U.S. patent application number 10/836339 was filed with the patent office on 2004-11-25 for zinc-modified composite polybasic salt, method of preparing the same and use thereof.
Invention is credited to Igarashi, Hiroshi, Ishida, Hitoshi, Komatsu, Yoshinobu, Kondo, Masami, Minagawa, Madoka, Sato, Teiji, Sato, Tetsu.
Application Number | 20040234442 10/836339 |
Document ID | / |
Family ID | 16335851 |
Filed Date | 2004-11-25 |
United States Patent
Application |
20040234442 |
Kind Code |
A1 |
Komatsu, Yoshinobu ; et
al. |
November 25, 2004 |
Zinc-modified composite polybasic salt, method of preparing the
same and use thereof
Abstract
A composite metal polybasic salt containing a trivalent metal,
zinc metal and a divalent metal as metal components and having a
novel crystal structure, and a method of preparing the same. The
invention further deals with a composite metal polybasic salt which
has anion-exchanging property, which by itself is useful as an
anion-exchanger, capable of introducing anions suited for the use
upon anion-exchange, and finds a wide range of applications, and a
method of preparing the same. The composite metal polybasic salt
has a particular chemical composition and X-ray diffraction peaks,
exhibiting peaks at 2.theta.=2 to 15.degree., 2.theta.=19.5 to
24.degree. and 2.theta.=33 to 50.degree., and a single peak at
2.theta.=60 to 64.degree. in the X-ray diffraction
(Cu-.alpha.).
Inventors: |
Komatsu, Yoshinobu;
(Chuo-ku, JP) ; Ishida, Hitoshi; (Chuo-ku, JP)
; Igarashi, Hiroshi; (Chuo-ku, JP) ; Kondo,
Masami; (Chuo-ku, JP) ; Minagawa, Madoka;
(Chuo-ku, JP) ; Sato, Tetsu; (Chuo-ku, JP)
; Sato, Teiji; (Chuo-ku, JP) |
Correspondence
Address: |
SHERMAN & SHALLOWAY
413 North Washington Street
Alexandria
VA
22314
US
|
Family ID: |
16335851 |
Appl. No.: |
10/836339 |
Filed: |
May 3, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10836339 |
May 3, 2004 |
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09786427 |
Mar 6, 2001 |
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09786427 |
Mar 6, 2001 |
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PCT/JP00/04555 |
Jul 7, 2000 |
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Current U.S.
Class: |
423/420.2 ;
252/62; 423/518 |
Current CPC
Class: |
C01G 9/006 20130101;
C01G 9/00 20130101; C01P 2002/22 20130101; C07F 5/069 20130101;
B01J 41/10 20130101 |
Class at
Publication: |
423/420.2 ;
423/518; 252/062 |
International
Class: |
C01G 009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 8, 1999 |
JP |
195121/99 |
Claims
1. A composite metal polybasic salt having a chemical composition
represented by the following general formula
(1),M.sup.2.sub.aZn.sub.bM.s-
up.3.sub.x(OH).sub.y(A).sub.z.nH.sub.2O (1)wherein M.sup.2 is a
divalent metal other than Zn, M.sup.3 is a trivalent metal, A is an
inorganic or organic anion, and a, b, x, y and z are numbers
satisfying the following formulas, i) 0.ltoreq.a, 0<b ii)
3x+2(a+b)-y-mz=0 (wherein m is a valency of anion A), iii)
0.3.ltoreq.(a+b)/x.ltoreq.2.5, iv) 1.5.ltoreq.y/(x+a+b).ltoreq.3.0,
and v) 4.0.ltoreq.(x+a+b)/z.ltoreq.20.0, and n is a number of not
larger than 7, exhibiting diffraction peaks at 2.theta.=2 to
15.degree., 2.theta.=19.5 to 24.degree. and 2.theta.=33 to
50.degree., and a single peak at 2.theta.=60 to 64.degree. in the
X-ray diffraction (Cu-.alpha.).
2. A composite metal polybasic salt according to claim 1, wherein
an X-ray diffraction (Cu-.alpha.) peak at 2.theta.=33 to 50.degree.
is a single peak.
3. A composite metal polybasic salt according to claim 1 or 2,
wherein the divalent metal (M.sup.2) in said formula is
magnesium.
4. A composite metal polybasic salt according to any one of claims
1 to 3, wherein the trivalent metal (M.sup.3) in said formula is
aluminum.
5. A composite metal polybasic salt according to any one of claims
1 to 4, wherein the anions (A) in said formula are sulfuric acid
ions.
6. A composite metal polybasic salt according to any one of claims
1 to 4, wherein the anions (A) in said formula are carbonic acid
ions.
7. A composite metal polybasic salt according to any one of claims
1 to 4, wherein the anions (A) in said formula are silicic acid
ions.
8. A composite metal polybasic salt according to any one of claims
1 to 4, wherein the anions (A) in said formula are organocarboxylic
acid ions.
9. A composite metal polybasic salt according to any one of claims
1 to 4, wherein the anions (A) in said formula are phosphoric acid
ions.
10. A composite metal polybasic salt according to any one of claims
1 to 9, wherein said composite metal polybasic salt has a laminate
asymmetric index (Is) defined by the following formula (2),Is=tan
.theta..sub.2/tan .theta..sub.1 (2)wherein .theta..sub.1 is an
angle subtended by a peak perpendicular in the X-ray diffraction
peak of a predetermined spacing and a peak tangent on the narrow
angle side, and .theta..sub.2 is an angle subtended by the peak
perpendicular at the above peak and a peak tangent on the wide
angle side, which is not smaller than 1.5 at a peak of 2.theta.=33
to 50.degree..
11. A method of preparing a composite metal polybasic salt by
reacting a water-soluble salt of a trivalent metal with an oxide, a
hydroxide or a water-soluble salt of a divalent metal including
zinc as an essential component under the conditions of a pH of from
3.8 to 9.0 and a temperature of not lower than 50.degree. C. and,
if necessary, executing the ion exchange in the presence of an acid
or a soluble salt of acid.
12. An additive for resins comprising a composite metal polybasic
salt of any one of claims 1 to 10.
13. A heat insulator comprising a composite metal polybasic salt of
any one of claims 1 to 10.
14. An anion-exchanger comprising a composite metal polybasic salt
of any one of claims 1 to 10.
15. An anion-exchanger according to claim 14, wherein the anions of
the composite metal polybasic salt are sulfuric acid ions.
Description
TECHNICAL FIELD
[0001] The present invention relates to a composite metal polybasic
salt having a novel crystalline structure, a method of preparing
the same and use thereof.
BACKGROUND ART
[0002] As synthetic composite metal hydroxides, there have
heretofore been known a hydrotalcite-type synthetic mineral (e.g.,
Japanese Examined Patent Publication (Kokoku) No. 32198/1972) and a
salt of lithium aluminum composite hydroxide. (e.g., Japanese
Examined Patent Publication (Kokoku) No. 2858/1995).
[0003] There has further been known a polybasic aluminum-magnesium
salt. Japanese Examined Patent Publication (Kokoku) No. 38997/1974
teaches a method of producing a polybasic aluminum salt by reacting
a polybasic aluminum sulfate with a magnesium hydroxide at a molar
ratio of Al/Mg=1/2 to 4/3 in the presence of water. There has been
further stated that the polybasic aluminum magnesium salt can be
effectively used as an antacid.
[0004] Japanese Unexamined Patent Publication (Kokai) No.
204617/1985 teaches a method of preparing a magaldrate expressed by
the formula Al.sub.5Mg.sub.10(OH).sub.31(SO.sub.4).sub.2.xH.sub.2O
by reacting an active aluminum hydroxide with a stoichiometric
amount of water-soluble- sulfate-containing compound, active
magnesium oxide and(or) magnesium hydroxide in the presence of
water and, if necessary, drying the resulting magaldrate paste.
[0005] Japanese Unexamined Patent Publication (Kokai) No.
102085/1989 discloses a novel aluminum magnesium hydroxy compound
represented by the formula AlxMgy(OH).sub.35-zR.sub.2.nH.sub.2O
[wherein R is a residue RC00- of monocarboxylic acid, and, indexes
x, y and z satisfy the following conditions 3.ltoreq.x.ltoreq.9,
4.ltoreq.y.ltoreq.13, 3.ltoreq.z.ltoreq.5 and 3x+2y=35].
[0006] Japanese Unexamined Patent Publication (Kokai) No.
164432/1989 discloses an aluminum magnesium hydroxy compound having
a layer-structure represented by the general formula
AlxMgy(OH).sub.35-zR.sub.2.nH.sub.2O [wherein R is a residue RC00-
of monocarboxylic acid, RC00- having 2 to 22 carbon atoms, and
indexes x, y and z satisfy the following conditions
3.ltoreq.x.ltoreq.9, 4.ltoreq.y.ltoreq.13, 3.ltoreq.z.ltoreq.5 and
3x+2y=35], and a gel composition containing an oleophilic organic
compound which is in the liquid form at room temperature
(20.degree. C.).
[0007] Japanese Examined Patent Publication (Kokoku) No. 59977/1989
discloses a crystalline basic aluminum magnesium carbonate
represented by the formula
Al.sub.2Mg.sub.6(OH).sub.12(CO.sub.3).sub.2.xH.sub.2O [wherein
x.gtoreq.4].
[0008] Further, Japanese Examined Patent Publication (Kokoku) No.
52409/1991 discloses a method of producing a hydroxyaluminum
magnesium sulfate by reacting a solid magnesium hydroxide and/or
magnesium oxide with an aqueous solution of aluminum sulfate at an
atomic ratio of magnesium:aluminum of from 1:1 to 3:1 until the pH
of the reaction mixture becomes 4.0 to 8.0, removing the
water-soluble component from the reaction mixture by a known
method, followed, if necessary, by drying.
[0009] A conventional composite polybasic salt can be represented
by a magaldrate comprising aluminum and magnesium. However, the
present inventors have succeeded in synthesizing a novel composite
metal polybasic salt that has an explicit crystal structure
different from those of zinc-modified hydrotalcites.
[0010] The inventors have further discovered that the composite
metal polybasic salt can be effectively used as an additive for
resins, as a heat insulator and as an anion-exchanger.
DISCLOSURE OF THE INVENTION
[0011] The object of the present invention is to provide a
composite metal polybasic salt containing zinc metal as an
essential component and further containing a trivalent metal and a
divalent metal (metals other than zinc, the same holds
hereinafter), as metal components, and having a novel crystal
structure, and a method of preparing the same.
[0012] Another object of the present invention is to provide a
composite metal polybasic salt which has anion-exchanging property,
which by itself is useful as an anion-exchanger, capable of
introducing anions suited for the use upon anion-exchange, and
finds a wide range of applications, and a method of preparing the
same.
[0013] According to the present invention, there is provided a
composite metal polybasic salt having a chemical composition
represented by the following general formula (1),
M.sup.2.sub.aZn.sub.bM.sup.3.sub.x(OH).sub.y(A).sub.z.nH.sub.2O
(1)
[0014] wherein M.sup.2 is a divalent metal other than Zn, M.sup.3
is a trivalent metal, A is an inorganic or organic anion, and a, b,
x, y and z are numbers satisfying the following formulas,
[0015] i) 0.ltoreq.a, 0<b
[0016] ii) 3x+2(a+b)-y-mz=0 (wherein m is a valency of anion
A),
[0017] iii) 0.3.ltoreq.(a+b)/x.ltoreq.2.5,
[0018] iv) 1.5.ltoreq.y/(x+a+b).ltoreq.3.0, and
[0019] v) 4.0.ltoreq.(x+a+b)/z.ltoreq.20.0, and
[0020] n is a number of not larger than 7,
[0021] exhibiting diffraction peaks at 2.theta.=2 to 15.degree.,
2.theta.=19.5 to 24.degree. and 2.theta.=33 to 50.degree., and a
single peak at 2.theta.=60 to 64.degree. in the X-ray diffraction
(Cu-.alpha.).
[0022] In the present invention, it is desired that an X-ray
diffraction peak at 2.theta.=33 to 50.degree. is a single peak.
[0023] In the present invention, further, it is desired that the
trivalent metal (M.sup.3) in the above formula is aluminum, and the
divalent metal (M.sup.2) in the above formula is magnesium. When
M.sup.2 is magnesium, it is desired that (a+b)/x is not larger than
2.0. When a is zero, it is allowed that b/x is not larger than
2.5.
[0024] In the present invention, it is desired that the anions (A)
in the above formula are sulfuric acid ions. The sulfuric acid ions
have anion-exchanging property, and can be exchanged with carbonic
acid ions, organocarboxylic acid ions, phoshoric acid ions, silicic
acid ions (inclusive of condensed silicic acid ions), oxygen acid
ions of halogen, aluminic acid ions or sulfonic acid ions.
[0025] The composite metal polybasic salt of the present invention
exhibits X-ray diffraction peaks at the above-mentioned Bragg angle
(irradiation angle theta). For example, the Al--Zn--SO.sub.4
composite metal polybasic salt of Example 3 has the following X-ray
diffraction image:
1 2 .theta. Relative intensity 10.97.degree. 100% 21.03.degree. 35%
34.27.degree. 57% 60.97.degree. 38%
[0026] Among the above X-ray diffraction peaks, a peak at
2.theta.=33 to 50.degree. is singular, and a laminate asymmetric
index (Is) defined by the following formula (2),
Is=tan .theta..sub.2/tan .theta.hd 1 (2)
[0027] wherein .theta..sub.1 is an angle subtended by a peak
perpendicular in the X-ray diffraction peak of a predetermined
spacing and a peak tangent on the narrow angle side, and
.theta..sub.2 is an angle subtended by the peak perpendicular at
the above peak and a peak tangent on the wide angle side,
[0028] is not smaller than 1.5 at a peak of 2.theta.=33 to
50.degree..
[0029] According to the present invention, there is further
provided a method of preparing a composite metal polybasic salt by
reacting a water-soluble salt of a trivalent metal with an oxide, a
hydroxide or a water-soluble salt of a zinc metal and a divalent
metal under the conditions of a pH of from 3.8 to 9.0 and a
temperature of not lower than 50 .ANG.KC and, preferably, not lower
than 80.degree. C. and, if necessary, executing the ion exchange in
the presence of an acid or a soluble salt of acid.
[0030] According to the present invention, further, there is
provided an additive for resins, a heat insulator and an
anion-exchanger comprising the composite metal polybasic salt.
[0031] In the anion-exchanger, it is desired that the anions of the
composite metal polybasic salt are sulfuric acid ions.
BRIEF DESCRIPTION OF DRAWINGS
[0032] FIG. 1 is a diagram comparing infrared-ray absorption
spectra of zinc-modified composite metal polybasic salts which are
the products of the present invention with that of a
hydrotalcite;
[0033] FIG. 2 is a diagram illustrating an X-ray diffraction image
of an Al--Zn-type composite metal polybasic salt of the present
invention;
[0034] FIG. 3 is a diagram illustrating an X-ray diffraction image
of an Al--Zn--Mg-type composite metal polybasic salt of the present
invention;
[0035] FIG. 4 is a diagram illustrating an X-ray diffraction image
of a known magaldrate;
[0036] FIG. 5 is a diagram-illustrating an X-ray diffraction image
of a USP standard magaldrate;
[0037] FIG. 6 is a diagram illustrating an X-ray diffraction image
of a Zn-type hydrotalcite;
[0038] FIG. 7 is a diagram illustrating an X-ray diffraction image
of a salt of lithium aluminum composite hydroxide;
[0039] FIG. 8 is a diagram illustrating how to find a laminate
asymmetric index;
[0040] FIG. 9 is a scanning-type electron microphotograph showing
the granular structure of the Al--Zn-type composite metal polybasic
salt in which the anions are sulfuric acid ions;
[0041] FIG. 10 is a scanning-type electron microphotograph showing
the granular structure of the Al--Zn--Mg-type composite metal
polybasic salt in which the anions are sulfuric acid ions;
[0042] FIG. 11 is a scanning-type electron microphotograph showing
the granular structure of the Al--Zn-type composite metal polybasic
salt in which the anions are stearic acid ions;
[0043] FIG. 12 is a diagram illustrating a relationship between the
feeding molar ratio of Zn/M.sup.3+ in the starting materials and
the molar ratio of Zn/M.sup.3+ in the product in relation to the
Al--Zn-type composite metal polybasic salt which is the product of
the present invention;
[0044] FIG. 13 is a diagram illustrating an increase in the molar
ratio of SO.sub.3/Al in the product accompanying an increase in the
molar ratio of Zn/Al in relation to the Al--Zn-type composite metal
polybasic salt which is the product of the present invention;
[0045] FIG. 14 is a diagram illustrating X-ray diffraction images
of a product of when the feeding molar ratio Zn/Al of starting
materials is changed in relation to the Al--Zn-type composite metal
polybasic salt which is the product of the present invention;
and
[0046] FIG. 15 is a diagram illustrating X-ray diffraction images
of a product of when the feeding molar ratio Zn/(Zn+Mg) of starting
materials is changed in relation to the Al--Zn--Mg-type composite
metal polybasic salt which is the product of the present
invention.
BEST MODE FOR CARRUING OUT THE INVENTION
Composite Metal Polybasic Salt
[0047] A first feature of the composite metal polybasic salt
(hereinafter often referred to as PBS) of the present invention is
that it has a chemical composition expressed by the above-mentioned
formula (1). That is, the number x of mols of the trivalent metal,
the number (a+b) of mols of the divalent metal, the number y of
mols of hydroxyl groups and the number z of mols of anions all lie
within ranges satisfying the above formulas (i) to (iii).
[0048] A hydrotalcite which is a representative example of the
known composite metal polybasic salt or of the composite metal
hydroxide salt, typically, has a chemical composition expressed by
the following formula (4),
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.nH.sub.2O (4)
[0049] and (a+b)/x in the above-mentioned formula (iii) corresponds
to 3.0. In the composite metal polybasic salt of the present
invention, however, (a+b)/x is not larger than 2.5 and,
particularly, not larger than 2.0, and has a chemical composition
different from that of the hydrotalcite.
[0050] A zinc-modified hydrotalcite has a chemical composition
expressed by the following formula (5),
[Mg.sub.yZn.sub.z].sub.1-xAl.sub.x(OH).sub.2A.sub.x/n.mH.sub.2O
(5)
[0051] wherein A is a divalent or a monovalent anion, y, z and x
are numbers satisfying the conditions 0.15<z/(y+z)<0.4,
0<x<0.6, n is a valency of anion A, and m is an integer,
[0052] which is different from the chemical composition of the
composite metal polybasic salt of the present invention.
[0053] As another example of the composite metal polybasic salt,
there has been known a salt of lithium-aluminum composite hydroxide
salt represented by the following formula (6),
[Al.sub.2Li(OH).sub.6].sub.nX.mH.sub.2O (6).
[0054] This compound does not contain a divalent metal but contains
a monovalent metal, making a difference from the composite metal
polybasic salt of the present invention. Even if two mols of a
monovalent metal is equivalent to a mol of a divalent metal,
(a+b)/x in the above-mentioned formula (iii) corresponds to 0.25
when X is CO.sub.3 or SO.sub.3 (n=2). In the composite metal
polybasic salt of the present invention, (a+b)/x is not smaller
than 0.3 and its chemical composition is also different from that
of the known salt of lithium aluminum composite hydroxide.
[0055] It is considered that the composite metal polybasic salt of
the present invention has the following chemical structure. In this
compound, a [Zn-M.sup.2+](OH).sub.6 octahedral layer of which
[Zn-M.sup.2+] is isomorphous-substituted by M.sup.3+ serves as a
basic layer, and anions such as sulfuric acid radicals are
incorporated among the basic layers in a form to be balanced with
excess of cations due to the substitution. The layered crystal
structure is formed by a stack of many basic structures.
[0056] Anions such as sulfuric acid radicals present in the
composite metal polybasic salt have anion-exchanging property and
can be substituted with carbonic acid ions, organocarboxylic acid
ions, phosphoric acid ions, silicic acid ions (condensed silicic
acid ions), oxygen acid ions of halogen, aluminic acid ions or
sulfonic acid ions.
[0057] The content Qo (milliequivalent/100 g) of sulfuric acid
radicals in the composite metal polybasic salt is from 290 to 270
milliequivalent/100 g.
[0058] As the divalent metal M.sup.2+ constituting the composite
metal polybasic salt of the present invention, there can be
exemplified Be, Mg, Ca, Ba, Sr, Cd, Mn, Fe, Co, Ni, Cu, Pd, Sn, Pt
and Pb. Among them, a metal of the Group II of periodic table and,
particular, Mg is preferred.
[0059] As the trivalent metal M.sup.3+ constituting the composite
metal polybasic salt, there can be exemplified Al, Sc, Ti, V, Cr,
Mn, Fe, Co, Ni, Ga, Y, Ru, Rh, In, Sb, La, Ce, Nd, Pm, Sm, Eu, Gd,
Tb, Dy, Ho, Er, Tm, Yb, Lu, Os, Ir, Au, Bi, Ac and Th. Among them,
Al is preferred.
[0060] As the anions A constituting the composite metal polybasic
salt, there can be exemplified inorganic anions and organic anions.
As the inorganic anions, there can be exemplified oxygen acid ions
such as of S, P, Al, Si, N, B, V, Mn, Mo, W, Cr, Te and Sn, as well
as carbonic acid anions.
[0061] As the organic anions, there can be exemplified carboxylic
acid anions such as of acetic acid, propionic acid, butyric acid,
palmitic acid, stearic acid, myristic acid, oleic acid, linolic
acid, adipic acid, fumaric acid, maleic acid, citric acid, tartaric
acid, malic acid, cyclohexanecarboxylic acid, benzoic acid,
salicylic acid, phthalic acid and terephthalic acid; sulfonic acid
ions such as of methane sulfonic acid, toluene sulfonic acid,
lignin sulfonic acid and dodecylbenzene sulfonic acid; aromatic
primary amines such as sulfanilic acid, aniline, o-toluidine,
m-toluidine, metanilic acid and benzylamine as well as hydrochloric
acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid
and hydrofluoric acid thereof.
[0062] FIG. 1 in the accompanying drawings shows infrared-ray
absorption spectra of the composite metal polybasic salts of the
present invention in comparison with the infrared-ray absorption
spectrum of a hydrotalcite.
[0063] That is, FIG. 1(A) is an infrared-ray absorption spectrum of
an Al--Zn-type composite metal polybasic salt in which the anions
are sulfuric acid ions, FIG. 1(B) is an infrared-ray absorption
spectrum of an Al--Zn--Mg-type composite metal polybasic salt in
which the anions are sulfuric acid ions, FIG. 1(C) is an
infrared-ray absorption spectrum of an Al--Zn-type composite metal
polybasic salt in which the anions are monohydrogen phosphoric acid
ions, FIG. 1(D) is an infrared-ray absorption spectrum of an
Al--Zn--Mg-type composite metal polybasic salt in which the anions
are monohydrogen phosphoric acid ions, FIG. 1(E) is an infrared-ray
absorption spectrum of an Al--Zn-type composite metal polybasic
salt in which the anions are stearic acid ions, FIG. 1(F) is an
infrared-ray absorption spectrum of an Al--Zn--Mg-type composite
metal polybasic salt in which the anions are stearic acid ions,
FIG. 1(G) is an infrared-ray absorption spectrum of an Al--Zn-type
composite metal polybasic salt in which the anions are silicic acid
ions, and FIG. 1(H) is an infrared-ray absorption spectrum of a
hydrotalcite in which the anions are carbonic acid ions.
[0064] From these infrared-ray absorption spectra, it is learned
that the composite metal polybasic salts of the present invention
exhibit characteristic absorptions due to the hydroxyl group at
wave numbers of from 3800 to 2700 cm.sup.-1 and characteristic
absorptions due to the incorporated anions at wave numbers of from
900 to 1500 cm.sup.-1. In particular, the composite metal polybasic
salts of the present invention exhibit sharp absorption peaks in
the far infrared regions of a wave number of not larger than 2000
cm.sup.-1, and are useful as a heat insulator for absorbing heat
rays.
[0065] Further, the Al--Zn-type composite metal polybasic salt in
which the anions are stearic acid ions, exhibits characteristic
absorptions due to the methylene group at wave numbers of from 3000
to 2800 cm.sup.-1 and characteristic absorptions due to carboxylate
ions at wave numbers of from 1650 to 1500 cm.sup.-1.
[0066] The composite metal polybasic salt (PBS) of the present
invention has a novel crystal structure which is quite different
from those of the hydrotalcite and a salt of lithium aluminum
composite hydroxide.
[0067] FIG. 2 in the attached drawings shows an X-ray diffraction
image of the PBS of the Al--Zn type according to the present
invention, and FIG. 3 shows an X-ray diffraction image of the PBS
of the Al--Zn--Mg type according to the present invention.
[0068] FIGS. 4 and 5 are diagrams of X-ray diffraction images of
known magaldrates, FIG. 6 is a diagram of an X-ray diffraction
image of a zinc-type hydrotalcite, and FIG. 7 is a diagram of an
X-ray diffraction image of a salt of lithium aluminum composite
hydroxide.
[0069] The composite metal polybasic salt of the present invention
in which the anions are sulfuric acid ions exhibits substantially
four diffraction peaks in the X-ray diffraction (Cu-.alpha.) at
2.theta.=10 to 12.degree., 2.theta.=20 to 22.degree., 2.theta.=33
to 50.degree. and 2.theta.=60 to 64.degree., the diffraction peak
at 2.theta.=60 to 64.degree. being a single peak and, preferably,
the diffraction peak at 2.theta.=33 to 50.degree. being a single
peak, too.
[0070] On the other hand, the hydrotalcite (FIG. 6) exhibits two
diffraction peaks in the range of 2.theta.=38 to 50.degree., and
another two diffraction peaks in the range of 2.theta.=60 to
63.degree.. Thus, the above two compounds exhibit quite different
X-ray diffraction images.
[0071] Further, the known magaldrate exhibits diffraction peaks at
2.theta.=10 to 12.degree., 2.theta.=22 to 24.degree., 2.theta.=33
to 35.degree., 2.theta.=38 to 40.degree., 2.theta.=45 to 47.degree.
and 2.theta.=60 to 64.degree.. Thus, the two compounds exhibit
quite different X-ray diffraction images.
[0072] Similar differences are also recognized even in the case of
a salt of lithium aluminum composite hydroxide (FIG. 7).
[0073] From the diffraction peaks of the X-ray diffraction images
of the plane (001) at 2.theta.=10 to 12.degree. of the composite
metal polybasic salt of the present invention and the magaldrate,
further, it will be leaned that the crystals of the composite metal
polybasic salt of the invention are developing in the direction of
the C-axis. Further, the composite metal polybasic salt which is a
product of the present invention has a degree of orientation
(I.sub.0) represented by the following formula (3),
I.sub.0=I.sub.11/I.sub.61 (2)
[0074] wherein I.sub.11 is an X-ray diffraction peak intensity at
2.theta.=10 to 12.degree., and I.sub.61 is an X-ray diffraction
peak intensity at 2.theta.=60 to 64.degree.,
[0075] of larger than 2, which is quite different from that of the
known magaldrate (I.sub.0<1). From this fact, the composite
metal polybasic salt which is a product of the present invention
has a large particle composed of primary particles that are
expanding in the direction of AB-axis. The primary particle is
composed of the basic layer. Accordingly, the product of the
present invention disperses well in the resin making it possible to
strikingly improve transparency of the blended resin,
chlorine-trapping property, resistance against acid and heat
resistance.
[0076] As will be obvious from FIG. 8, further, the composite metal
polybasic salt of the present invention has a feature in the X-ray
diffractive fine structure called laminate asymmetry.
[0077] That is, it is obvious that the diffraction peak at
2.theta.=33 to 50.degree. exhibited by the composite metal
polybasic salt of the present invention is an asymmetric peak.
[0078] In other words, it will be understood that the asymmetric
peak rises relatively sharply on the narrow angle side (side on
where 2.theta. is small) and is mildly inclined on the wide angle
side (side on where 2.theta. is large). The asymmetric peak becomes
conspicuous particularly at 2.theta.=33 to 50.degree.. Asymmetry
similarly appears even at a peak of 2.theta.=60 to 64.degree.
though the degree of asymmetry is small.
[0079] In this specification, the laminate asymmetric index (Is) is
defined as described below. That is, an X-ray diffraction chart
shown in FIG. 8 is obtained by a method described in an Example
appearing later. A maximum inclination peak tangent a on the narrow
angle side and a maximum inclination peak tangent b on the broad
angle side, are drawn on a peak at 2.theta.=33 to 50.degree., and a
perpendicular c is drawn from a point where the tangent a
intersects the tangent b. Next, an angle .theta.1 subtended by the
tangent a and the perpendicular c, and an angle .theta.2 subtended
by the tangent b and the perpendicular c, are found. The laminate
asymmetric index (Is) is found from these angles in compliance with
the above formula (2).
[0080] The laminate asymmetric index (Is) is 1.0 when the peak is
completely symmetrical, and increases as the breaking angle becomes
larger than the rising angle.
[0081] The laminate asymmetric index (Is) has the following
meaning. It was pointed out already that the PBS of the present
invention has a laminar crystal structure in which basic layers of
M.sup.2.sub.aZn.sub.bM.sup.3.sub.x(OH).sub.y are stacked one upon
the other. However, it is believed that the sizes (lengths and
areas) of the basic layers are not uniform but are varying over
wide ranges and, besides, the basic layers are twisted or curved
forming a structure which is not plane.
[0082] In the PBS of the present invention, therefore, the anions
easily exchange ions offering a large ion-exchange capacity and a
large ion-exchange rate. When this is used as an additive for a
resin for trapping, for example, chlorine ions, then, an excellent
ability is exhibited.
[0083] When heated from room temperature up to a temperature of
200.degree. C., the composite metal polybasic salt of the present
invention exhibits a weight reduction ratio of not larger than 15%
by weight and, particularly, not larger than 5% by weight, and
offers a distinguished advantage that it does not develop foaming
at a resin-working temperature when it is mixed into the resin. The
hydrotalcite has a defect of developing foaming as the water
separates at the resin-working temperature. The composite metal
polybasic salt of the present invention is free from this
problem.
[0084] The hydrotalcite exhibits a very large endothermic peak due
to the vaporization of water in a temperature range of from 190 to
240.degree. C., whereas the PBS does not exhibit such a large
endothermic peak proving its excellent resistance against the
foaming.
[0085] The composite metal polybasic salt of the present invention
varies the surface area to a large extent depending upon the kind
of anions to be exchanged, and, for example, possesses a small
specific surface area and a small porous volume when the anions are
sulfuric acid ions. In this case, the PBS of the present invention
has a BET specific surface area of not larger than 10 m.sup.2/g
and, particularly, in a range of from 0.3 to 7 m.sup.2/g, and a
porous volume of those pores having diameters of from 17 to 3000
angstroms as found by the BJH method of from 0.0005 to 0.05 ml/g
and, particularly, from 0.02 to 0.035 ml/g. When the anions are
silicic acid ions, on the other hand, the PBS of the present
invention has a large specific surface area and a large porous
volume, e.g., has the BET specific surface area of about 150
m.sup.2/g and the porous volume of those pores having diameters of
from 17 to 3000 angstroms of about 0.4 ml/g as found by the BJH
method.
[0086] The composite metal polybasic salt of the present invention
has a volume based median diameter (D.sub.50) of, generally, from
0.1 to 50 .mu.m and, particularly, from 2 to 10 .mu.m as measured
by the laser diffraction method.
[0087] The particles have various shapes ranging from a plate-like
crystalline particulate shape to an agglomerated shape depending
upon the kind of divalent metal M.sup.2+ of the composite metal
polybasic salt.
[0088] FIGS. 9 and 10 are scanning-type electron microphotographs
showing the granular structures of an Al--Zn-type composite metal
polybasic salt and of an Al--Zn--Mg-type composite metal polybasic
salt in which the anions are sulfuric acid ions, and FIG. 11 is a
scanning-type electron microphotograph showing the granular
structure of an Al--Zn-type composite metal polybasic salt in which
the anions are stearic acid ions.
[0089] From these photographs, the Al--Zn-type composite metal
polybasic salt comprises primary particles which are plate-like
crystalline particles.
Method of Preparation
[0090] According to the present invention, the composite metal
polybasic salt is prepared by reacting a water-soluble salt of a
trivalent metal with an oxide, a hydroxide or a water-soluble salt
of zinc alone or of zinc and a divalent metal under the conditions
of a pH of from 3.8 to 9.0 and a temperature of not lower than
50.degree. C. and, if necessary, executing the ion exchange in the
presence of an acid or a soluble salt of acid.
[0091] As the water-soluble salt of a trivalent metal such as Al or
the like, there can be used any one of a chloride, a nitrate or a
sulfate that is soluble in water. From the standpoint of easy
synthesis, however, it is desired in the present invention to
synthesize the composite metal polybasic salt in the form of a
sulfate. It is therefore most desired to use the composite metal
polybasic salt in the form of a sulfate.
[0092] The starting Zn and divalent metal can be used in any form
of an oxide, a hydroxide or a water-soluble salt. From the
standpoint of synthesis, however, it is most convenient to use an
oxide such as zinc flower or a hydroxide such as magnesium
hydroxide. Even when a water-soluble salt such as a chloride, a
nitrate or a sulfate of zinc and a divalent metal is used, it is
possible to synthesize a composite metal polybasic salt according
to the present invention by controlling the pH in the control
system to lie within the above-mentioned range, as a matter of
course.
[0093] In the present invention, it is important to carry out the
reaction of the above-mentioned starting materials while
maintaining the pH at the time when the reaction is finished to lie
within a range of from 3.8 to 9.0 and, particularly, from 4.0 to
8.0, and maintaining the reaction temperature to be not lower than
50.degree. C. and, particularly, from 80 to 180.degree. C.
[0094] When the pH of the reaction system lies outside the above
range, it becomes difficult to form the composite metal polybasic
salt. That is, the composite metal polybasic salt has a feature in
that it possesses both the hydroxyl group and the anionic group
that are bonded. When the pH becomes larger than the above range,
it becomes difficult to introduce the anionic group. When the pH
becomes smaller than the above range, on the other hand, it becomes
difficult to introduce the hydroxyl group.
[0095] When the temperature becomes lower than the above-mentioned
range, it becomes difficult to synthesize the composite metal
polybasic salt.
[0096] The reacting and mixing ratio of the trivalent metal
compound and zinc alone or zinc and the divalent metal compound is
so set that the composition ratio of the above-mentioned general
formula (1) is satisfied. In general, the molar ratio of
(Zn+M.sup.2+)/M.sup.3+ in the product tends to become smaller than
the feeding molar ratio of (Zn+M.sup.2+)/M.sup.3+ in the starting
material.
[0097] FIG. 12 in the accompanying drawing illustrates a
relationship between the feeding molar ratio of Zn/Al in the
starting material and the molar ratio of Zn/Al in the product in
relation to the Al--Zn-type composite metal polybasic salt. The
relationship between the two is almost linear, from which it will
be understood that the molar ratio of Zn/Al in the final product
can be determined by determining the feeding molar ratio.
[0098] When ZnO is used as the starting M.sup.2 material and
Al.sub.2(SO.sub.4).sub.3 is used as a starting M.sup.3 material, it
is desired that the feeding molar ratio of Zn/M.sup.3+ is in a
range of from 2.0 to 4.0 and, particularly, from 2.0 to 3.6.
[0099] There also exists a predetermined relationship among the
feeding molar ratio of Zn/M.sup.3+ in the starting material, the
molar ratio of Zn/M.sup.3+ in the product and the molar ratio of
A/M.sup.3+ in the product. In general, the molar ratio of
A/M.sup.3+ in the product increases with an increase in the molar
ratio of Zn/M.sup.3+.
[0100] FIG. 13 illustrates a relationship between the above two,
from which it will be learned that the molar ratio of SO.sub.3/Al
in the product monotonously increases with an increase in the molar
ratio of Zn/Al.
[0101] This phenomenon is considered to be as described below.
[0102] It was pointed out already that in the PBS of the present
invention, a [Zn-M.sup.2+](OH).sub.6 octahedral layer of which
[Zn-M.sup.2+] is isomorphous-substituted by M.sup.3+ serves as a
basic layer, and anions such as sulfuric acid radicals are
incorporated among the basic layers in a form to be balanced with
excess of cations due to the substitution. When the sulfuric acid
radicals are all incorporated in a form to be balanced by excess of
cations, the molar ratio of SO.sub.3/Al becomes 0.5. Therefore, the
fact of FIG. 13 tells that in a state where the molar ratio of Al
is small, nearly ideal state holds. However, as the molar ratio of
Al increases, the degree of incorporation of the sulfuric acid
radicals decreases and the bonds with the hydroxyl groups
increase.
[0103] FIG. 14 shows an X-ray diffraction image of a product of
when the feeding molar ratio Zn/Al of the starting material is
changed in relation to the Al--Zn composite metal polybasic salt.
These results tell that the crystal structure of the present
invention is stably formed when the molar ratio of Zn/Al lies
within a range of from 2.4 to 3.6.
[0104] FIG. 15 shows an X-ray diffraction image of the Al--Zn--Mg
composite polybasic salt of when the molar ratio Zn/(Zn+Mg) of the
product is changed. These results tell that the crystal structure
of the present invention is stably formed within a range of
0<Zn/(Zn+Mg) mol %.ltoreq.100.
[0105] In synthesizing the composite metal polybasic salt of the
present invention, there is no particular limitation on the order
of mixing the two starting materials. For example, an aqueous
solution or slurry of an oxide of zinc alone or of zinc and a
divalent metal, of a hydroxide thereof or of water-soluble salts
thereof may be added to an aqueous solution of trivalent metal
salts. Conversely, an aqueous solution of trivalent metal salts may
be added to an aqueous solution or slurry of an oxide of zinc alone
or of zinc and a divalent metal, of a hydroxide thereof or of
water-soluble salts thereof, or they may be simultaneously added
together.
[0106] The reaction can be completed by maintaining the reaction
mixture at the above-mentioned temperature for about 2 to 72 hours
with stirring. Though not generally required, the reaction may be
conducted under the hydrothermal conditions by using a pressurized
container. The reaction product is washed with water, subjected to
the solid-liquid separation operation such as filtration, dried at
60 to 150.degree. C., and, if necessary, is heat-treated at 150 to
230.degree. C. to obtain a product.
[0107] In the composite metal polybasic salt of the present
invention, a variety of anions can be introduced by the
ion-exchange method. As the starting composite metal polybasic salt
to be used for the anion-exchange, it is desired to use the
composite metal polybasic salt of the sulfuric acid type.
[0108] As the anions to be subjected to the ion-exchange, there is
used an alkali metal salt such as sodium salts of the
above-mentioned anions. For example, a sodium bicarbonate or a
sodium carbonate is used for introducing carboxylic acid radicals,
a sodium carboxylate or a sodium sulfonate is used for introducing
organic acid anions, a sodium phosphate, a monohydrogen sodium
phosphate or a dihydrogen sodium phosphate is used for introducing
phosphoric acid radicals, and a sodium silicate is used for
introducing silicic acid radicals, to which only, however, the
invention is in no way limited.
[0109] Anions based on the ion exchange can be introduced by
bringing a composite metal polybasic salt of the sulfuric acid type
in the form of a powder or a wet cake into uniform contact with an
aqueous solution of a salt of the above-mentioned anions at a
temperature of from 0 to 100.degree. C. In general, the
ion-exchange processing is completed by executing the contact for
from about 5 minutes to about 3 hours.
[0110] The obtained product is subjected to the filtration, washing
with water, drying and, if necessary, to the pulverization and
classification to obtain a product.
[0111] The composite metal polybasic salt of the present invention
can be used in its own form as an additive for resins, as an
anion-exchanger or as a heat insulator. If necessary, however, it
may be coated with an organic assistant or an inorganic assistant
and can, then, be used for a variety of applications.
[0112] As the organic assistant, there can be exemplified such
coating agents as metal soaps such as calcium salt, zinc salt,
magnesium salt and barium salt of stearic acid, palmitic acid or
lauric acid; silane coupling agent, aluminum coupling agent,
titanium coupling agent, zirconium coupling agent, various waxes,
and unmodified or modified resins (e.g., rosin, petroleum resin,
etc.). The composite metal polybasic salt of the present invention
can be treated for its surfaces with the above coating agent and
can be used for a variety of applications.
[0113] It is desired to use the coating agent in an amount of from
0.5 to 10% by weight and, particularly, from 1 to 5% by weight with
respect to the PBS.
[0114] As the inorganic assistant, there can be exemplified regular
particles of fine particulate silica such as aerosil and
hydrophobically treated aerosil, silicates such as calcium silicate
and magnesium silicate, metal oxides such as calcia, magnesia and
titania, metal hydroxide such as magnesium hydroxide and aluminum
hydroxide, metal carbonates such as calcium carbonate, synthetic
zeolites of the A-type, P-type, etc, and acid-treated products
thereof or metal ion-exchanged product thereof, with which the PBS
can be blended or sprinkled.
[0115] It is desired to use these inorganic assistants in an amount
of from 0.01 to 200% by weight and, particularly, from 0.1 to 100%
by weight per the PBS.
[0116] As additives, there may be further blended urea,
ethyleneurea, propyleneurea, 5-hydroxypropyleneurea,
5-methoxypropyleneurea, 5-methylpropyleneurea, parabanic acid,
4,5-dimethoxyethyleneurea, pyrrolidene, piperidine, morpholine,
dicyandiamide, 2-hydrazobenzothiazole, potassium permanganate,
benzalkonium chloride, iodophor, hydrazine, hydrazine sulfate,
aluminum sulfate hydrazine sulfate complex salt, organic/inorganic
antibacterial agent (iodophor and silver-exchanged zeolite), and
optical catalyst (anatase-type titanium oxide, etc.).
Use
[0117] The PBS of the present invention has excellent properties as
described above. By utilizing these properties, the PBS can be used
in such applications as an additive for resins, an ion
(anion)-exchanger, a heat insulator, a base member for cosmetics, a
de-odoring/antibacterial agent, a flame retardant, an ultraviolet
ray-absorbing agent, a nanocomposite starting material, etc.
[0118] The composite metal polybasic salt of the present invention
is useful as an additive for thermoplastic resins, thermosetting
resins and various rubbers.
[0119] That is, the composite metal polybasic salt of the present
invention does not develop foaming that is caused when the water
separates at the resin-working temperature, can be easily blended
in the resin, and exhibits excellent heat stability since it
contains components such as zinc alone or zinc and divalent metals,
trivalent metal components and hydroxyl groups that impart
heat-stabilizing property to the resins. Besides, the composite
metal polybasic salt has anion-exchanging property and exhibits
excellent property for trapping chlorine ions. Moreover, the
composite metal polybasic salt absorbs far infrared rays and
exhibits excellent heat-retaining property.
[0120] Besides, the product of the invention containing zinc
exhibits excellent antibacterial property and de-odoring
property.
[0121] Thus, the composite metal polybasic salt of the present
invention can be blended in the resins as a heat stabilizer, as a
halogen catcher, as a heat-retaining agent, as an antibacterial
agent, as a de-odoring agent or as an anti-blocking agent.
[0122] As the thermoplastic resin to be blended with the composite
metal polybasic salt of the present invention, there can be
preferably exemplified an olefin resin and, particularly, a low-,
an intermediate- or a high-density polyethylene, an isotactic
polypropylene, a syndiotactic polypropylene, or a polypropylene
polymer which is a copolymer thereof with an ethylene or an
.alpha.-olefin, a linear low-density polyethylene, an
ethylene/propylene copolymer, a polybutene-1, an ethylene/butene-1
copolymer, a propylene/butene-1 copolymer, an
ethylene/propylene/butene-1 copolymer, an ethylene/vinyl acetate
copolymer, an tonically crosslinked olefin copolymer (ionomer), or
an ethylene/acrylic acid ester copolymer, which may be used in a
single kind or being blended in two or more kinds.
[0123] The additive for resins of the present invention can also be
used for other known resin films, fibers and resin-molded articles,
such as polyamides like nylon 6, nylon 6-6, nylon 6-10, nylon 11
and nylon 12, thermoplastic polyesters such as polyethylene
terephthalate and polybutylene terephthalate, as well as
polycarbonate, polysulfone, vinyl chloride resin, vinylidene
chloride resin and vinyl fluoride resin.
[0124] When used as a blending agent for resins, it is desired that
the composite metal polybasic salt is used in an amount of from
0.01 to 200 parts by weight and, particularly, in an amount of from
0.1 to 100 parts by weight per 100 parts by weight of the
thermoplastic resin.
[0125] The thermoplastic resins, various rubbers and thermosetting
resins can be blended with the composite metal polybasic salt of
the present invention as an additive for modifying the resins.
[0126] As the elastomer polymer for rubbers, there can be
exemplified a nitrile-butadiene rubber (NBR), a styrene-butadiene
rubber (SBR), a chloroprene rubber (CR), a polybutadiene (BR), a
polyisoprene (PI), a butyl rubber, a natural rubber, an
ethylene-propylene rubber (EPR), an ethylene-propylene-diene rubber
(EPDM), a polyurethane, a silicone rubber and an acrylic rubber. As
the thermoplastic elastomer, there can be exemplified a
styrene-butadiene-styrene block copolymer, a
styrene-isoprene-styrene block copolymer, a hydrogenated
styrene-butadiene-styrene block copolymer, a hydrogenated
styrene-isoprene-styrene block copolymer, and a partially
crosslinked olefinic thermoplastic elastomer.
[0127] As the thermosetting resin, there can be exemplified a
phenol-formaldehyde resin, a furan-formaldehyde resin, a
xylene-formaldehyde resin, a ketone-formaldehyde resin, a
urea-formaldehyde resin, a melamine-formaldehyde resin, an alkyd
resin, an unsaturated polyester resin, an epoxy resin, a
bismaleimide resin, a triallylcyanulate resin, a thermosetting
acrylic resin and a silicone resin, which may be used in a
combination of two or more kinds.
[0128] In this case, the composite metal polybasic salt of the
present invention is used in an amount of from 0.01 to 200 parts by
weight and, particularly, in an amount of from 0.1 to 100 parts by
weight per 100 parts by weight of the thermoplastic resin,
thermosetting resin or elastomer.
EXAMPLES
[0129] The present invention will now be described by way of
Examples to which only, however, the present invention is in no way
limited. The testing was conducted in compliance with the following
methods.
[0130] (1) X-ray diffraction measurement.
[0131] Measured for Cu-K.alpha. by using a RAD-IB system
manufactured by Rigaku Denki Co.
2 Target Cu Filter curved crystalline graphite monochrometer
Detector SC Voltage 40 KVP Current 20 mA Count full-scale 700 c/s
Smoothing point 25 Scanning speed 1.degree./min Step sampling
0.02.degree. Slit DS1.degree. RS 0.15 mm SS1.degree. Irradiating
angle 6.degree.
[0132] (2) Infrared ray absorption spectral analysis.
[0133] Measured by using an infrared absorption spectral analyzer,
Model A-302, manufactured by Nippon Bunko Co.
[0134] (3) Differential thermal analysis.
[0135] Measured by using a TAS-100-TG8110 manufactured by Rigaku
Co. under the measuring conditions of using a standard substance
.alpha.-Al.sub.2O.sub.3, raising the temperature at a rate of
10.degree. C./min. in the air at 20 to 320.degree. C.
[0136] (4) Observation using a scanning-type electron
microscope.
[0137] Observed by using a scanning electron microscope, S-570,
manufactured by Hitachi, Ltd.
[0138] (5) Specific surface area/porous volume.
[0139] Measured in compliance with the BET method by using
Sorptomatic Series 1900 manufactured by Carlo Erba Co.
[0140] (6) Average particle diameter.
[0141] The average particle diameter (median diameter; .mu.m) was
measured by using a laser-diffraction particle size analyzer
(Coulter R LS-130) manufactured by Coulter Co.
Example 1
[0142] 221.58 Grams of zinc oxide of a purity of 99.6% and
ion-exchanged water were added into a 2000-ml beaker so that the
total volume was 750 ml, and the mixture was stirred and dispersed
to prepare a ZnO slurry.
[0143] 720 Grams of an aluminum sulfate (Al.sub.2O.sub.3=7.68%,
SO.sub.3=18.1%) was gradually poured into the ZnO slurry at room
temperature with stirring, and the mixture was messed-up to 1500
ml. Thereafter, the temperature was elevated to 90.degree. C. to
conduct the reaction for 5 hours.
[0144] After the reaction, the reaction product was filtered,
washed with 3000 ml of hot water, dried at 110.degree. C. and was
pulverized to obtain a white powder.
[0145] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
3 Al.sub.1.00Zn.sub.1.44(OH).sub.4.99(SO.sub.4).sub.0.45.1.-
0H.sub.2O 2 .theta. Relative intensity 11.03.degree. 100%
21.40.degree. 32% 34.27.degree. 45% 60.87.degree. 26%
Example 2
[0146] A white powder was obtained through the same operation as in
Example 1 but changing the reaction time to 25 hours.
[0147] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
4 Al.sub.1.00Zn.sub.1.48(OH).sub.5.09(SO.sub.4).sub.0.43.1.-
0H.sub.2O 2 .theta. Relative intensity 10.73.degree. 100%
20.63.degree. 33% 34.13.degree. 46% 60.93.degree. 28%
Example 3
[0148] A white powder was obtained through the same operation as in
Example 1 but changing the amount of zinc oxide into 265.90 g.
[0149] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
5 Al.sub.1.00Zn.sub.1.92(OH).sub.5.89(SO.sub.4).sub.0.48.0.-
9H.sub.2O 2 .theta. Relative intensity 10.97.degree. 100%
21.03.degree. 35% 34.27.degree. 57% 60.97.degree. 38%
[0150] An X-ray diffraction image of the polybasic salt is shown in
FIG. 9.
Example 4
[0151] 153.21 Grams of magnesium hydroxide (MgO=64.2%), 22.16 g of
zinc oxide of a purity of 99.6%, 14.56 g of ammonium chloride and
ion-exchanged water were added into a 2000-ml beaker so that the
total volume was 750 ml, and the mixture was stirred and dispersed
to prepare a Mg(OH).sub.2--ZnO mixture slurry.
[0152] 720 Grams of an aluminum sulfate (Al.sub.2O.sub.3=7.68%,
SO.sub.3=18.1%) was gradually poured into the slurry at room
temperature with stirring, and the mixture was messed-up to 1500
ml. Thereafter, the temperature was elevated to 90.degree. C. to
conduct the reaction for 5 hours.
[0153] After the reaction, the reaction product was filtered,
washed with 3000 ml of hot water, dried at 110.degree. C. and was
pulverized to obtain a white powder.
[0154] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
6 Al.sub.1.00Mg.sub.0.93Zn.sub.0.25(OH).sub.4.68(SO.sub.4).-
sub.0.34.1.3H.sub.2O 2 .theta. Relative intensity 10.29.degree.
100% 20.27.degree. 58% 35.37.degree. 24% 61.43.degree. 28%
Example 5
[0155] 136.19 Grams of magnesium hydroxide (MgO=64.2%), 45.20 g of
sodium hydroxide of a purity of 96% and ion-exchanged water were
added into a 2000-ml beaker so that the total volume was 750 ml,
and the mixture was stirred and dispersed to prepare a Mg(OH).sub.2
slurry.
[0156] 720 Grams of an aluminum sulfate (Al.sub.2O.sub.3=7.68%,
SO.sub.3=18.1%) and 300 g of a zinc sulfate aqueous solution
(ZnO=14.7%, SO.sub.3=14.5%) were gradually poured into the
Mg((OH).sub.2 slurry with stirring, and the mixture was messed-up
to 1500 ml. Thereafter, the temperature was elevated to 90.degree.
C. to conduct the reaction for 5 hours.
[0157] After the reaction, the reaction product was filtered,
washed with 3000 ml of hot water, dried at 110.degree. C. and was
pulverized to obtain a white powder.
[0158] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
7 Al.sub.1.00Mg.sub.0.72Zn.sub.0.51(OH).sub.4.77(SO.sub.4).-
sub.0.35.1.2H.sub.2O 2 .theta. Relative intensity 10.43.degree.
100% 20.49.degree. 50% 35.15.degree. 32% 61.44.degree. 30%
Example 6
[0159] 450 Grams of a zinc sulfate aqueous solution (ZnO=14.7%,
SO.sub.3=14.5%) and ion-exchanged water were added into a 2000-ml
beaker so that the total volume was 1000 ml. While stirring the
aqueous solution, an aqueous solution of sodium hydroxide was
gradually added thereto until the pH was 7.0, and the reaction was
continued for one hour. After the reaction, the reaction product
was filtered and washed with 6000 ml of hot water to obtain a
Zn(OH).sub.2 cake. The whole amount of the cake was dispersed in
the ion-exchanged water in a 2000-ml beaker and to which were
further added 119.16 g of magnesium hydroxide (MgO=64.2%) and the
ion-exchanged water so that the volume was 750 ml. The mixture was
stirred and dispersed to prepare a Mg(OH).sub.2--Zn(OH).sub.2
mixture slurry.
[0160] 720 Grams of an aluminum sulfate (Al.sub.2O.sub.3=7.68%,
SO.sub.3=18.1%) was gradually poured into the slurry at room
temperature with stirring, and the mixture was messed-up to 1500
ml. Thereafter, the temperature was elevated to 90.degree. C. to
conduct the reaction for 5 hours.
[0161] After the reaction, the reaction product was filtered,
washed with 3000 ml of hot water, dried at 110.degree. C. and was
pulverized to obtain a white powder.
[0162] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
8 Al.sub.1.00Mg.sub.0.52Zn.sub.0.75(OH).sub.4.77(SO.sub.4).-
sub.0.37.1.2H.sub.2O 2 .theta. Relative intensity 10.34.degree.
100% 20.51.degree. 49% 34.52.degree. 31% 61.03.degree. 27%
[0163] An X-ray diffraction image of the polybasic salt is shown in
FIG. 10.
Example 7
[0164] 1.79 Grams of NaOH was dissolved in 300 ml of ion-exchanged
water in a 500-ml beaker. 12.19 Grams of stearic acid was added
thereto, and the mixture was heated at 80.degree. C. and was
stirred to prepare a sodium stearate solution.
[0165] Separately, 10 g of the fine white powder obtained in
Example 3 was dispersed in 200 ml of ion-exchanged water. The
mixture was added to the above sodium stearate solution and was
heated at 90.degree. C. and was stirred for two hours. After the
reaction, the reaction product was filtered, washed with 1000 ml of
hot water and was dried at 110.degree. C. using a blower-drier
overnight.
[0166] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
9 Al.sub.1.00Zn.sub.1.48(OH).sub.5.09(C.sub.18H.sub.35O.sub-
.2).sub.0.43.0.4H.sub.2O 2 .theta. Relative intensity 2.26.degree.
22% 3.53.degree. 62% 5.30.degree. 61% 21.07.degree. 100%
34.17.degree. 45% 60.77.degree. 33%
[0167] The X-ray diffraction image of the polybasic salt is shown
in FIG. 11.
Example 8
[0168] 15.62 Grams of sodium stearate was dissolved in 300 ml of
ion-exchanged water in a 500-ml beaker, and was heated at
80.degree. C. and was stirred to prepare a sodium stearate
solution.
[0169] Separately, 10 g of the fine white powder obtained in
Example 6 was dispersed in 200 ml of ion-exchanged water. The
mixture was added to the above sodium stearate solution and was
heated at 90.degree. C. and was stirred for two hours. After the
reaction, the reaction product was filtered, washed with 1000 ml of
hot water and was dried at 110.degree. C. using a blower-drier
overnight.
[0170] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
10 Al.sub.1.00Mg.sub.0.52Zn.sub.0.75(OH).sub.4.81(C.sub.18H-
.sub.35O.sub.2).sub.0.37.0.6H.sub.2O 2 .theta. Relative intensity
2.26.degree. 17% 3.58.degree. 19% 7.20.degree. 51% 20.97.degree.
100% 35.37.degree. 13% 61.03.degree. 7%
Example 9
[0171] 9.39 Grams of Na.sub.2HPO.sub.4.12H.sub.2O (purity of 99%)
was introduced into a 500-ml beaker, and to which ion-exchanged
water was added to prepare 200 ml of an Na.sub.2HPO.sub.4
solution.
[0172] Separately, 10 g of the fine white powder obtained in
Example 2 was dispersed in 100 ml of ion-exchanged water. The
mixture was added to the above Na.sub.2HPO.sub.4 solution and was
heated at 90.degree. C. and was stirred for two hours. After the
reaction, the reaction product was filtered, washed with 1000 ml of
hot water, dried at 110.degree. C. for 12 hours, and was pulverized
to obtain a fine white powder.
[0173] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
11 Al.sub.1.00Zn.sub.1.49(OH).sub.5.17(HPO.sub.4).sub.0.41.-
1.0H.sub.2O 2 .theta. Relative intensity 8.10.degree. 68%
15.01.degree. 78% 22.58.degree. 100% 34.18.degree. 79%
61.20.degree. 63%
Example 10
[0174] A white powder was obtained through the same operation as in
Example 9 but using Na.sub.2HPO.sub.4.12H.sub.2O (purity, 99%) in
an amount of 9.13 g and using the fine white powder obtained in
Example 6 instead of the fine white powder obtained in Example
2.
[0175] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
12 Al.sub.1.00Mg.sub.0.58Zn.sub.0.80(OH).sub.5.10(HPO.sub.4-
).sub.0.33.1.2H.sub.2O 2 .theta. Relative intensity 8.50.degree.
43% 14.63.degree. 43% 22.50.degree. 100% 35.27.degree. 85%
61.37.degree. 77%
Example 11
[0176] 19.5 Grams of a sodium silicate solution No. 3
(SiO.sub.2=22.0%, Na.sub.2O=7.08%) was introduced into a 500-ml
beaker, and to which ion-exchanged water was added to prepare 200
ml of a sodium silicate aqueous solution.
[0177] Separately, 26.4 g of the reaction product (solid content of
37.9%) after washed obtained in Example 3 was dispersed in 100 ml
of ion-exchanged water. The mixture was added to the above sodium
silicate solution and was heated at 50.degree. C. and was stirred
for two hours. After the reaction, the reaction product was
filtered, washed with hot water, dried at 110.degree. C. for 12
hours and was pulverized to obtain a fine white powder.
[0178] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
13 Al.sub.1.00Zn.sub.1.92(OH).sub.5.89(SO.sub.4).sub.0.18(S-
i.sub.3O.sub.7).sub.0.30.1.3H.sub.2O 2 .theta. Relative intensity
8.80.degree. 100% 14.27.degree. 13% 22.21.degree. 43% 34.05.degree.
79% 60.70.degree. 57%
Comparative Example 1
[0179] Synthesis of a magaldrate.
[0180] 100.34 Grams of an aluminum sulfate (Al.sub.2O.sub.3=7.68%,
SO.sub.3=18.1%) was added to 1112.4 g of an Al(OH).sub.3 paste
(Al.sub.2O.sub.3=1.50%), and to which was further added 60.00 g of
magnesium hydroxide (MgO=64.2%) with vigorous stirring. And then,
the resulting mixture is left quietly for 24 hours to maintain the
reaction.
[0181] The paste after the reaction was dried at 110.degree. C. and
was pulverized to obtain a white powder.
[0182] From the X-ray analysis, the obtained fine powder was a
mixture of a magaldrate disclosed in Japanese Examined Patent
Publication (Kokoku) No. 58210/1990 and an aluminum hydroxide
(gibbsite).
[0183] FIG. 3 shows an X-ray diffraction image of the magaldrate
disclosed in Japanese Examined Patent Publication (Kokoku) No.
58210/1990 and FIG. 4 shows an X-ray diffraction image of a
USP-referred standard magaldrate. Since these drawings do not show
a scale of angles, the angles refer to values of the Journal of
Pharmaceutical Science, Vol. 6, p. 325, 1978.
14 2 .theta. Relative intensity 11.42.degree. 57% 23.22.degree. 44%
34.91.degree. 78% 39.16.degree. 30% 46.07.degree. 37% 60.95.degree.
100% 62.32.degree. 85%
Comparative Example 2
[0184] Synthesis of a zinc-modified hydrotalcite.
[0185] 37.0 Grams of NaOH (purity of 96%) and 11.16 g of
Na.sub.2CO.sub.3 (purity of 99.7%) were added to ion-exchanged
water with stirring, and the mixture was heated at 40.degree. C. To
this aqueous solution was gradually poured an aqueous solution
obtained by adding 45.96 g of MgCl.sub.2.6H.sub.2O (19.73% as MgO),
10.33 g of ZnCl.sub.2 (59.12% as ZnO) and 37.33 g of
AlCl.sub.3.6H.sub.2O (20.48% as Al.sub.2O.sub.3) to 500 ml of
ion-exchanged water, such that the molar ratio of CO.sub.3/Al was
0.7. The mixture was hydrothermally reacted at 170.degree. C. for
20 hours with stirring.
[0186] After the reaction, the reaction product was filtered,
washed with 6000 ml of hot water, dried at 110.degree. C. and was
pulverized to obtain a white powder.
[0187] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
15 Al.sub.6Mg.sub.1.5Zn.sub.0.5(OH).sub.16(CO.sub.3).nH.sub- .2O 2
.theta. Relative intensity 11.67.degree. 100% 23.47.degree. 59%
34.82.degree. 15% 39.42.degree. 9% 46.89.degree. 8% 60.96.degree.
10% 62.03.degree. 11%
[0188] An X-ray diffraction image of the hydrotalcite is shown in
FIG. 6.
Comparative Example 3
[0189] Synthesis of a lithium aluminum composite hydroxide.
[0190] 25.00 Grams of sodium hydroxide (NaOH content of 96%) and
7.44 g of sodium carbonate (Na.sub.2CO.sub.3 content of 99.7%) were
added to 2 liters of distilled water with stirring, and the mixture
was heated at 40.degree. C. Then, to this solution was gradually
added an aqueous solution which was obtained by adding 4.33 g of
lithium chloride (52.90% as Li.sub.2O) and 49.78 g of aluminum
chloride (20.48% as Al.sub.2O.sub.3) to 500 ml of distilled water
such that the molar ratio of Al/Li was 2.0. The reaction was
conducted with stirring at a temperature of 90.degree. C. for 20
hours. The obtained reaction suspension was filtered, washed with
water, dried at 70.degree. C. and was, then, pulverized using a
small sample mill to obtain a white powder.
[0191] The composition of the obtained fine powder was analyzed to
be as follows. Properties were as shown in Table 1.
16 Li.sub.2Al.sub.4(OH).sub.12CO.sub.3.nH.sub.2O 2 .theta. Relative
intensity 11.77.degree. 100% 20.20.degree. 11% 23.61.degree. 59%
36.07.degree. 29% 40.63.degree. 14% 48.03.degree. 18% 63.23.degree.
11% 64.53.degree. 9%
[0192] An X-ray diffraction image of the salt of lithium aluminum
composite hydroxide is shown in FIG. 7.
17TABLE 1 Laminate Specific Average asymmetric Degree of surface
Porous particle indexes orientation area volume diameter Is Io
(m.sup.2/g) (ml/g) (.mu.m) (a + b)/x y/(a + b + x) b/(a + b)
Example No. 1 3.57 3.80 5.50 0.025 6.2 1.44 2.05 1.00 2 2.73 3.55
6.02 0.029 6.2 1.48 2.05 1.00 3 2.35 2.67 4.90 0.025 5.2 1.92 2.02
1.00 4 4.40 3.54 3.91 0.020 4.3 1.18 2.15 0.21 5 5.36 3.29 3.84
0.027 4.6 1.23 2.14 0.41 6 10.42 3.76 4.70 0.031 4.9 1.27 2.12 0.59
7 7.18 3.1 1.92 2.02 1.00 8 1.69 3.0 1.27 2.12 0.59 9 3.85 4.8 1.49
2.08 1.00 10 7.83 146 0.425 4.2 1.38 2.14 0.58 11 3.79 4.1 1.92
2.02 1.00 Comparative Example No. 1 1.36 0.57 -- -- -- 2 -- -- 3.00
2.00 0.25 3 -- -- 0.25 2.00 --
[0193] a, b, x, y and z are indexes of
M.sup.2.sub.aZn.sub.bM.sup.3.sub.x(-
OH).sub.y(A).sub.z.nH.sub.2O.
[0194] According to the present invention, it is made possible to
obtain a composite metal polybasic salt having a chemical
composition represented by the following general formula (1),
M.sup.2.sub.aZn.sub.bM.sup.3.sub.x(OH).sub.y(A).sub.z.nH.sub.2O
(1)
[0195] wherein M.sup.2 is a divalent metal other than Zn, M.sup.3
is a trivalent metal, A is an inorganic or organic anion, and a, b,
x, y and z are numbers satisfying the following formulas,
[0196] 0.ltoreq.a, 0<b
[0197] 3x+2(a+b)-y-mz=0 (wherein m is a valency of anion A),
[0198] 0.3.ltoreq.(a+b)/x.ltoreq.2.5,
[0199] 1.5.ltoreq.y/(x+a+b).ltoreq.3.0, and
[0200] 4.0.ltoreq.(x+a+b)/z.ltoreq.20.0, and
[0201] n is a number of not larger than 7,
[0202] exhibiting diffraction peaks at 2.theta.=2 to 15.degree.,
2.theta.=19.5 to 24.degree. and 2.theta.=33 to 50.degree., and a
single peak at 2.theta.=60 to 64.degree. and, more preferably, a
single peak at 2.theta.=33 to 50.degree. in the X-ray diffraction
(Cu-.alpha.). The zinc-modified composite metal polybasic salt is
useful as an additive for resins, as a heat-insulating agent and as
an anion-exchanger.
* * * * *