JPS60106523A - Dispersant composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to amorphous aqueous solutions of alkali/alkaline earth metal salts of naphthalene sulfonic acid/formaldehyde condensation products. Mixed alkali metal salts of naphthalene sulfonic acid formaldehyde high molecular weight condensation products containing about 40-60% water by weight are substantially stable against the formation of crystalline precipitates at low temperatures of about θ to 5°C. . These mixed salt baths are particularly useful as dispersants when mixed with typical cement formulations to make cement pastes, mortars, concrete, etc.

Salts of naphthalene sulfonic acid-formaldehyde condensates (hereinafter sometimes simply abbreviated as NSF) are well known and are disclosed in US Pat. No. 3,686,133 and US Pat.
No. 194,919 describes it in detail as a dispersant for cement. Individual salts such as sodium or potassium have been used commercially as superplasticizers for concrete products.

They exhibit water usage reductions of 15-25% depending on usage, cement content and other factors. This means that earlier hardening, lower cement content, and shorter heat setting times are possible for producing high-strength concrete. In particular, energy cost savings for heat curing of concrete at low temperatures are realized when NSF surfactants (dispersants) are used due to their short curing times and low moisture content. During storage of NSF, a crystalline precipitate of hydrates forms at temperatures of 0-5°C. Although this crystalline precipitate is not detrimental to the function of the surfactant in the cement composition, it does cause problems when the aqueous solution is transferred from bulk storage containers (if used for the transfer of the surfactant). (This is because the supply lines that are supplied may become clogged with sediment.) A single salt solution of potassium or sodium containing by-product sulfate and sulfonate salts will either form a glassy crystalline precipitate at temperatures between 0 and 5°C or, surprisingly, the two salts will be virtually identical. It has been found that Lund's product at a concentration does not form a precipitate and therefore eliminates the problems associated with cold storage of such blends.

The object of the invention is an aqueous solution of a mixed alkali metal or ammonium salt of the condensation product of naphthalene sulfonic acid and formaldehyde, which
An object of the present invention is to provide an aqueous solution that remains substantially free of precipitates at temperatures of . Another object of the invention is to provide a method for producing such salts.

The high molecular weight condensation product salt NSF is extremely effective in dispersing cement particles and is described in US Pat. No. 3,686.
No. 133, the dispersant only contains a single metal ion M such as sodium, potassium or lithium as shown in the following general formula (1).

However, the salt of the present invention has the following general formula [1] and the general formula (If
) and Blend 9 of the general formula (1) [i.e. a heterogeneous composition of the general formula 11B depending on the preparation method used].

1, M 803-(NAP)('I'H)-(Gh-
(NAPHTH)-8o3M]□1-HI1. X 5
03-(NAPHTH)-((1(2-(NAPHTH)
)-So3X], -Hl, M5o3-(NAPHT
H)-[(](□-(NAPHTH)-8o3X)n-
H [where M is an ion alternately selected from sodium, potassium, lithium or ammonium;
is an ion different from M selected from sodium, potassium, lithium or ammonium (provided that M and X are different in the composition);
H) is a naphthalene ring radical, n is 5 to about 20
．． It is preferably a value of 9 to 12].

Naphthalene polymer chains are understood to be both linear and branched and mixtures thereof. The blend also contains small amounts of similar by-product metal sulfate salts that form part of the manufacturing reaction. The M/X molar ratio in the surfactant solution is
may be within the range of

The aqueous solution contains a mixed salt containing a small amount of by-product metal salts at a concentration of 30 to 60%.
Including weight%. Compositions containing 38-42% solids are usually preferred.

Generally, these compositions are prepared by condensing molten naphthalene with oleum to produce naphthalene sulfonic acid derivatives with various substituted regioisomers, and then condensing the naphthalene sulfonic acid derivatives with water and formaldehyde at a temperature of about 90°C. It is produced by causing a polynuclear condensation product of the following general formula to be produced.

H8O3(NAPHTH) -(CHz (NAPHTH)
H) SOa HE 5-20-H This can then be made into a salt form by adding at least two alkali metal and/or ammonium hydroxides or carbonates simultaneously or sequentially. At this time, a small amount of by-product sulfate is also produced. These compositions can also be prepared by melding two or more salts containing a single cationic component. These compositions are then diluted with water to give a solids content of 30-60% (40-70% water).
It is said to be an aqueous solution of The compositions include alkaline earth or alkali metal salts of gluconic acid (e.g., U.S. Pat. No. 3,686).
．． 133), polyols, and epoxy resins (see, e.g., U.S. Pat. No. 4,194,919), and U.S. Pat.
127.417 to form a cementitious mixture.

Typical operations for the preparation of NSF surfactant solutions of the invention and examples of the invention are shown below, but the invention is not limited thereto. All "parts" and "%" are by weight unless otherwise indicated.

Production method A) To prepare the IJ salt, 18,113 parts of a melt of an NSF condensate consisting of 2.9% by weight of sulfuric acid and 1% by weight of unreacted formaldehyde was added to 50
The sodium hydroxide solution was stirred for about 1 hour with 4,598 parts of sodium hydroxide until the temperature of the mixture was about 7
The feed rate was such that the temperature was maintained at 1°C. The pH of the solution was 3.7-4.0 after the addition of IJium hydroxide. The solution was further neutralized by adding 40 parts of solid sodium carbonate to provide a slightly alkaline surfactant solution. This aqueous solution contained 39.8% Na salt of naphthalene sulfonic acid/formaldehyde condensate, about 3.4% by-product sodium sulfate and sodium sulfonate, and its solids content was about 43.2%. Similar products of 30-60% solids can be produced by increasing or decreasing the amount of water above.

Process B The potassium salt of the naphthalene sulfonic acid/formaldehyde condensate can be made by Process A above using similar reaction conditions, but of course replacing the sodium hydroxide and sodium carbonate with equivalent amounts of potassium hydroxide and potassium carbonate. must be used.

Production Method C To produce the ammonium salt of N5F, a 28% ammonium hydroxide solution was used in an equivalent amount to the sodium hydroxide and sodium carbonate in Production Method A above, and the solution was adjusted to pH 8.
．． Add at a temperature of 60-80° C. until the temperature reaches 5-9.5.

Example 1 To make a mixed salt of sodium and potassium, process A
300 g of N3F condensate melt was added to a 500 rug round bottom flask (equipped with a stirrer, thermometer, and pH meter).

The mixture was heated to 60° C. (with a dropping funnel, condenser and heating mantle). 21. under gentle stirring conditions.
47.511 of a bath solution containing 39 g (0.381 mol) of potassium hydroxide was added to the melt over the course of 1 hour, maintaining the temperature at 60 DEG -80 DEG C.

The pH of the reaction solution was approximately 1.0. Then, a 50% sodium hydroxide bath was performed under the same conditions at a pH of 8.5N10.
It was added until it reached 5. The total amount of sodium hydroxide is equivalent to 16.78.9 (0.4195 mol).

The molar ratio of sodium ions and potassium ions is approximately 1
．． It was 1. When the pH of the reaction solution stabilized within the range of 8.5-10.5, the amount of total solids was estimated and diluted with water to 42±2%. The resulting 366.29 product had a total solids content of 42.1%, a K)N of 9.9, and a viscosity of 29.
18 centipoise and concrete flow value 151.5
Met.

Its concrete flow value is ASTM-C-305-65
2.1 of Portland Cement Type I containing 1.2% of the above NSF dispersant.
The mixture was mixed with water, placed in a flow cone, and flowed onto a flat plate for measurement. This measured value was compared with that of a standard product containing no dispersant. Example 2 To make the sodium and ammonium static salt of NSF, 1120 g of the condensate melt (from Process A above) was
Place in a 2e round bottom flask with stirrer, thermometer, pH meter, dropping pouch, condenser and heating mantle 6
Heated to 0°C. To this was added 122I 50% sodium hydroxide (1,525 mol) over a period of about 1.5 hours at a temperature of 60-80<0>C under gentle stirring. Next, 206 g of 28% ammonium hydroxide solution 1 to 6
It was added at 0-80°C until the pH was 8.5-9.5. The molar ratio of sodium ions/ammonium ions was Q, 93/1. The total solid content was adjusted to 40% with water to give a pH of 9.1 and a concrete flow value of 185.7.
A product (total weight 1.434 g) was obtained.

NSF compositions (two types) with sodium ion/potassium ion molar ratios of 3/1 and 5.6/1 were prepared by using various amounts of sodium hydroxide and hydrium hydroxide according to the procedure of Example 1. did.

Examples 5 to 10 By Zolend the product of manufacturing method A and the products of manufacturing methods B and C in various ratios by a simple mixing method, a molar ratio of 1/
A mixture containing 3 to 5 sodium ions, potassium ions and ammonium ions could be produced.

The low temperature stability of the dispersant solutions obtained in each of the above manufacturing methods and Examples was tested. In one test, each solution was heated to 0°C.
The amount of precipitate formed in the solution was compared visually. This comparison shows that only sodium salts, which produce a large amount of precipitate, and only potassium salts have a maximum precipitation amount of 1.
It was rated 0 and this was done. The results are shown in Table 1.

Another freezing test was conducted in which each sample was
The sample was frozen at a temperature of 0.degree. C., then taken out from the freezer and thawed at room temperature (20.degree. C.), and then the amount of precipitate was evaluated using the same criteria as above. The results are also shown in Table 1.

Table 1 NSF Low Temperature Stability Test Example 10 Typical cement compositions made from dispersants were tested according to ASTM-C-494 procedures and yielded 100 pounds (45,36 kg) of cement 13
-19ii, tyx (0.38-0.56 g) met the requirements for type A water-reducing drug mixtures and type F high-range water-reducing drug mixtures.

Patent applicant: IGBA Americas, Inc. 9 (4 others)

Claims (1)

[Claims] (1) The following general formula %) [M and or different and alternately selected from at least two ions selected from the group consisting of Na, Li, K or NH4 (NAPHTH) is a naphthalene radical; n is a value from 5 to 20. ~60% and a small amount of the above ionic sulfate and the molar ratio of M/X from G to C
an aqueous solution of the dispersant composition which does not form a substantially precipitate at a temperature of 0 to 5<0>C. (2) The composition according to claim 1, wherein M and X are selected from Na ions and Na ions. (3) The composition of claim 1 comprising 38-48% of a mixed salt blend in which M and X are selected from Na ions and Na ions, the molar ratio of M/X being about 1/1. thing. (4) The composition according to claim 1, wherein M and X are selected from ions and NH4 ions. (5) The composition according to claim 1, wherein M and X are selected from Na ions and NH4 ions. (6) M and X are Na ions, K ions and NH4
The composition according to claim 1, wherein the composition is selected from two ions. (General formula % formula %) is a diradical] and contains an aqueous solution of naphthalene sulfonic acid formaldehyde condensation product containing unreacted sulfuric acid; A composition according to claim 1, produced by reacting two hydroxides or carbonates: (8) involving at least two hydroxides or carbonates in a sequential reaction; (9) The composition according to claim 7, which is produced by simultaneously involving a small amount (at least two kinds of hydroxides or carbonates) in the reaction. The composition according to scope item 7. Mixing the composition of general formula (1), which is Qo), M, b''-Na ion and X crab ion, and the composition of general formula (If). The composition according to claim 1 manufactured by αυ The composition according to claim 10 and M7
! +ZNH4 The composition according to claim 1, which is produced by mixing with the composition of general formula (1). Q21 1 The composition according to claim 1, comprising an alkaline earth metal salt or an alkali metal salt of luconic acid. a9 Claim 1 that includes a hydraulic cement mixture
The composition described in Section.