to 2.0 moles of formaldehyde per mole of sulfonic acid, and the condensation product of the free acid is converted to ammonium hydroxide, hydroxide. Neutralization with sodium or potassium hydroxide produced the desired salt. In Examples 6, 9, 10 and 11, calcium hydroxide was used to precipitate unreacted sulfuric acid as calcium sulfate. The precipitation was carried out and the condensation products of the free acids in the liquid were neutralized with ammonium hydroxide, sodium hydroxide or potassium hydroxide. Additional data for Examples 1-14 is provided below.

[Table]
Examples 15-27 The procedure of Example 1 was repeated except that 1 mole of styrenated phenol was replaced with 2.5 moles of oleum (20
% _SO3 ) to produce benzylphenolsulfonic acid, the benzylphenolsulfonic acid is condensed with 0.6 to 2.0 moles of formaldehyde per mole of sulfonic acid, and the condensation product of the free acid is purified with sodium hydroxide, water. Neutralized with potassium oxide or zinc hydroxide. Additional data for Examples 15-27 are provided below.

Table Examples 28-36 The procedure of Example 1 was repeated except that 1 mole of styrenated phenol was mixed with 2.25 moles of fuming sulfuric acid (20
% _SO3 ) to produce benzylphenolsulfonic acid, the benzylphenolsulfonic acid is condensed with 0.6 to 2.0 moles of formaldehyde per mole of sulfonic acid, and the condensation product of the free acid is purified with sodium hydroxide, water. Neutralized with potassium oxide or zinc hydroxide. Additional data for Examples 28-36 are provided below.

Reference Example 1 This reference example illustrates the use of a condensation product of benzylphenolsulfonic acid and formaldehyde as a dispersant in high brine-cement content. The ammonium salts of the condensation products described in Examples 1-4 were used in an 18% brine-API class A cement slurry. Slurry of 18% by weight sodium chloride solution
Total weight using 327g and 860g cement
It was prepared by forming a slurry of 1187 g or a total volume of 600 ml. The slurry was prepared by pouring the brine solution plus dispersant into the metal container of a Waring blender. Cement was added over 15 seconds while mixing on low speed. The blender container was then capped and mixed at high speed. The slurry was then poured into a beaker and slurried for 20 minutes using a direct drive mixer. The slurry was then transferred into the sample viscosity cup of a Huang Viscometer Model No. 35. Using a viscometer rotating at 600 rpm, the sample cup was raised to the appropriate level and viscosity readings were taken after 60 seconds of continuous rotation. The table shows the condensation products, CH ₂ O/
Additional data on RSO ₃ H molar ratio and high brine-cement slurry viscosity is shown.

[Table] Reference Example 2 The procedure of Reference Example 1 was repeated, but using API Class H cement instead of API Class A cement, and the results shown in the table below were obtained.

【table】

[Table] Brine-cement slurry and
2% dispersant.
Reference Example 3 The procedure of Reference Example 1 was repeated, but with higher brine. Using a fresh water-APIH type cement slurry and 0.56% dispersant based on the weight of cement in place of the APIH type cement slurry, the results set forth in the table below were obtained.

[Table] Reference Example 4 This reference example reveals the effect of the condensation product of benzylphenolsulfonic acid and formaldehyde at various dispersant concentrations in the presence and absence of HEC (hydroxyethyl cellulose). . The table shows the results obtained using the condensation product of Example 8 in the presence and absence of HEC.

Table Reference Example 5 This reference example reveals the compressive strength of the 18% brine-APIH mold containing the condensation product of Example 8. Data on compressive strength is
It was taken on day 7 according to the procedure in ASTM standard C39-72. These results are shown in the table. Table 18% Brine-Cement Slurry Compressive Strength at 7th Day Example Compressive Strength at 7th Day (Average PSI) Blank 2417 3 2349 4 2531 Reference Example 6 This reference example is a concrete superplasticizer. The compressive strength of the condensation products of Examples 3 and 4 when used as Concrete samples were prepared according to the procedure of ASTM standard C192-76 and
And their compressive strength was measured according to the procedure of ASTM standard C39-72. The results of these tests are shown in the table.

Table Examples 37-40 The procedure of Example 1 is repeated, except that 1 mole of styrenated phenol is mixed with 3 moles of fuming sulfuric acid (20%
SO ₃ ) to form benzylphenolsulfonic acid, the benzylphenolsulfonic acid is condensed with 1.6 moles of formaldehyde per mole of sulfonic acid, and the condensation products of the free acids are converted to magnesium hydroxide, calcium hydroxide, The results of these tests neutralized with monoethanolamine and ammonium acetate tetrahydrate are shown in the table.

Table Example 41 Condensation of Monobenzylated Phenolsulfonic Acid with Formaldehyde and Neutralization with Potassium Hydroxide Procedure A Sulfonation In a 1 volume reaction flask equipped with a stirrer, a thermometer and an ice bath, 100 g of monobenzylic acid are added. phenol (monostyrenated phenol with a molecular weight of 198) was added, followed by 166 g of H ₂ SO ₄ [20% SO ₃ , 3.33 moles, assigned molecular weight of H ₂ SO ₄ (20% SO ₃ ) = 100].
was slowly added over 2 hours at 30-40°C. After all the acid was added, the reaction mixture was stirred for an additional 2 hours. It was then heated at 75-80°C for 1 hour. Then 144.0 g of water was added at 70-80°C. B Polymerization and Neutralization In a reactor similar to that described in Part A, 200 g
(0.244 mol) of sulfonated product, 37% of 31.6 g
of formaldehyde (0.390 mol) and 200 g of water were added. The reaction mixture was then heated to 95°C for 24 hours. At the end of this period, the product was cooled to room temperature and an acid number of 179 was determined using phenolphthalein as indicator. Based on this acid value, 200g of free acid is converted into 80g of free acid at 30-40℃.
Neutralized with 45% KOH. The resulting polymer has a pH of 7.5
(10% solution) was 31% potassium salt. Example 42 Condensation of dibenzylated phenolsulfonic acid with formaldehyde and neutralization with potassium hydroxide A Sulfonation In a reactor as described in Example 41, 100 g
(0.342 mol) of dibenzylated phenol (distyrenated phenol) was charged. _{114.0g H2SO4}
(20% _SO3 , 3.33 mol) was added over 2 hours at 50-60<0>C. The reaction mixture was added for an additional 2 hours at 50-60°C. Then set it to 75-80
Heated at ℃ for 2 hours. After this, add 116.0g of water to 70g.
Added at ~80°C. B Polymerization and Neutralization To the same reactor as in Example 41 was added 200 g (0.207 mol) of the sulfonated product, 27.0 g of 37% formaldehyde (0.332 mol) and 2.00 g of water. The reaction mixture was then heated at 95°C for 24 hours. At the end of this period, it was cooled to room temperature and an acid number of 140 was measured using phenolphthalein as indicator. Based on this acid number, 200g of free polymer is mixed with 62g of 45% KOH at 30%
Neutralized at -40°C. The neutralized product has a pH of
7.5 (10% solution) of 31% potassium salt. Example 43 Condensation of tribenzylated phenols (64%) and dibenzylated phenols (34%) with sulfonic acid and formaldehyde and neutralization with potassium hydroxide A Sulfonation In a reactor as described in Example 41, 50 g
(0.124 mol: molecular weight 403 based on hydroxylation of the blend) of tri- and dibenzylated phenols (prepared by alkylating the phenols with styrene to the indicated degree of substitution). 74.4 g of H ₂ SO ₄ (20% SO ₃ , 0.744 mol) at 25
Added over 2 hours at ~45°C. The reaction mixture was added for an additional 2 hours at 45°C. Then it was heated at 75-85°C for 45 minutes. Then 67.0g of water was added at 70-80°C. B Polymerization and Neutralization In a reactor as described in Example 41, 177 g
(0.115 mol) of sulfonated product, 37% of 18.6 g
Formaldehyde (0.230 moles) and 177.0 g of water were added. The reaction mixture was then heated at 95°C for 24 hours. It was then cooled to room temperature and an acid number of 173.6 was measured as an indicator. Based on this acid number, 300 g of free acid was neutralized with 116 g of 45% KOH. The finished product has a pH of 7.0 (10% solution)
It was a 31% potassium salt. Reference Example 7 The procedure of Reference Example 1 was repeated, except that API Class H cement was used instead of API Class A cement. The results of this test are shown in the table.

Reference Example 8 The procedure of Reference Example 1 was repeated, except that API Class H cement was used in place of API Class A cement in the freshwater cement slurry. The results for the tested polymers are listed in the table.

[Table] Luamine
Blank No dispersant
141
Example 44 Condensation of 4',4-isopropylidenediphenolsulfonic acid with formaldehyde and neutralization with potassium hydroxide A Sulfonation In a reactor as described in Example 41, 73.0 g of
Charged with H ₂ SO ₄ (20% SO ₃ , 0.730 mol). Then, 50 g of 4',4-isopropylidene diphenol (0.219 mol) was added slowly at room temperature.
The exothermic reaction caused the temperature to rise to 70-80°C, at which time all of the 4',4-isopropylidene diphenol was added. The reaction mixture was then heated to 110°C for 3.0 hours. Then 123.0 g of water was added under reflux,
The sulfonated product was cooled to room temperature. B Polymerization and Neutralization In a reactor as described in Example 47, 100 g
(0.089 mol) of sulfonated product (A), 7.2 g of 37
% formaldehyde (0.089 mol) and 63.0 g
water was supplied. The reaction mixture was then heated to 95 °C for 24
heated for an hour. It was then cooled to room temperature and an acid number of 140 was measured using phenolphthalein as indicator. Based on this acid number, 150 g of acid was neutralized with 50 g of KOH (45%). The resulting product was a 30% potassium salt with a pH of 7.6 (10% solution). Reference Example 9 The procedure of Reference Example 1 was repeated except that API Class H cement was used in place of API Class A cement in the freshwater cement slurry. The results for the tested products are listed in the table.

Reference Example 10 The procedure of Reference Example 1 was repeated except that 0.86 g (0.1% hydroxyethyl cellulose, HEC) based on the weight of cement was added to the 18% brine/cement slurry. The results of the tested products are
Shown in Table XI.

Table Example 45 Condensation of p-phenylphenolsulfonic acid with formaldehyde and neutralization with potassium hydroxide A Sulfonation In a reactor as described in Example 41, 97.9 g of p-phenylphenol (0.294 mol) was added slowly at room temperature. Due to the exothermic reaction, the temperature is
Raised to 70-80 °C and now all the phenylphenol was added. The reaction mixture was then incubated at 110 °C for 3.5
heated for an hour. Then 145.0 g of water was added under reflux and the product was cooled to room temperature. B Polymerization and Neutralization In a reactor as described in Example 41, 100 g
(0.100 mol) of sulfonated product, 8.9 g (0.100
mol) of 37% formaldehyde and 51.0 g of water were added. The reaction mixture was then heated at 95°C for 24 hours. It was then cooled to room temperature and an acid number of 190.4 was measured using phenolphthalein as an indicator. Based on this acid value, 140g of acid is 58
Neutralized with 45% KOH. Final product is PH8.0
(10% solution) was 31% potassium salt. Example 46 Condensation of p-phenylphenolsulfonic acid and naphthalenesulfonic acid with formaldehyde and neutralization with potassium hydroxide Polymerization and neutralization In a reactor as described in Example 41, 50 g of the sulfonation of Example 45 are added. reaction product (0.0645 mol),
30.7 g naphthalene sulfonic acid (0.1290 mol) and 18.8 g 37% formaldehyde (0.232 mol)
and 11.0 g of water at 60°C. The reaction mixture was then heated under reflux (103°C) for 24 hours. It was then cooled to room temperature and the acid number of 151.2 was measured using phenolphthalein as indicator.
Based on this acid value, 189g of this acid can be converted into 64g of 45
Neutralized with %KOH. The final product was 33% potassium salt with a pH of 8.0 (10% solution). Example 47 Condensation of Styrenated Phenolsulfonic Acid and Naphthalenesulfonic Acid with Formaldehyde and Neutralization Polymerization and Neutralization with Potassium Hydroxide Into the same reactor as Example 41, 330 g of the sulfonated product of the example (0.0355 mol ) and 8.45g
of naphthalenesulfonic acid (0.0355 mol), 6.9 g
37% formaldehyde and 38.0 g of water were added at 60°C. The sulfonated product was the styrenated phenolsulfonic acid of the example containing 80% monostyrenated phenol and 20% distyrenated phenol. The reaction mixture was then heated to reflux (105°C) for 24 hours. It was then cooled to room temperature and an acid number of 168 was measured using phenolphthalein as an indicator. Based on this acid value,
81 g of acid was neutralized with 29 g of 45% KOH. The resulting polymer was 33% potassium salt with a pH of 8.5 (10% solution). Example 48 Condensation of p-phenylphenolsulfonic acid and xylene sulfonic acid with formaldehyde and neutralization with potassium hydroxide A Sulfonation and polymerization of xylene sulfonic acid In a similar reactor as described in Example 41, 106 g of xylene are added. (1.0 mol) was supplied. While stirring rapidly, add 150g of salted H ₂ SO ₄ (20% SO ₃ ) to 20-40%
The mixture was added over 2 hours at ℃. The reaction mixture was then heated to 90-95°C for 2.25 hours. It was then cooled to room temperature and 138.0 g of water was added at 30-40°C. 200 g of the sulfonated product (0.508 mol) was then added to 20.5 g of 37% formaldehyde (0.254 mol) and heated under reflux for 8 hours. At the end of this period, all formaldehyde had reacted as determined by standard Na ₂ SO ₄ titration procedure. B Condensation of xylene sulfonic acid and p-phenylphenolsulfonic acid with formaldehyde and neutralization with potassium hydroxide In a reactor as described in Example 41, 50 g
(0.645 mol) of the sulfonation product of Example 45(A),
56 g (0.0645 moles) of the sulfonated product of Example 48(A), 12.5 g (0.155 moles) of 37% formaldehyde and 76 g of water were added. The reaction mixture was then heated to reflux (103° C.) for 24 hours. It was then cooled to room temperature and an acid number of 196 was measured using phenolphthalein as an indicator. Based on this value, 83.8g of acid in 192.5g of this copolymer
Neutralized with 45% potassium hydroxide. The final product is
It was a 33% potassium salt with a pH of 8.5 (10% solution). Example 49 Condensation of xylene sulfonic acid and distyrenated phenolsulfonic acid with formaldehyde and neutralization with potassium hydroxide A Sulfonation of distyrenated phenols In a reactor as described in Example 41, 100 g
(0.325 g) of distyrenated phenol (molecular weight
308, based on OH number). While stirring,
146 g (1.461 mol) of fuming H ₂ SO ₄ (20% SO ₃ )
The addition was carried out over a period of 2 hours at 50-60°C. 60 reactions
Continued for an additional 2 hours at °C and 1 hour at 95 °C.
Then 132.6g of water was added at 80-90°C and the reaction mixture was cooled to room temperature. B. Polymerization and Neutralization In a reactor as described in Example 41, 7.5 g of the sulfonated product of Example 49(A) (0.0644 mol) and 55.90 g of the sulfonated product of Example 48(A) are added. (0.0644 mol), 12.5 g of 37% formaldehyde (0.1547 mol) and 100 g of water were added. The reaction components were then heated to reflux for 2.4 hours. It was then cooled to room temperature and an acid number of 180 was measured using phenolphthalein as an indicator. Based on this acid number, 192.5g of free acid polymer can be mixed with 76.95g of polymer.
Neutralized with 45% KOH. The resulting polymer has a pH of 8.0
(10% solution) was 34% potassium salt. Reference Example 11 The procedure of Reference Example 1 was repeated, but using API Class H cement in an 18% brine/cement slurry. Results for all products tested
Listed in Table XII.

[Table] Reference Example 12 The viscosity of cement slurry to which a condensation product according to the present invention and a comparative condensation product were added was measured. Condensation product dispersant used: Condensation product (potassium salt) obtained in Example 42 of the present invention Dispersant B: Condensation product disclosed in Example 1 of JP-A-56-34719 Measurement of viscosity 327 g and 860 g of 18% by weight sodium chloride solution
A slurry of 1187 g and 600 ml was obtained by mixing the cement. This slurry was prepared by adding 1% by weight of dispersant A or B, based on the weight of the brine and cement slurry, into the metal container of a Waring blender.
This was obtained by feeding for several seconds while mixing at low speed, then capping the container and mixing at high speed for 35 seconds. Each slurry was then placed in a metal beaker and mixed for 20 minutes using a direct drive mixer. Then fann the slurry
The mixture was transferred to a viscosity measurement cup of a viscometer (model No. 35). While operating the viscometer at 600 revolutions per minute,
Raised the cup to a suitable level. After continuous rotation for 60 seconds, the viscosity scale was read at 25°C. A slurry to which no dispersant was added was also measured in the same manner. Huang viscometer results of these condensation products in 18% brine-cement slurry are shown in the table. Table: Viscosity of sample slurry No dispersant Too high to measure A 144 B 223 Furthermore, the condensation product of the present invention and/or its salt was added to the cement slurry as a dispersant, a viscosity reducer,
The manner in which it is used as a wear reducing agent will be summarized. 1 (a) cement and water, (b) cement and brine, (c)
A slurry selected from the group consisting of cement, gravel, sand and water; and (d) cement, gravel, sand and brine is mixed with an effective amount of a condensation product of the invention and/or a salt thereof to achieve a viscosity. forming a slurry with reduced
Slurry manufacturing method. 2. The method according to item 1 above, wherein the slurry is a slurry of cement and brine. 3. The method according to item 1, wherein the slurry is a slurry of cement, gravel, sand, and brine. 4. A slurry produced by the method described in item 1 above. 5. A slurry produced by the method described in item 2 above. 6. A slurry produced by the method described in item 3 above.

Claims (1)

[Scope of Claims] 1 (a) A substituted phenolsulfonic acid having 1 to 8 sulfonic acid groups selected from the group consisting of arylphenolsulfonic acid and aralkylphenolsulfonic acid, per mole of substituted phenolsulfonic acid. Substituted phenols condensed with 0.5 to 4 moles of formaldehyde at 60 to 120°C, or (b) having 1 to 8 sulfonic acid groups selected from the group consisting of (i) arylphenolsulfonic acids and aralkylphenolsulfonic acids; condensing the sulfonic acid and (ii) the arylsulfonic acid with 0.5 to 4 moles of formaldehyde per mole of substituted phenolsulfonic acid and arylsulfonic acid at 60 to 120°C;
A method for producing a condensation product and a salt thereof, wherein the weight ratio of substituted phenolsulfonic acid to arylsulfonic acid is 0.95:0.05 to 0.05:0.95. 2 formulas where R is an aryl group, _R1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, _R2 is hydrogen or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3, and b is 0 to 1. The method according to claim 1, wherein the substituted phenol is 3. The salt-forming cation is selected from the group consisting of sodium, potassium, lithium, ammonium, zinc, calcium, barium, magnesium, aluminum, methylamine, monoethanolamine, diethanolamine, triethanolamine and isopropanolamine. The manufacturing method according to item 1. 4. The process according to claim 1, wherein 1 mole of aralkylphenol is sulfonated with 3 moles of a sulfonating agent to produce aralkylphenolsulfonic acid, and then 1 mole of aralkylphenolsulfonic acid is condensed with 1.8 moles of formaldehyde. Method for producing potassium salt. 5. The process according to claim 1, wherein 1 mole of aralkylphenol is sulfonated with 3 moles of a sulfonating agent to produce aralkylphenolsulfonic acid, and then 1 mole of aralkylphenolsulfonic acid is condensed with 1.4 moles of formaldehyde. Method for producing sodium salt. 6. The process according to claim 1, wherein 1 mole of aralkylphenol is sulfonated with 3 moles of a sulfonating agent to produce aralkylphenolsulfonic acid, and then 1 mole of aralkylphenolsulfonic acid is condensed with 1.2 moles of formaldehyde. Method for producing ammonium salts. 7. The production method according to claim 1, wherein the aralkylphenolsulfonic acid is monobenzylphenolsulfonic acid. 8. The production method according to claim 1, wherein the aralkylphenolsulfonic acid is dibenzylphenolsulfonic acid. 9. The production method according to claim 1, wherein the aralkylphenolsulfonic acid is tribenzylphenolsulfonic acid. 10. The production method according to claim 1, wherein the aralkylphenolsulfonic acid is isopropylidene diphenolsulfonic acid. 11 Claim 1 in which the arylphenolsulfonic acid is phenylphenolsulfonic acid
Manufacturing method described in section. 12. The manufacturing method according to claim 1, wherein the arylsulfonic acid is naphthalenesulfonic acid. 13. The manufacturing method according to claim 1, wherein the arylsulfonic acid is xylene sulfonic acid. 14 (a) sulfonation of 1 mole of substituted phenols with 1 to 8 moles of sulfonating agent at 20 to 120°C to form substituted phenolsulfonic acids, and then (b) sulfonation of substituted phenolsulfonic acids with 0.5 to 4 moles of formaldehyde. at 60-120°C to form a condensation product of the free acid, and then optionally (c) neutralizing the condensation product of the free acid with a base to form a salt of the condensation product. A manufacturing method according to claim 1. 15 (a) sulfonation of 1 mole of substituted phenol with 1 to 8 moles of sulfonating agent at 20 to 120°C to form a substituted phenolsulfonic acid, and then (b) addition of an arylsulfonic acid to the substituted phenolsulfonic acid. forming a mixture of substituted phenolsulfonic acid and arylsulfonic acid, where the weight ratio of substituted phenolsulfonic acid to arylsulfonic acid is from 0.95:0.05 to 0.05:0.95, and then (c) substituted phenolsulfonic acid and arylsulfonic acid; 0.5 to 1 mole of mixture with acid
condensation with 4 moles of formaldehyde at 60-120°C to form a condensation product of the free acid, and then optionally (d) neutralizing the condensation product of the free acid with a base to form a salt of the condensation product. The manufacturing method according to claim 1, which comprises: producing. 16. The production method according to claim 14, wherein the aralkyl phenol is monobenzyl phenol. 17. The production method according to claim 14, wherein the aralkyl phenol is dibenzylphenol. 18. The production method according to claim 14, wherein the aralkyl phenol is tribenzylphenol. 19. The production method according to claim 14, wherein the aralkyl phenol is isopropylidene diphenol. 20 Claim 1 in which the arylphenolsulfonic acid is phenylphenolsulfonic acid
The manufacturing method described in Section 4. 21. The manufacturing method according to claim 15, wherein the arylsulfonic acid is naphthalenesulfonic acid. 22. The manufacturing method according to claim 15, wherein the arylsulfonic acid is xylene sulfonic acid.