US 2006O183879A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2006/0183879 A1
Yamato et al. (43) Pub. Date: Aug. 17, 2006
(54) PROCESS FOR PRODUCING A Publication Classification
NAPHTHALENESULFONATE
FORMALDEHYDE CONDENSATE (51) Int. Cl.
C08G I4/02 (2006.01)
(75) Inventors: Fujio Yamato, Wakayama-shi (JP); (52) U.S. Cl. .............................................................. 528/129
Shuichi Fujita, Wakayama-shi (JP)
Correspondence Address: (57) ABSTRACT
BRCH STEWART KOLASCH & BRCH
PO BOX 747
FALLS CHURCH, VA 22040-0747 (US) The invention provides a process capable of easily produc
ing a water-soluble salt of a naphthalenesulfonate formal
(73) Assignee: Kao Corporation, Tokyo (JP) dehyde condensate with a reduced amount of unreacted
(21) Appl. No.: 11/341,633 formaldehyde. When naphthalenesulfonic acid is subjected
to condensation reaction with formaldehyde to produce a
(22) Filed: Jan. 30, 2006 naphthalenesulfonate formaldehyde condensate, a sulfite is
added to the reaction system after the conclusion of the
(30) Foreign Application Priority Data condensation reaction. When a cement dispersant composi
tion is obtained, the process includes a step of neutralizing
Jan. 31, 2005 (JP)...................................... 2005-023965 the condensate.
US 2006/0183879 A1 Aug. 17, 2006

PROCESS FOR PRODUCING A condensate, and a cement composition containing cement,

NAPHTHALENESULFONATE FORMALDEHYDE water and the cement dispersant.
CONDENSATE
0008 Further, the present invention relates to a process
TECHNICAL FIELD
for producing a cement dispersant, including a condensation
reaction step (I) of condensation-reacting naphthalene
0001. The present invention relates to a process for sulfonic acid with formaldehyde, a step (II) of adding a
producing a naphthalenesulfonate formaldehyde conden Sulfite to a reaction system containing the condensate
sate, a naphthalenesulfonate formaldehyde condensate pro obtained in the condensation reaction step (I), and a step (III)
duced by the process or a water-soluble salt thereof, a of removing a water-insoluble material from the reaction
cement dispersant containing the same, and a cement com system in the step (II), neutralization of the condensate being
position having the same added thereto. carried out after the condensation reaction step (I).
0009. In addition, the present invention relates to a
BACKGROUND OF THE INVENTION cement dispersant containing a naphthalenesulfonate form
aldehyde condensate containing 110 mg/kg or less, or 110
0002. A water-soluble salt of a naphthalenesulfonic acid/ ppm or less, of formaldehyde and having a weight-average
formaldehyde condensate (also referred to hereinafter as molecular weight of 10000 or more, or a water-soluble salt
naphthalene-based condensate salt) is a polymer produced thereof.
by condensation reaction with formaldehyde, and has been
used often in cement dispersants (JP-B 41-11737, "Cement DETAILED DESCRIPTION OF THE
Gijutsu Nenpo 1964, Cement Bunsanzai Ni Kansuru Ken INVENTION
kyu' (Cement Technology Annual Report 1964, Study on
Cement Dispersant), pp. 200-204). When the naphthalene 0010. In the condensation reaction of naphthalene
based condensate salt is added as a cement dispersant to a sulfonic acid with formaldehyde, (1) a reduction in the ratio
cement composition, the fluidity of the composition is of formaldehyde to be charged, (2) an increase in the degree
increased. As a result, preferable effects such as a decrease of conversion of formaldehyde by increasing the reaction
in the water cement ratio of the cement composition and an temperature, etc., can be anticipated as a method of reducing
increase in concrete strength are known to be exhibited. the amount of unreacted formaldehyde in the naphthalene
based condensate.
0003 JP-A 4-211046 and JP-A 5-320120 disclose a
reduction in free or unreacted formalin in production of 0011. However, the method (1) not only hinders poly
naphthalenesulfonate formaldehyde condensates. merization, but also requires the condensation time to be
significantly prolonged for attaining a predetermined
0004. In recent years, the sick house syndrome caused by molecular weight. Because the condensation reaction is
formaldehyde becomes problematic, and it is estimated that conducted generally in an aqueous system in production of
unreacted formaldehyde remaining in the naphthalene-based a naphthalene condensate, the reaction temperature in the
condensate salt becomes problematic from now on. A method (2) cannot be increased to a high temperature of 100
cement dispersant containing such naphthalene-based con to 105° C. or more. In any of the methods (1) and (2), it is
densate salt or a cement composition containing the same is difficult to polymerize the condensate for attaining a suitable
expected to be applicable as a product having stabilized molecular weight for use as a cement dispersant, thus failing
qualities, reducing the amount of formaldehyde released to attain predetermined dispersing performance and neces
from its hardened product, and less burdening the environ sitating significant prolongation of the condensation time.
ment with a load.
0012. The present invention relates to provide a process
SUMMARY OF THE INVENTION capable of easily producing a water-soluble salt of a naph
thalenesulfonate formaldehyde condensate reducing the
0005 The present invention relates to a process for amount of unreacted formaldehyde, having stabilized quali
producing a naphthalenesulfonate formaldehyde conden ties, less burdening the environment with a load, and being
sate, that is, a condensate of naphthalenesulfonic acid and Suitable as a cement dispersant.
formaldehyde, including a condensation reaction step (I) of 0013. According to the present invention, there is pro
condensation-reacting naphthalenesulfonic acid with form
aldehyde, a step (II) of adding a sulfite to the reaction system vided a process capable of easily producing a water-soluble
containing the condensate obtained in the condensation salt of a naphthalenesulfonate formaldehyde condensate
reaction step (I), and a step (III) of removing a water reducing the amount of unreacted formaldehyde, having
insoluble material from the reaction system in the step (II). stabilized qualities, less burdening the environment with a
load, and being Suitable as a cement dispersant. Accordingly,
0006 The present invention also relates to a process for there can be provided a water-soluble salt of a naphthale
producing a water-soluble salt of a naphthalenesulfonate nesulfonate formaldehyde condensate reducing the amount
formaldehyde condensate, including the above shown steps of unreacted formaldehyde, having stabilized qualities, and
(I) to (III), neutralization of the condensate being carried out less burdening the environment with a load, a cement
after the condensation reaction step (I). dispersant containing the water-soluble salt, and a cement
0007 Also, the present invention relates to a naphthale composition containing the dispersant.
nesulfonate formaldehyde condensate or a water-soluble salt 0014 Unlike the conventionally proposed methods (1)
thereof, which is obtainable by the process of the invention and (2) above, a method of removing unreacted formalde
described above, a cement dispersant containing the water hyde as a water-insoluble material with a sulfite is proposed
soluble salt of a naphthalenesulfonic acid/formaldehyde in the present invention.
US 2006/0183879 A1 Aug. 17, 2006

0.015 That is, the present invention relates to a process agent, it is possible to employ calcium hydroxide, sodium
for producing a naphthalenesulfonate formaldehyde conden hydroxide and calcium carbonate, among which calcium
sate, including a condensation reaction step (I) of conden carbonate is preferable from the viewpoint of exhibiting the
sation reaction of naphthalenesulfonic acid with formalde effect of the sulfite added (the effect of converting unreacted
hyde, a step (II) of adding a Sulfite to a reaction system formaldehyde into a water-insoluble material). That is, the
containing the condensate obtained in the condensation neutralizing agent is added preferably in 1.0 to 1.1 moles to
reaction step (I), and a step (III) of removing a water 1 mole of naphthalenesulfonic acid, and is added preferably
insoluble material from the reaction system in the step (II), in 1.0 to 1.1 moles to 1 mole of the unreacted sulfuric acid.
or to a process for producing a water-soluble salt of a Such water-soluble salt is obtained usually as an aqueous
naphthalenesulfonate formaldehyde condensate, including a solution in which the water-soluble salt was dissolved.
condensation reaction step (I) of condensation reaction of 0021 Hereinafter, one example of the process for pro
naphthalenesulfonic acid with formaldehyde, a step (II) of ducing a water-soluble salt of a naphthalenesulfonate form
adding a sulfite to a reaction system containing the conden aldehyde condensate as a cement dispersant is briefly
sate obtained in the condensation reaction step (I), and a step described.
(III) of removing a water-insoluble material from the reac
tion system in the step (II) wherein neutralization of the 0022 First, for obtaining naphthalenesulfonic acid, sul
furic acid is used in a molar ratio of 1.2-1.4 moles to 1 mole
condensate is carried out after the condensation reaction step
(I); in this manner, after the conclusion of the condensation of naphthalene, and reacted at 150 to 165° C. for 2 to 5 hours
reaction of naphthalenesulfonic acid with formaldehyde, to give a sulfonated product. Then, 0.95 to 0.99 mole of
unreacted formaldehyde is removed as a water-insoluble formalin is added dropwise as formaldehyde to 1 mole of the
material by adding a sulfite to the reaction system. sulfonated product at 85 to 95° C. over 3 to 6 hours, and
subjected to condensation reaction at 95 to 105° C. step
0016. The sulfite selected in the present invention is (1). Water, a neutralizing agent (for example calcium car
excellent in the ability to form an insoluble material of bonate) and sulfite are added to the condensate thereby
formaldehyde and can exhibit an effect of sufficiently neutralizing it at 80 to 95°C. and simultaneously converting
removing formaldehyde. Given other inorganic salts, such unreacted aldehyde into a water-insoluble material step (II)
effect cannot be sufficiently attained. Accordingly, the and neutralization. The neutralizing agent is added prefer
amount of unreacted formaldehyde can be reduced without ably in 1.0- to 1.1-molar excess to naphthalenesulfonic acid
requiring a change in the condensation reaction conditions and unreacted sulfuric acid respectively. The sulfite is added
or prolongation of the condensation time. In the process of preferably in 0.5- to 5-molar excess relative to 1 mole of
the present invention, an aqueous Solution containing a unreacted formaldehyde. The amount of unreacted formal
water-soluble salt of a naphthalenesulfonate formaldehyde dehyde in the reaction system can be measured according to
condensate dissolved therein can be obtained and thus used a method described in the Examples below. Thereafter, in the
in many ways to serve preferably as a cement dispersant. step of removing a water-insoluble material in a conven
0017. A water-soluble salt of a naphthalenesulfonate tional way, preferably by separation with filtration, step
formaldehyde condensate with a formaldehyde content of (III), an aqueous solution of a water-soluble salt of the
110 mg/kg or less can be obtained. naphthalenesulfonate formaldehyde condensate is obtained.
This aqueous solution can be used as it is or as a cement
0018. The sulfite used in the present invention is prefer dispersant composition to which other ingredients are Suit
ably a monovalent metal salt Such as Sodium salt or a ably added. The solids content of the aqueous solution varies
divalent metal salt Such as calcium salt or magnesium salt, depending on use, and for use as a cement dispersant, the
among which the calcium salt is preferable from the view solids content is preferably 30 to 45 wt %. If necessary, the
point of removing formaldehyde as a water-insoluble mate aqueous solution can be dried and powdered to give a
rial. powdered water-soluble salt of a naphthalenesulfonate form
0.019 From the viewpoint of reaction efficiency, burden aldehyde condensate which can then be used as powdered
on a filtration step, and reduction in the amount of unreacted cement dispersant. Drying and powdering can be carried out
formaldehyde, the amount of the sulfite added is preferably by spray drying, drum drying, freeze drying etc.
0.5 to 5 moles, more preferably 0.8 to 3 moles, further more 0023 The weight-average molecular weight of the naph
preferably 1 to 3 moles, relative to 1 mole of unreacted thalenesulfonate formaldehyde condensate or a water
formaldehyde present in the reaction system after the con soluble salt thereof, obtainable by the process of the present
densation reaction. invention, is preferably 10000 or more, more preferably
0020 When a water-insoluble salt of the naphthalene 10000 to 15000. This molecular weight is measured by
Sulfonate formaldehyde condensate is produced, it is pref liquid chromatography (with polystyrene Sodium sulfonate
erable from viewpoints such as prevention of corrosion of a as standard).
container that the neutralization of the condensate is carried 0024 Water solubility referred to in a water-soluble salt
out after the condensation reaction step (I). The neutraliza of the naphthalenesulfonate formaldehyde condensate
tion is carried out preferably before the step (III). In the step means that an aqueous solution having a solids content of 10
(II), a neutralizing agent is preferably added together with wt % or more can be prepared therefrom.
the sulfite thereby forming a water-insoluble material of 0025. When the naphthalenesulfonate formaldehyde con
unreacted formaldehyde and simultaneously neutralizing the densate is used as a cement dispersant, the amount of the
reaction system. From the viewpoint of preventing corrosion condensate is preferably 0.05 to 3 parts by weight, more
of a storing container, the neutralization is carried out preferably 0.1 to 2 parts by weight, still more preferably 0.2
preferably until the pH of the reaction system comes to be to 1 part by weight, relative to 100 parts by weight of
in the range of 4 to 12 at 20° C., and as the neutralizing Cement.
US 2006/0183879 A1 Aug. 17, 2006

0026. By mixing the cement dispersant of the present 0038 Column type: G4000SW-G2000SW (7.8qpx
invention with cement and water, a cement composition is 300 mm)
obtained. The watercement ratio (W/C) is preferably 20 to 0039 Eluent: 30 mM aqueous sodium acetate
60%, more preferably 25 to 50%, still more preferably 30 to
45%. 0040 solution/acetonitrile=6/4
0027. The cement is cement such as ordinary portland 0041) Flow rate: 0.7 ml/min
cement, belite cement, moderate-heat portland cement, high 0042. Detector: UV 280 nm
early-strength portland cement, ultila high-early-strength
portland cement and Sulfate-resistant cement, which may (Evaluation of Performance as Cement Dispersant)
further contain blast furnace slag, fly ash, silica fume, lime 0043. The performance of the naphthalene-based conden
stone powder (calcium carbonate powder) etc. sate Salt as a cement dispersant was evaluated. 1000 g
0028. Further, the cement composition may contain normal portland cement (manufactured by Taiheiyo Cement)
aggregate. The aggregate includes sand and gravel. The and a solution prepared by dissolving, in 300 g water, the
hydraulic composition can be used as mortar and concrete. naphthalene-based condensate in an amount 1 wt % (in
0029. The cement composition of the present invention terms of solids content) relative to the cement were mixed
with each other with a mortar mixer based on JIS-R5201 at
can be used not only in the field of fresh concrete and low speed for 1 minute and at high speed for 2 minutes, and
vibrated concrete products but also in any fields of various then introduced into a Vicatindentation cone. The surface of
kinds of concrete such as self-leveling concrete, refractory the cone surface was made even, and the spread (mm) after
concrete, plaster concrete, gypsum slurry, lightweight or raising was measured.
heavyweight concrete, AE concrete, repairing concrete, pre
packed concrete, tremie concrete, grout concrete, ground Comparative Example 1
improvement concrete, and concrete in the cold.
0044) 44 g water was added to a sulfonated product
EXAMPLES obtained by reacting 1.28 moles of sulfuric acid with 1 mole
of naphthalene at 150 to 160° C. for 3 hours, and then 0.98
0030 The present invention is described by reference to mole (this amount of formalin is expressed in terms of the
the Examples below. The Examples are provided for merely content of formaldehyde; this hereinafter applies) of (37%)
illustrating the present invention and not intended to limit formalin was dropped into it at 90° C. over 3 hours. After
the present invention. dropping, the condensation reaction was carried out at 98 to
0031. In the Comparative Examples and the Examples 102°C. for 10 hours. The resulting condensate was neutral
ized with water and a neutralization amount of calcium
below, naphthalene-based condensate salts were produced carbonate. After neutralization, the pH value was about 6.
and evaluated for their performance as cement dispersants. Thereafter, the reaction mixture was filtered, and the con
The results are shown in Table 1.
centration of a calcium salt of the naphthalene-based con
(Method of Measuring the Amount of Unreacted Formalde densate (referred to hereinafter as Casalt) was adjusted to a
hyde) solids content of 40 wt %. The amount of unreacted form
aldehyde was 660 ppm (mg/kg), and the molecular weight of
0032. The amount of unreacted formaldehyde in the the Casalt was 13200. The resulting aqueous solution was
reaction system was quantified by dissolving 1 g reaction used as a cement dispersant to evaluate performance.
product containing a naphthalene-based condensate (solids
content 40 wt %) in 100 ml distilled water, then treating this Comparative Example 2
aqueous solution to convert it into a 2,4-dinitrophenyl
hydrazine derivative thereof and then quantify it by liquid 0045 44 g water was added to a sulfonated product
chromatography. As the standard Substance, a 2,4-dinitro obtained by reacting 1.28 moles of sulfuric acid with 1 mole
phenyl hydrazine derivative of formaldehyde was used. The of naphthalene at 150 to 160° C. for 3 hours, and then 0.95
measurement conditions for liquid chromatography are as mole of (37%) formalin was dropped into it at 80 to 90° C.
follows: over 3 hours. After dropping, the condensation reaction was
carried out at 98 to 102° C. for 10 hours. The resulting
0033 Column type: L-Column-ODS (4.6px 150 mm) condensate was neutralized with water and a neutralization
0034) Eluent: waterfacetonitrile=1/1 amount of calcium carbonate. After neutralization, the pH
value was about 6. Thereafter, the reaction mixture was
0035 Flow rate: 1.0 ml/min filtered to adjust the solids content of the Casalt to 40 wt %.
0036) Detector: UV 360 nm The amount of unreacted formaldehyde was 450 ppm (mg/
kg), and the molecular weight of the Casalt was 8500. The
(Molecular Weight of the Naphthalene-Based Condensate resulting aqueous solution was used as a cement dispersant
Salt) to evaluate performance.
0037. The molecular weight of the naphthalene-based Comparative Example 3
condensate salt, expressed in terms of weight-average
molecular weight, was determined by preparing 0.2% aque 0046) 44 g water was added to a sulfonated product
ous Solution thereof and measuring it by liquid chromatog obtained by reacting 1.28 moles of sulfuric acid with 1 mole
raphy. As the standard Substance, polystyrene Sodium Sul of naphthalene at 150 to 160° C. for 3 hours, and then 0.95
fonate was used. The measurement conditions for liquid mole of (37%) formalin was dropped into it at 90° C. over
chromatography are as follows: 3 hours. After dropping, the condensation reaction was
US 2006/0183879 A1 Aug. 17, 2006

carried out at 98 to 102° C. for 18 hours. The resulting Examples 1 to 9

condensate was neutralized with water and a neutralization
amount of calcium carbonate. After neutralization, the pH 0049. After condensation reaction was carried out by the
value was about 6. Thereafter, the reaction mixture was synthesis method in Comparative Example 1, the resulting
filtered to adjust the solids content of the Casalt to 40 wt %. condensate was neutralized with water, a neutralization
The amount of unreacted formaldehyde was 410 ppm (mg/ amount of calcium carbonate, and the type of Sulfite shown
kg), and the molecular weight of the Casalt was 11100. The in Table 1 and Sulfite in an amount corresponding to the
resulting aqueous solution was used as a cement dispersant amount of unreacted formaldehyde in Table 1. After neu
to evaluate performance. tralization, the pH value was about 6. Thereafter, the Casalt
was filtered and adjusted in the same manner as in Com
Comparative Example 4 parative Example 1 to a solids content of 40 wt %. The
amount of unreacted formaldehyde and the molecular
0047. 44 g water was added to a sulfonated product weight of the condensate salt are shown in Table 1. The
obtained by reacting 1.28 moles of sulfuric acid with 1 mole resulting aqueous solution was used as a cement dispersant
of naphthalene at 150 to 160° C. for 3 hours, and then 0.98 to evaluate performance.

TABLE 1.
Compound added after
Amount of condensation reaction

unreacted Added Dispersing

formaldehyde(ppm amount Molecular performance
or mg/kg) Kind (moles) weight (mm)
Comparative 660 13200 253
example 450 8500 194
410 11100 223
440 16300 245
6SO Sodium carbonate 1.O 13200 252
Example 45 Calcium sulfite O.8 13100 2S4
18 Calcium sulfite 1.O 13400 251
19 Calcium sulfite 1.5 13500 257
18 Calcium sulfite 2.0 13200 253
21 Calcium sulfite 3.0 13700 250
23 Calcium sulfite S.O 13100 258
32 Magnesium sulfite 1.O 13300 255
105 Sodium sulfite 1.O 13200 252
43 Sodium sulfite 1.5 13400 2S4

*In Table 1, the amount of sulfite added is an amount (moles) per mole of unreacted formaldehyde.

mole of (37%) formalin was dropped into it at 90° C. over 1. A process for producing naphthalenesulfonate formal
3 hours. After dropping, the condensation reaction was dehyde condensate, comprising a condensation reaction step
carried out at 98 to 102° C. for 18 hours. The resulting (I) of condensation-reacting naphthalenesulfonic acid with
condensate was neutralized with water and a neutralization formaldehyde, a step (II) of adding a sulfite to the reaction
amount of calcium carbonate. After neutralization, the pH system comprising the condensate obtained in the conden
value was about 6. Thereafter, the reaction mixture was sation reaction step (I), and a step (III) of removing a
filtered to adjust the solids content of the Casalt to 40 wt %. water-insoluble material from the reaction system in the step
The amount of unreacted formaldehyde was 440 ppm (mg/ (II).
kg), and the molecular weight of the Casalt was 16300. The 2. A process for producing a water-soluble salt of a
resulting aqueous solution was used as a cement dispersant naphthalenesulfonate formaldehyde condensate, comprising
to evaluate performance. a condensation reaction step (I) of condensation-reacting
naphthalenesulfonic acid with formaldehyde, a step (II) of
Comparative Example 5 adding a sulfite to the reaction system comprising the
condensate obtained in the condensation reaction step (I),
0.048. After condensation reaction was carried out by the and a step (III) of removing a water-insoluble material from
synthesis method in Comparative Example 1, the resulting the reaction system in the step (II), neutralization of the
condensate was neutralized with water, a neutralization condensate being carried out after the condensation reaction
amount of calcium carbonate, and sodium carbonate in an step (I).
amount corresponding to the amount of unreacted formal 3. The process according to claim 1 or 2, wherein the
dehyde shown in Table 1. After neutralization, the pH value sulfite is a divalent metal salt.
was about 6. Thereafter, the Casalt was filtered and adjusted 4. The process according to claim 1 or 2, wherein the
in the same manner as in Comparative Example 1 to have a sulfite is added in an amount of 0.5 to 5 moles per mole of
solid content of 40 wt %. The amount of unreacted form unreacted formaldehyde.
aldehyde and the molecular weight of the condensate salt are 5. A naphthalenesulfonate formaldehyde condensate or a
shown in Table 1. The resulting aqueous solution was used water-soluble salt thereof, which is obtainable by the process
as a cement dispersant to evaluate performance. of claim 1.
US 2006/0183879 A1 Aug. 17, 2006

6. A naphthalenesulfonate formaldehyde condensate or a 10. A cement composition comprising cement, water and
water-soluble salt thereof, which is obtainable by the process the cement dispersant of any one of claim 7 to 9.
of claim 2. 11. A process for producing a cement dispersant, com
7. A cement dispersant comprising the water-soluble salt prising a condensation reaction step (I) of condensation
of a naphthalenesulfonate formaldehyde condensate accord reacting naphthalenesulfonic acid with formaldehyde, a step
ing to claim 5. (II) of adding a sulfite to the reaction system comprising the
8. A cement dispersant comprising the water-soluble salt condensate obtained in the condensation reaction step (I),
of a naphthalenesulfonate formaldehyde condensate accord
ing to claim 6. and a step (III) of removing a water-insoluble material from
9. A cement dispersant comprising a naphthalenesulfonate the reaction system in the step (II) neutralization of the
formaldehyde condensate containing formaldehyde in an condensate being carried out after the condensation reaction
amount of 110 mg/kg or less and having a weight-average step (I).
molecular weight of 10000 or more, or a water-soluble salt
thereof.