U.S. patent application number 15/282872 was filed with the patent office on 2017-01-26 for composition based on magnesium sulfate and diammonium hydrogenphosphate.
This patent application is currently assigned to K+S Kali GmbH. The applicant listed for this patent is K+S Kali GmbH. Invention is credited to Ulrich Kleine-Kleffmann, Ralf WEBER.
Application Number | 20170022420 15/282872 |
Document ID | / |
Family ID | 48428418 |
Filed Date | 2017-01-26 |
United States Patent
Application |
20170022420 |
Kind Code |
A1 |
WEBER; Ralf ; et
al. |
January 26, 2017 |
COMPOSITION BASED ON MAGNESIUM SULFATE AND DIAMMONIUM
HYDROGENPHOSPHATE
Abstract
The present invention relates to compositions obtainable by
reaction of a hydrate of magnesium sulfate with diammonium
hydrogenphosphate and a further inorganic substance, especially
anhydrous magnesium sulfate. The invention also relates to the
production of the compositions and to the use thereof as flame
retardants.
Inventors: |
WEBER; Ralf; (Kaufungen,
DE) ; Kleine-Kleffmann; Ulrich; (Bad Hersfeld,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
K+S Kali GmbH |
Kassel |
|
DE |
|
|
Assignee: |
K+S Kali GmbH
Kassel
DE
|
Family ID: |
48428418 |
Appl. No.: |
15/282872 |
Filed: |
September 30, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14397344 |
Oct 27, 2014 |
9487706 |
|
|
PCT/EP2013/001247 |
Apr 25, 2013 |
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15282872 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
F16L 59/028 20130101;
C09K 21/04 20130101 |
International
Class: |
C09K 21/04 20060101
C09K021/04; F16L 59/02 20060101 F16L059/02 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 27, 2012 |
EP |
12166027.8 |
Claims
1. Composition, obtainable through conversion of at least one
hydrate of the magnesium sulfate with di-ammonium hydrogen
phosphate ((NH.sub.4).sub.2)HPO.sub.4) and with a further inorganic
material which is selected under zeolite, anhydrous calcium
chloride and anhydrous magnesium sulfate and their mixtures.
2-20. (canceled)
Description
[0001] This invention concerns compositions which are available
through the conversion of a hydrate of the magnesium sulfate with
di-ammonium hydrogen phosphate and a further inorganic substance,
in particular anhydrous magnesium sulfate. The invention also
concerns the manufacture of the compositions and their utilization
as flame-retardants.
[0002] For the thermal insulation of new and old constructions,
insulation materials are employed which are manufactured in many
cases of renewable or recycled organic fiber materials, such as
excelsior, wood chipboard, sheep's wool or scrap-paper. Since such
materials are often comparatively inflammable, flame-retardant is
generally added to them during their processing to insulation
materials. Certain salts and salt mixes are used as
flame-retardants, which are usually mixed with the organic fiber
materials in fine-ground form. In this connection, mixtures of
borates with further salts, such as in particular magnesium sulfate
(MgSO.sub.4 7H2O) have proven themselves, where magnesium sulfate
contributes to the flame retardation, particularly through its high
hydrate content. Since recently the toxicological harmlessness of
borates and boric acid is coming increasingly into question, a
requirement exists for alternatives.
[0003] Basically it is known that ammonium phosphates, such as for
example (NH.sub.4).sub.3PO.sub.4, (NH.sub.4).sub.2HPO.sub.4 and
(NH.sub.4)H.sub.2PO.sub.4, have fire-hampering effects. Own
experiments of the inventors, however, have indicated that borates
cannot simply be replaced by ammonium phosphates. Thus, with the
grinding of mixtures of magnesium sulfate and ammonium phosphates,
rubber-type masses arise instead of the required powder masses,
which furthermore frequently bind with the grinding equipment.
These mixtures accordingly have insufficient processing
characteristics, which exclude their employment in any large-scale
technical process.
[0004] In U.S. Pat. No. 4,374,171 as well as a series of further
flame-suppressing salts, magnesium sulfate and ammonium hydrogen
phosphate can also be listed. However, U.S. Pat. No. 4,374,171 does
not manifest either mixtures of these salts or mixed salts
available from them. In particular, U.S. Pat. No. 4,374,171 does
not manifest any compositions which result from the conversion of a
hydrate of the magnesium sulfate with diammonium hydrogen phosphate
and anhydrous magnesium sulfate.
[0005] The invention has as its basis the task of providing a
composition obtainable from magnesium sulfate which includes no
borate, rather indicates fire-protection and processing properties
which are comparable with those of mixtures of magnesium sulfate
and borate.
[0006] Surprisingly, it was thought that, through the conversion of
magnesium sulfate hydrates, such as magnesium sulfate, with
di-ammonium hydrogen phosphate and anhydrous magnesium sulfate,
compositions could be manufactured which would solve the task and,
in particular, would have the required processing characteristics.
The compositions thus obtained can therefore be especially well
processed with insulation materials, particularly into such
substances which are based on organic fiber materials.
[0007] The subject of the invention are compositions which can be
obtained through the conversion of at least one hydrate of the
magnesium sulfate with di-ammonium hydrogen phosphate
((NH.sub.4).sub.2HPO.sub.4) and a further inorganic material or a
further inorganic substance, where the further inorganic material
or the further inorganic substance is selected under anhydrous
magnesium sulfate, zeolite, anhydrous calcium chloride and their
mixtures.
[0008] The invention-related compositions are solid, generally
crystalline or at least mainly crystalline compositions. Unlike
compositions, which are available through the conversion of
hydrates of the magnesium sulfate with ammonium phosphate, ammonium
hydrogen phosphate and ammonium di-hydrogen phosphate, they
indicate useful processing characteristics and, in particular, can
be processed without problems with insulation materials, based on
organic fiber materials, to insulating materials which are provided
with good fire protection. Furthermore, the invention-related
compounds are easily accessible through simple processes and can be
manufactured in individual form, somewhat in powder form.
[0009] It is assumed that the property of the further inorganic
material to bind water is the reason for the useful properties of
the invention-related compositions.
[0010] The compositions of the existing invention available through
the above-designated conversion generally include a compound of
Formula I
[(NH.sub.4).sub.2Mg(HPO.sub.4).sub.2.mH.sub.2O] (I),
or a mixture of the compound of Formula (I) with a compound of
Formula II
[(NH.sub.4).sub.2Mg(SO.sub.4).sub.2].nH.sub.2O (II),
where m is usually in the range 2 to 6, and preferably 3 to 5, as
well as n is usually in the range 4 to 8, and preferably 5 to 7. In
Formula I m means 4 in particular, and in Formula II n means 6 in
particular.
[0011] In accordance with a further preferred implementation form,
the invention-related compounds additionally include a hydrate of
the magnesium sulfate, which includes per mol MgSO41 to 10,
preferably 4 to 8, and in particular 6 equivalents H.sub.2O.
[0012] Preferably the composition includes 30 to 100 wt. %, in
particular 40 to 80 wt. %, a compound of Formula I or a mixture of
compounds of Formulae I and II, as well as 0 to 70 wt. %, in
particular 20 to 60 wt. %, of the hydrate of the magnesium sulfate,
with reference to the total weight of the composition in each
case.
[0013] A preferred implementation form of the invention concerns
compositions which are obtainable as a further inorganic material
through the conversion of at least one hydrate of the magnesium
sulfate with di-ammonium hydrogen phosphate
((NH.sub.4).sub.2HPO.sub.4) and with anhydrous magnesium
sulfate.
[0014] The invention-related compositions in each case preferably
include less than 20 wt. %, in particular less than 15 wt. %, and
especially less than 10 to wt. %, of compounds which are different
from the compounds of Formulae I and II, as well as the magnesium
sulfate hydrate, with reference to the total weight of the
composition.
[0015] Provided that the compositions are obtainable through the
conversion of at least one hydrate of the magnesium sulfate with
di-ammonium hydrogenphosphate ((NH.sub.4).sub.2HPO.sub.4) and with
a further inorganic material, which is selected among zeolites,
anhydrous calcium chloride and their mixtures, the content of
substances which are different from the compounds of Formulae I and
II, as well as the magnesium sulfate hydrate, are also more than 20
wt. %, e.g. up to 50 wt. %, and then preferably in the range 5 to
50 wt. %, in particular in the range 10 to 30 wt. %, with reference
to the total weight of the composition in each case. In case of
substances which are different from the compounds of Formulae I and
II, as well as the magnesium sulfate hydrate, it is a question in
this case in particular of zeolites, anhydrous calcium chloride and
hydrates of the calcium chloride, e.g. calcium chloride
hexahydrate.
[0016] The identity and the content of compounds of Formulae I and
II, of the magnesium sulfate hydrate and of most further compounds,
which are possibly present in the invention-related compositions,
can be determined by means of X-ray powder diffractometry through
comparison of a powder diffractogram with corresponding
reference-powder diffractograms. Such methods are known to the
specialist sector and can be implemented in a known manner, for
example with the aid of the powder X-ray diffractometry software:
"EVA" Ver. 12.0.0.0 of the Co. Bruker AXS, database: Powder
Diffraction Files (PDF-2, Release 1999; Data Sets 1-49, plus 70-86)
of the International Center for Diffraction Data (ICDD).
[0017] From the absence of reflexes, which are characteristic for
the yield compounds, in particular di-ammonium hydrogen phosphate
and anhydrous magnesium sulfate or anhydrous calcium chloride, it
can furthermore be concluded that their respective content is small
in accordance with qualitative evaluation of the RDA diagram. The
characteristic reflexes for MgSO.sub.4 in the form of the
anhydrate, magnesium sulfate and further possible starting
materials and by-products, can be taken from the literature or
relevant data-bases of the International Center for Diffraction
Data (JCPDS).
[0018] The compound of Formula I included in the invention-related
compositions, in an X-ray powder diffractogram recorded at
25.degree. C. (Cu-K.sub..alpha. radiation: .lamda.=1.5413 .ANG.),
generally indicates at least 3, and in particular at least 5, and
especially at least 7 or all d-values of the following Table 1,
where it indicates preferably at least 3, in particular at least 5,
and especially at least 7, of the respective reflexes, whose
relative intensity is at least 30%, with reference to the intensity
of the strongest peak (100% rel. intensity). The measured
intensities can deviate from the indicated values to a certain
degree, since they depend on the sample preparation in a known
manner. In Table 1 the characteristic reflexes of the Compound I
are indicated as network designation separation distances d (in
angstroms), which can be calculated with the Bragg relationship
from 2.THETA. values.
TABLE-US-00001 TABLE 1 d-value (.ANG.) Rel. intensity (%) 5.1910
.+-. 0.0005 100 5.9150 .+-. 0.0005 79 4.3100 .+-. 0.0005 51 3.4624
.+-. 0.0005 35 5.9572 .+-. 0.0005 34 3.0122 .+-. 0.0005 33 3.9016
.+-. 0.0005 32 2.5845 .+-. 0.0005 28 3.3563 .+-. 0.0005 21 3.5925
.+-. 0.0005 21 2.5757 .+-. 0.0005 20 5.7450 .+-. 0.0005 19
[0019] Correspondingly, the compound of Formula II, possibly
included in the invention-related compositions, indicate in a X-ray
powder diffractogram recorded at 25.degree. C. (Cu-K.sub..alpha.
radiation: .lamda.=1.5413 .ANG.) at least 3, and in particular at
least 5, and especially at least 7, or all d-values of the
following Table 2, where it indicates preferably at least 3, in
particular at least 5, and especially at least 7, of the respective
reflexes, whose relative intensity is at least 30%, with reference
to the intensity of the strongest peak (100% rel, intensity). The
measured intensities can deviate from the indicated values to a
certain degree, since they depend on the sample preparation in a
known manner. In Table 2 the characteristic reflexes of the
compound II are indicated as network designation separation
distances d (in angstroms), which can be calculated with the Bragg
relationship from 2.THETA. values.
TABLE-US-00002 TABLE 2 d-value (.ANG.) Rel. intensity (%) 4.2054
.+-. 0.0005 100 3.8022 .+-. 0.0005 85 4.2633 .+-. 0.0005 58 5.3750
.+-. 0.0005 55 3.1510 .+-. 0.0005 54 3.0123 .+-. 0.0005 34 2.7834
.+-. 0.0005 34 4.1391 .+-. 0.0005 31 5.1510 .+-. 0.0005 30 4.3235
.+-. 0.0005 26 3.0529 .+-. 0.0005 23 2.4623 .+-. 0.0005 22
[0020] The further compounds possibly included in the
invention-related compositions can be identified in an X-ray powder
diffractogram of an invention-related composition recorded at
25.degree. C. (Cu-K.sub..alpha. radiation: .lamda.=1.5413 .ANG.) by
means of the reflexes indicated in the following Table 3, where,
for identification, typically at least 3 of the indicated d-values
with a relative intensity of at least 30% are referred to. The
measured intensities can deviate from the indicated values to a
certain degree, since they depend on the sample preparation in a
known manner. For zeolite, the corresponding reflexes can be taken
from the following database: Database of Zeolite Structures:
http://izasc.ethz.ch/fmi/xsl/IZA-SC/xrd.xsl
TABLE-US-00003 TABLE 3 Contamination d-value (.ANG.) Rel. intensity
(%) (NH.sub.4).sub.2SO.sub.4 4.3208 .+-. 0.0005 100 4.3766 .+-.
0.0005 53 3.0407 .+-. 0.0005 47 3.8800 .+-. 0.0005 30 2.9850 .+-.
0.0005 26 NH.sub.4H.sub.2PO.sub.4 5.3243 .+-. 0.0005 100 3.0673
.+-. 0.0005 90 3.0779 .+-. 0.0005 85 3.7507 .+-. 0.0005 55 2.0091
.+-. 0.0005 40 MgSO.sub.4.cndot.6 H.sub.2O 3.4050 .+-. 0.0005 100
4.8150 .+-. 0.0005 75 3.3510 .+-. 0.0005 70 3.3130 .+-. 0.0005 70
MgSO.sub.4 3.5300 .+-. 0.0005 100 3.6100 .+-. 0.0005 70 4.1500 .+-.
0.0005 30 MgHPO.sub.4.cndot.3 H.sub.2O 3.0407 .+-. 0.0005 100
3.4616 .+-. 0.0005 66 3.0858 .+-. 0.0005 54 5.9452 .+-. 0.0005 52
4.7141 .+-. 0.0005 47 CaCl.sub.2.cndot.6 H.sub.2O 3.9380 100 2.1596
93 6.8207 82 3.4211 75 2.7904 74 2.5826 67 2.2736 62 2.5780 46
1.7065 24 1.4884 19 1.9773 17 1.9689 16 1.9690 16 1.4920 12 1.8991
11 1.4550 10 1.5658 7 1.5658 7 1.5689 6 1.7670 6 1.7106 5 1.2255 5
1.1891 5 1.3930 5 CaCl.sub.2 3.0634 .+-. 0.0005 100 4.4780 .+-.
0.0005 85 2.3337 .+-. 0.0005 52 2.8579 .+-. 0.0005 32 1.9091 .+-.
0.0005 29 2.2390 .+-. 0.0005 28 2.3628 .+-. 0.0005 25 2.1000 .+-.
0.0005 21 3.4843 .+-. 0.0005 17 1.9013 .+-. 0.0005 13 1.5317 .+-.
0.0005 12 1.8640 .+-. 0.0005 12 1.7902 .+-. 0.0005 11 1.6923 .+-.
0.0005 8 1.2528 .+-. 0.0005 7 1.5567 .+-. 0.0005 6 1.2080 .+-.
0.0005 6 3.1200 .+-. 0.0005 5 1.5600 .+-. 0.0005 5 1.2506 .+-.
0.0005 5
[0021] Preferred compositions of the invention indicate a mol ratio
of phosphorus to sulfur which is generally in the range 2:1 to 1:5,
preferably in the range 1.5:1 to 1:4, and in particular in the
range 1:1 to 1:3. The mol ratio of phosphorus to sulfur of the
compositions can be determined, for example, through elemental
analysis.
[0022] Preferred compositions of the invention indicate a mol ratio
of phosphorus to magnesium, which is generally in the range 2:1 to
1:5, preferably in the range 1.5:1 to 1:4, and in particular in the
range 1:1 to 1:3. The mol ratio of phosphorus to magnesium of the
compositions can be determined for example through elemental
analysis.
[0023] Furthermore, those compositions of the invention are
preferred which indicate a water content of 5 to 50 wt. %, in
particular 10 to 40 wt %, and especially of 10 to 30 wt. %, with
reference to the total weight of the composition. The water content
of the compositions can be determined for example through
Karl-Fischer titration.
[0024] The invention-related compositions have preferably a
phosphorus content, calculated as phosphate, of 10 to 40 wt. %, in
particular 15 to 35 wt. %, and especially 15 to 30 wt. %, with
reference to the total weight of the composition.
[0025] Furthermore, a process for the manufacture of the
invention-related compositions has been found, which is
characterized in that at least one hydrate of the magnesium
sulfate, such as magnesium sulfate, converts with di-ammonium
hydrogen phosphate ((NH.sub.4).sub.2HPO.sub.4) together with a
further inorganic material, which is selected under zeolite,
anhydrous calcium chloride and anhydrous magnesium sulfate and
their mixtures.
[0026] Preferably, the further inorganic material is used for the
manufacture of the invention-related material in such quantities
that the weight content of the further inorganic material, in each
case with reference to the total amount of hydrate of the magnesium
sulfate di-ammonium hydrogen phosphate and further inorganic
material in the reaction mixture, is in the range 5 to 50 wt. %, in
particular in the range 10 to 30 wt. %.
[0027] Preferably, the hydrate of the magnesium sulfate is used in
such quantities that the water content, in each case with reference
to the total amount of hydrate of the magnesium sulfate di-ammonium
hydrogen phosphate and further inorganic material in the reaction
mixture, is in the range 5 to 50 wt. %, in particular 10 to 40 wt.
%, and especially 10 to 30 wt. %.
[0028] Preferably, the hydrate of the magnesium sulfate and
(NH.sub.4).sub.2HPO.sub.4 is used in such a quantity ratio so that
in the composition obtained after the conversion of phosphorus to
sulfur, the mol ratio is generally in the range 2:1 to 1:5,
preferably in the range 1.5:1 to 1:4, and in particular in the
range 1:1 to 1:3.
[0029] In a preferred implementation form of the invention,
anhydrous magnesium sulfate is used as a further inorganic
substance, i.e. in the invention-related process, the hydrate of
the magnesium sulfate, anhydrous magnesium sulfate and
(NH.sub.4).sub.2HPO.sub.4 are converted with each other.
[0030] In this preferred implementation form of the
invention-related process, the hydrate of the magnesium sulfate,
anhydrous magnesium sulfate and (NH.sub.4).sub.2HPO.sub.4 is
preferably used in such a quantity ratio that, in the composition
received after the conversion, the mol ratio of phosphorus to
sulfur is generally in the range 2:1 to 1:5, preferably in the
range 1.5:1 to 1:4, and in particular in the range 1:1 to 1:3.
[0031] In this preferred implementation form of the
invention-related process, the hydrate of the magnesium sulfate and
anhydrous magnesium sulfate is preferably used in a mol ratio in
the range 1:4 to 4:1, preferably 1:3 to 3:1, and especially 1:2.5
to 2:1.
[0032] In a further implementation form of the invention, anhydrous
calcium chloride is used as a further inorganic substance, i.e. in
the invention-related process, the hydrate of the magnesium
sulfate, anhydrous calcium chloride and (NH.sub.4).sub.2HPO.sub.4
are converted with each other.
[0033] In a further implementation form of the invention, a zeolite
is used as a further inorganic substance, i.e. in the
invention-related process the hydrate of the magnesium sulfate, at
least one zeolite and (NH.sub.4).sub.2HPO.sub.4 are converted with
each other. Preferably, the zeolite involves a zeolites dehydrated
at least in part, i.e. the zeolite typically includes not more than
50% of the quantity at water that it is able to bind. In
particular, a zeolite to a large extent or completely dehydrated is
used, i.e. the zeolite typically includes not more than 10% of the
quantity at water that it is able to bind. Suitable zeolites are
known to the specialist. Both natural and artificial zeolite, in
particular those zeolites which are suited as molecular sieves and
can bind water. Examples of suitable artificial zeolite are the
zeolites of the type zeolite A, zeolite X, zeolite Y, zeolite L,
ZSM5 and ZSM11. Examples of suitable natural zeolite are at least
in-part dehydrated forms of the faujasites, of the mordenites and
the stilbites.
[0034] In accordance with a group of preferred implementation forms
of the invention-related process, magnesium sulfate is employed as
a hydrate of the magnesium sulfate (MgSO.sub.4. 7H.sub.2O).
[0035] In particular, for the conversion according to the
invention-related process, a mixture composed of a hydrate of the
magnesium sulfate, the further inorganic component part, in
particular anhydrous magnesium sulfate, and
(NH.sub.4).sub.2HPO.sub.4 are added together in the
above-designated quantity ratio and mixed well with each other, for
example by means of a suitable extruder, by means of a suitable
agitator, kneading device or comminution equipment. Preferably, the
mixing is implemented by grinding by means of suitable equipment,
such as in particular impact or impingement mills, among other
things also jaw crushers, rotating crushers, roll crushers, hammer
crushers, dog crushers, worm-drive crushers, rolling mills, impact
and centrifuging mills.
[0036] The conversion according to the invention-related process is
exothermic. In this case, it has proved advantageous to implement
the conversion of the co-reactants magnesium sulfate hydrate,
di-ammonium hydrogen phosphate and the further inorganic component
part in the process with utilization of the heat of reaction.
Preferably a temperature of 70.degree. C. is not exceeded in this
case. Where appropriate, the reaction mixture is therefore cooled.
In particular, the conversion is implemented with temperatures in
the range 10 to 70.degree. C.
[0037] On completion of the reaction, the composition formed is
generally allowed to cool down to ambient temperature. In this
case, a solid, crystalline, or at least a mainly crystalline mass
is obtained, which, at least if the mixing is implemented by
grinding, is present in a particular form. Generally, at least 90
wt. % of the particles will then have a diameter which is less than
2 mm, and preferably less than 1 mm. For example, at least 90 wt. %
of the particles can indicate a particle diameter in the range 0.01
to 2 mm and especially 0.1 to 1 mm. The particle diameter can be
determined by sieve analysis.
[0038] The process of the invention enables the manufacture of the
invention-related compositions in the above described quality and
with the above written specifications. The process furthermore
enables the manufacture of invention-related compositions, which
contain a compound of Formula I or a mixture of compounds of
Formulae I and II and, where appropriate, in addition one or more
hydrates of the magnesium sulfate. In particular, with the process
Compound I and, where appropriate, Compound II can be manufactured
in high yield, generally practically 100%, with reference to the
starting materials magnesium sulfate hydrate,
(NH.sub.4).sub.2HPO.sub.4 and magnesium sulfate anhydrate.
[0039] Preferably the compositions manufactured with the
invention-related process include 30 to 100 wt %, preferably 40 to
80 wt. %, of a compound of Formula I, and a mixture of compounds of
Formulae I and II, as well as 0 to 70 wt. %, preferably 20 to 60
wt. %, of a hydrate of the magnesium sulfate, with reference to the
total weight of the composition in each case. Furthermore, the
compositions of the invention manufactured with the
invention-related process have good processing characteristics as
indicated above.
[0040] The invention further concerns the utilization of the
invention-related compositions as flame-retardants in different
areas of application. The compositions are particularly suitable as
flame-retardants in insulating materials, especially in those which
are based on organic fiber materials, such as e.g. cellulose fibers
obtained from scrap-paper, wood fiber, as well as sheep's wool.
[0041] Correspondingly, the invention also concerns insulation
materials on the basis of organic fiber materials which were
treated with a composition of the invention acting as
flame-retardants. The processing is generally implemented by mixing
the fiber materials with an invention-related composition, for
example in a rotating barrel mixer or a shredding system.
[0042] An invention-related insulating material accessible in this
way usually includes a composition of the invention in a quantity
of 2 to 25 wt. %, in particular 5 to 20 wt. %, and especially 7 to
15 wt. %, with reference to the weight of the insulating
material.
[0043] The invention-related composition and the invention-related
processes are explained in more detail by the following
examples.
General Specification for Examples of 1 to 10
[0044] For the examples of 1 to 10, magnesium sulfate (technical
quality), anhydrous magnesium sulfate and an ammonium phosphate
salt are mixed in each case, where it involves
(NH.sub.4)H.sub.2PO.sub.4, a mixture of (NH.sub.4)H.sub.2PO.sub.4
and (NH.sub.4).sub.2HPO.sub.4 or (NH.sub.4).sub.2HPO.sub.4, in the
quantities indicated in Table 4. The mixtures, whose total weight
was 50 g in each case, were ground for 60 seconds in an IKA
universal mill type M20 (motor power 260 W) at approx. 20,000
rotations per minute. The temperature of the mixture was measured
before and directly after the grinding procedure, and is indicated
for every example in Table 4. In the same way, the pH values of 5
wt. % diluted suspensions of the compositions obtained in each case
after the grinding, are listed in Table 4.
TABLE-US-00004 TABLE 4 AP salt AP salt AP salt Temperature .sup.c)
Magnesium MgSO.sub.4 .sup.a) 1 .sup.b) 2 .sup.b) 3 .sup.b)
[.degree. C.] pH Example sulfate [g] [g] [g] [g] [g] Start End
Value .sup.d) 1 25.00 8.33 16.67 22 51 4.8 (23.degree. C.) 2 21.43
14.29 14.29 25 53 4.9 (24.degree. C.) 3 18.75 18.75 12.50 24 62 4.8
(25.degree. C.) 4 25.00 8.33 16.67 24 40 5.4 (24.degree. C.) 5
21.43 14.29 14.29 24 45 5.5 (23.degree. C.) 6 18.75 18.75 12.50 24
55 5.6 (23.degree. C.) 7 25.00 8.33 16.67 25 54 4.8 (23.degree. C.)
8 21.43 14.29 14.29 24 60 4.8 (23.degree. C.) 9 18.75 18.75 12.50
24 62 4.8 (23.degree. C.) 10 30.00 0 20.00 23 52 4.8 (23.degree.
C.) .sup.a) Anhydrous magnesium sulfate; .sup.b) Ammonium phosphate
salt 1 (AP salt 1) = ammonium dihydrogen phosphate
(NH.sub.4)H.sub.2PO.sub.4); AP salt 2 = mixture of ammonium
dihydrogen phosphate and di-ammonium hydrogen phosphate
(NH.sub.4)H.sub.2PO.sub.4/(NH.sub.4).sub.2HPO.sub.4); AP salt 3 =
di-ammonium hydrogen phosphate ((NH.sub.4).sub.2HPO.sub.4); .sup.c)
Temperatures of the reaction mixture before and directly after the
grinding procedure; .sup.d) pH values of the 5 wt. % diluted
suspension of the composition obtained after the conversion.
OBSERVATIONS
Example 1
[0045] The crushing material adhered in large part viscously and
plastically to the grinding wall and rotor; no powder had formed;
during grinding the mill ran stiff between 40 and 45 seconds.
Example 2
[0046] Similar to Example 1, however a little more ductile caking
deposits.
Example 3
[0047] Similar to Example 2, however even more ductile mass which
could scarcely be removed from the grinding chamber.
Example 4
[0048] Similar to Example 1, however a little less viscous; during
grinding the mill ran stiff between 15 and 20 seconds.
Example 5
[0049] Similar to Example 3; the mill ran stiff between 20 and 25
seconds.
Example 6
[0050] The crushed material was baked on and could be removed from
the mill with difficulty only; the mill ran stiff between 20 and 25
seconds.
Example 7
[0051] The crushing material was mainly fine and in powder form. A
thin, adhering layer was present on the grinding wall which could
not be easily detached; with opening the mill a light dust plume
could be observed; during grinding procedure no performance
reduction was audible.
Example 8
[0052] Similar to Example 7: The thin layer on the grinding wall
did not adhere fixed.
Example 9
[0053] Similar to Example 8; only in the upper area of the mill did
a thin layer adhere to the grinding wall, which could be easily
removed.
Example 10
[0054] A larger part of the crushing material adhering in the upper
area of the grinding chamber was moist and could be easily
detached. A further part adhered as a fixed layer in the lower
grinding chamber and was difficult to remove. During grinding
procedure, no performance reduction was observed.
Phase Analysis by Means of X-Ray Diffractometry (RDA):
[0055] The recording of the X-ray powder diffractograms is
implemented with a type D 8 Advance Diffractometer of the Co.
Bruker, AXS (298 K, Cu-K.alpha. radiation: .lamda.=1.5413 .ANG.),
increment: 0.018385738, step duration: 0.2 seconds, detector: Lynx
Eye. The phase analyses of the compositions obtained in Examples 1
to 10 are collated in Table 5. The allocation of the phases in
accordance with highest probability was implemented by means of
comparison material based on the Powder Diffraction Files (PDF-2,
Release 1999, Data Sets 1-49, plus 70-86) of the International
Center for Diffraction Data (ICDD). The detection limit was between
0.1 and 5%, according to phase.
TABLE-US-00005 TABLE 5 Phase relationships of the manufactured
compositions .sup.1) Example 1 2 3 4 5 6 7 8 9 10
(NH.sub.4).sub.2Mg(HPO.sub.4).sub.2.cndot.4 .sub.H2O ++ ++ ++ ++
(NH.sub.4).sub.2Mg(SO.sub.4).sub.2.cndot.6 .sub.H2O ++ ++ ++ ++ ++
++ ++ ++ ++ ++ (NH.sub.4).sub.2SO.sub.4 (++) (++) (++) (++)
MgSO.sub.4.cndot.6 .sub.H2O ++ ++ ++ + + + ++ ++ ++ - MgSO.sub.4 ++
++ ++ (+) ++ ++ (+) ++ ++ - MgHPO.sub.4.cndot.6 .sub.H2O
MgHPO.sub.4.cndot.3 .sub.H2O (+) (+) (+) (+) (+) (+)
NH.sub.4H.sub.2PO.sub.4 (+) (+) (+) (+) (+) (+) (+) (+) (+) (+)
(NH.sub.4).sub.2HPO.sub.4 - (+) (+) .sup.1): ++ Phase clearly
present; (++) Phase probably clearly present, due to
Superpositions, however, no definitive allocation could be carried
out; + Phase present as a secondary component part or as a trace;
(+) Phase probably present as a secondary component part or as a
trace, however, due to superpositions no definitive allocation
could be carried out; - Phase not verified or below the detection
limit.
[0056] As can be seen in Table 4, in cage of the products obtained
in Examples 4 to 9, it involves invention-related compositions,
since in Examples 1 to 3 only (NH.sub.4)H.sub.2PO.sub.4, however,
no (NH.sub.4).sub.2HPO.sub.4 was employed, and no anhydrous
MgSO.sub.4. was employed in Example 10. As described above in the
"Observations", the compositions of the Examples 7 to 9 have
significantly improved processing characteristics compared to all
others.
Composition Based on Magnesium Sulfate and Di-Ammonium Hydrogen
Phosphate
SUMMARY
[0057] The existing invention concerns compositions which are
available through conversion of a hydrate of the magnesium sulfate
with di-ammonium hydrogen phosphate and a further inorganic
substance, in particular anhydrous magnesium sulfate. The invention
also concerns the manufacture of the compositions' and their
utilization as flame-retardants.
* * * * *
References