U.S. patent application number 16/272417 was filed with the patent office on 2019-06-27 for mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for the production thereof and th.
This patent application is currently assigned to CLARIANT INTERNATIONAL LTD.. The applicant listed for this patent is CLARIANT INTERNATIONAL LTD.. Invention is credited to Harald BAUER, Sebastian HOEROLD, Martin SICKEN.
Application Number | 20190194543 16/272417 |
Document ID | / |
Family ID | 47278757 |
Filed Date | 2019-06-27 |
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United States Patent
Application |
20190194543 |
Kind Code |
A1 |
BAUER; Harald ; et
al. |
June 27, 2019 |
MIXTURES OF ALUMINUM PHOSPHITE WITH SPARINGLY SOLUBLE ALUMINUM
SALTS AND FOREIGN IONS, PROCESS FOR THE PRODUCTION THEREOF AND THE
USE THEREOF
Abstract
Mixtures of aluminum phosphite with sparingly soluble aluminum
salts and extraneous ions, process for preparation thereof and use
thereof The invention relates to mixtures of aluminum phosphite
with sparingly soluble aluminum salts and nitrogen-free extraneous
ions, comprising 80 to 99.898% by weight of aluminum phosphite of
the formula (I) Al.sub.2(HPO.sub.3).sub.3xH.sub.2O (I) in which x
is 0 to 4, 0.1 to 10% by weight of sparingly soluble aluminum salts
and 0.002 to 10% by weight of nitrogen-free extraneous ions; to a
process for preparation thereof and use thereof.
Inventors: |
BAUER; Harald; (Kerpen,
DE) ; HOEROLD; Sebastian; (Diedorf, DE) ;
SICKEN; Martin; (Koeln, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CLARIANT INTERNATIONAL LTD. |
Muttenz |
|
CH |
|
|
Assignee: |
CLARIANT INTERNATIONAL LTD.
Muttenz
CH
|
Family ID: |
47278757 |
Appl. No.: |
16/272417 |
Filed: |
February 11, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14362881 |
Jun 4, 2014 |
10202549 |
|
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PCT/EP2012/004909 |
Nov 28, 2012 |
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16272417 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C01P 2006/62 20130101;
C01P 2006/63 20130101; C01P 2006/11 20130101; C08K 3/32 20130101;
C01B 25/163 20130101; C01P 2004/61 20130101; C09K 21/04 20130101;
C01P 2006/64 20130101; C01P 2006/80 20130101; C01P 2006/82
20130101 |
International
Class: |
C09K 21/04 20060101
C09K021/04; C08K 3/32 20060101 C08K003/32; C01B 25/163 20060101
C01B025/163 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 5, 2011 |
DE |
10 2011 120 191.6 |
Claims
1.-5. (canceled)
6. A process for preparing a mixture of aluminum phosphite with
sparingly soluble aluminum salts and nitrogen-free extraneous ions,
where the mixture of aluminum phosphite comprises: 80 to 99.898% by
weight of an aluminum phosphite of the formula (I)
Al.sub.2(HPO.sub.3).sub.3xH.sub.2O (I) where x is 0 to 4; 0.1% to
10% by weight of the sparingly soluble aluminum salts; and 0.002 to
10% by weight of the nitrogen-free extraneous ions, the process
comprising crystallizing in a ratio of 2.5 to 3.5 mol of a non-salt
phosphorus source with 2 mol of a sparingly soluble aluminum salt
in the presence of an auxiliary acid at 50 to 180.degree. C. in a
solvent and at a solids concentration of 2 to 60%.
7. The process as claimed in claim 6, wherein the sparingly soluble
aluminum salts are selected from the group consisting of aluminum
hydroxide, aluminum hydroxychloride, polyaluminum hydroxyl
compounds, aluminum carbonates, hydrotalcites
(Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3xnH.sub.2O), dihydroxyaluminum
sodium carbonate (NaAl(OH).sub.2CO.sub.3), aluminum oxides,
aluminum oxide hydrate, mixed aluminum oxide hydroxides, basic
aluminum sulfate and alunite, and the non-salt phosphorus source is
selected from the group consisting of phosphorous acid, phosphorus
trioxide, phosphorus trichloride and hypophosphite.
8. The process as claimed in claim 6, wherein the auxiliary acid is
selected from the group consisting of hydrochloric acid,
hypochlorous acid, chlorous acid, chloric acid, hydrogen bromide,
hydrofluoric acid, hydrogen iodide, periodic acid, perchloric acid,
sulfuric acid, hydrogensulfate, sulfurous acid, hydrogensulfites,
peroxosulfuric acid, peroxodisulfuric acid; nitric acid, nitrous
acid, phosphoric acid, phosphorous acid, peroxophosphoric acid,
hypophosphorous acid, carbonic acid, silicic acid,
hexafluorosilicic acid, boric acid and carboxylic acids.
9.-10. (canceled)
11. A flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber comprising
0.1 to 45% by weight of a mixture of aluminum phosphite with
sparingly soluble aluminum salts and nitrogen-free extraneous ions;
55 to 99.9% by weight of thermoplastic or thermoset polymer or
mixtures thereof; 0 to 55% by weight of additives; and 0 to 55% by
weight of filler or reinforcing materials, where the sum of the
components is 100% by weight, and wherein the mixture of aluminum
phosphite with sparingly soluble aluminum salts and nitrogen-free
extraneous ions comprises: 80 to 99.898% by weight of an aluminum
phosphite of the formula (I) Al.sub.2(HPO.sub.3).sub.3xH.sub.2O (I)
where x is 0 to 4; 0.1 to 10% by weight of the sparingly soluble
aluminum salts; and 0.002 to 10% by weight of the nitrogen-free
extraneous ions.
12. A flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber comprising
0.1 to 45% by weight of a flame retardant mixture comprising 0.1 to
50% by weight of a mixture of aluminum phosphite with sparingly
soluble aluminum salts and nitrogen-free extraneous ions; 50 to
99.9% by weight of a flame retardant, 55 to 99.9% by weight of a
thermoplastic or thermoset polymer or mixtures thereof; 0 to 55% by
weight of additives; and 0 to 55% by weight of filler or
reinforcing materials, where the sum of the components is 100% by
weight, and wherein the mixture of aluminum phosphite with
sparingly soluble aluminum salts and nitrogen-free extraneous ions
comprises: 80 to 99.898% by weight of an aluminum phosphite of the
formula (I) Al.sub.2(HPO.sub.3).sub.3xH.sub.2O (I) where x is 0 to
4; 0.1 to 10% by weight of the sparingly soluble aluminum salts;
and 0.002 to 10% by weight of the nitrogen-free extraneous
ions.
13. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 11, wherein the flame retardant comprises
dialkylphosphinic acids and/or salts thereof; condensation products
of melamine and/or reaction products of melamine with phosphoric
acid and/or reaction products of condensation products of melamine
with polyphosphoric acid or mixtures thereof; nitrogen-containing
phosphates of the formulae (NH.sub.4).sub.yH.sub.3-y--PO.sub.4 and
(NH.sub.4--PO.sub.3).sub.z, where y is 1 to 3 and z is 1 to 10 000;
and benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin,
glycoluril, melamine, melamine cyanurate, dicyandiamide and/or
guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc
oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite,
dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium
hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide,
zinc borate, basic zinc silicate and/or zinc stannate.
14. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 11, wherein the flame retardant comprises melam, melem,
melon, dimelamine pyrophosphate, melamine polyphosphate, melam
polyphosphate, melon polyphosphate and/or melem polyphosphate
and/or mixed poly salts thereof and/or ammonium hydrogenphosphate,
ammonium dihydrogenphosphate and/or ammonium polyphosphate.
15. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 11, wherein the flame retardant comprises aluminum
hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium
phosphite, monophenylphosphinic acid and salts thereof, mixtures of
dialkylphosphinic acids and salts thereof and monoalkylphosphinic
acids and salts thereof, 2-carboxyethylalkylphosphinic acid and
salts thereof, 2-carboxyethylmethylphosphinic acid and salts
thereof, 2-carboxyethylarylphosphinic acid and salts thereof,
2-carboxyethylphenylphosphinic acid and salts thereof,
oxa-10-phosphaphenanthrene (DOPO) and salts thereof and adducts
onto para-benzoquinone, or itaconic acid and salts thereof.
16. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 12, wherein the flame retardant comprises
dialkylphosphinic acids and/or salts thereof; condensation products
of melamine and/or reaction products of melamine with phosphoric
acid and/or reaction products of condensation products of melamine
with polyphosphoric acid or mixtures thereof; nitrogen-containing
phosphates of the formulae (NH.sub.4).sub.yH.sub.3-yPO.sub.4 and
(NH.sub.4PO.sub.3).sub.z, where y is 1 to 3 and z is 1 to 10 000;
and benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin,
glycoluril, melamine, melamine cyanurate, dicyandiamide and/or
guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc
oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite,
dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium
hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide,
zinc borate, basic zinc silicate and/or zinc stannate.
17. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 12, wherein the flame retardant comprises melam, melem,
melon, dimelamine pyrophosphate, melamine polyphosphate, melam
polyphosphate, melon polyphosphate and/or melem polyphosphate
and/or mixed poly salts thereof and/or ammonium hydrogenphosphate,
ammonium dihydrogenphosphate and/or ammonium polyphosphate.
18. The flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber as claimed
in claim 12, wherein the flame retardant comprises aluminum
hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium
phosphite, monophenylphosphinic acid and salts thereof, mixtures of
dialkylphosphinic acids and salts thereof and monoalkylphosphinic
acids and salts thereof, 2-carboxyethylalkylphosphinic acid and
salts thereof, 2-carboxyethylmethylphosphinic acid and salts
thereof, 2-carboxyethylarylphosphinic acid and salts thereof,
2-carboxyethylphenylphosphinic acid and salts thereof,
oxa-10-phosphaphenanthrene (DOPO) and salts thereof and adducts
onto para-benzoquinone, or itaconic acid and salts thereof.
Description
[0001] The present invention relates to mixtures of aluminum
phosphite with sparingly soluble aluminum salts and extraneous
ions, to processes for preparation thereof and to the use
thereof.
[0002] The prior art discloses pure aluminum phosphites. These are
microporous compounds similar to zeolites, in which aluminum ions
and phosphite ions form a three-dimensional network of
multimembered rings. They may contain water of crystallization or
release water of crystallization with loss of the crystal structure
and thus form anhydrates. They are typically produced by
hydrothermal crystallization, i.e. above the boiling point of water
under the autogenous pressure thereof.
[0003] The raw materials used are aluminum sources, for example
readily soluble aluminum salts; the phosphorus sources used are
alkali metal phosphite or phosphorous acid.
[0004] To facilitate the crystallization (Yang. Shiyou Xuebao,
Shiyou Jiagong (2006), 22(Suppl.), 79-81), polynitrogen compounds
are added as structure-directing agents--also called templates. A
disadvantage is that templates can lower the thermal stability of
the product. Another disadvantage is that readily soluble aluminum
salts and alkali metal phosphites require the removal of the alkali
metal salts inevitably obtained.
[0005] Additionally known are mixtures of aluminum phosphite and
aluminum oxide or aluminum hydroxide.
[0006] It is an object of the present invention to provide mixtures
of aluminum phosphite with sparingly soluble aluminum salts and
extraneous ions, these mixtures being free of templates. It was a
further object to provide a process which does not require the
templates or the use of readily soluble aluminum or phosphite
salts.
[0007] It has been found that, surprisingly, the inventive mixtures
of aluminum phosphite with sparingly soluble aluminum salts and
extraneous ions are usable as synergists to flame retardants. These
flame retardant synergists need not themselves be flame-retardant,
but may significantly enhance the efficacy of flame retardants.
These flame retardant synergists are mixed together with the flame
retardants and further polymer additives by kneading and extrusion
with the polymer to be rendered flame-retardant. The resulting
polymer mixture is then flame-retardant. This processing operation
is effected at temperatures at which the polymer is in molten form
and which can distinctly exceed 320.degree. C. for a brief period.
Synergists must be able to withstand these temperatures without
decomposing, in order to retain their action. It has now been found
that, surprisingly, the inventive mixtures of aluminum phosphite
with sparingly soluble aluminum salts and extraneous ions are much
more thermally stable than pure aluminum phosphites.
[0008] In addition, the prior art discloses aluminum phosphite
hydrates. A disadvantage is the elimination of water which occurs
in the course of heating. This is harmful in the course of
processing of the synergist to give the flame-retardant polymer.
The object of the invention is achieved by the inventive mixtures
of aluminum phosphite with sparingly soluble aluminum salts and
extraneous ions, since these are substantially free of water of
crystallization.
[0009] The invention therefore relates to mixtures of aluminum
phosphite with sparingly soluble aluminum salts and nitrogen-free
extraneous ions, comprising [0010] 80 to 99.898% by weight of
aluminum phosphite of the formula (I)
[0010] Al.sub.2(HPO.sub.3).sub.3xH.sub.2O (I) [0011] in which x is
0 to 4, [0012] 0.1 to 10% by weight of sparingly soluble aluminum
salts and [0013] 0.002 to 10% by weight of nitrogen-free extraneous
ions.
[0014] Preference is given to mixtures comprising [0015] 88 to
99.79% by weight of aluminum phosphite of the formula (I) [0016] in
which x is 0 to 4, [0017] 0.2 to 5% by weight of sparingly soluble
aluminum salts and [0018] 0.01 to 7% by weight of nitrogen-free
extraneous ions.
[0019] Particular preference is given to mixtures comprising [0020]
94 to 99.4% by weight of aluminum phosphite of the formula (I)
[0021] in which x is 0 to 0.1, [0022] 0.3 to 3% by weight of
sparingly soluble aluminum salts and [0023] 0.3 to 3% by weight of
nitrogen-free extraneous ions.
[0024] The sparingly soluble aluminum salts are preferably aluminum
hydroxide, aluminum hydroxychloride, polyaluminum hydroxyl
compounds, aluminum carbonates, hydrotalcites
(Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3xnH.sub.2O), dihydroxyaluminum
sodium carbonate (NaAl(OH).sub.2CO.sub.3), aluminum oxides,
aluminum oxide hydrate, mixed aluminum oxide hydroxides, basic
aluminum sulfate and/or alunite.
[0025] The extraneous ions are preferably chlorides, complex
chlorides, bromides; hydroxides, peroxides, peroxide hydrates,
sulfites, sulfates, sulfate hydrates, acidic sulfates,
hydrogensulfates, peroxosulfates, peroxodisulfates; nitrates;
carbonates, percarbonates, stannates; borates, perborates,
perborate hydrates; formates, acetates, propionates, lactates
and/or ascorbates; and/or cations of the elements Li, Na, K, Mg,
Ca, Ba, Pb, Sn, Cu, Zn, La, Ce, Ti, Zr, V, Cr, Mn, Fe, Co and/or
Ni.
[0026] The invention also relates to a process for preparing
mixtures of aluminum phosphite with sparingly soluble aluminum
salts and nitrogen-free extraneous ions as claimed in one or more
of claims 1 to 5, which comprises crystallizing in a ratio of 2.5
to 3.5 mol of a non-salt phosphorus source with 2 mol of sparingly
soluble aluminum salt in the presence of an auxiliary acid at 50 to
180.degree. C. in a solvent and at a solids concentration of 2 to
60%.
[0027] Preferably, the sparingly soluble aluminum salts are
aluminum hydroxide, aluminum hydroxychloride, polyaluminum hydroxyl
compounds, aluminum carbonates, hydrotalcites
(Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3x nH.sub.2O), dihydroxyaluminum
sodium carbonate (NaAl(OH).sub.2CO.sub.3), aluminum oxides,
aluminum oxide hydrate, mixed aluminum oxide hydroxides, basic
aluminum sulfate and/or alunite, and the non-salt phosphorus source
is phosphorous acid, phosphorus trioxide, phosphorus trichloride
and/or hypophosphite.
[0028] The auxiliary acid is preferably hydrochloric acid,
hypochlorous acid, chlorous acid, chloric acid, hydrogen bromide,
hydrofluoric acid, hydrogen iodide, periodic acid, perchloric acid,
sulfuric acid, hydrogensulfate, sulfurous acid, hydrogensulfites,
peroxosulfuric acid, peroxodisulfuric acid; nitric acid, nitrous
acid, phosphoric acid, phosphorous acid, peroxophosphoric acid,
hypophosphorous acid, carbonic acid, silicic acid,
hexafluorosilicic acid, boric acid and/or carboxylic acids.
[0029] The invention also relates to the use of mixtures of
aluminum phosphite with sparingly soluble aluminum salts and
nitrogen-free extraneous ions as claimed in one or more of claims 1
to 5 as an intermediate for further syntheses, as a binder, as a
crosslinker or accelerator in the curing of epoxy resins,
polyurethanes, unsaturated polyester resins, as polymer
stabilizers, as crop protection compositions, as sequestrants, as a
mineral oil additive, as an anticorrosive, in washing and cleaning
composition applications, in electronics applications.
[0030] The present invention additionally provides for the use of
mixtures of aluminum phosphite with sparingly soluble aluminum
salts and nitrogen-free extraneous ions as claimed in one or more
of claims 1 to 5 as a flame retardant, especially flame retardant
for clearcoats and intumescent coatings, flame retardant for wood
and other cellulosic products, as a reactive and/or nonreactive
flame retardant for polymers, for production of flame-retardant
polymer molding compositions, for production of flame-retardant
polymer moldings and/or for rendering polyester and pure and
blended cellulose fabrics flame-retardant by impregnation, and as a
synergist in flame retardant mixtures.
[0031] The invention also relates to flame-retardant thermoplastic
or thermoset polymer molding compositions and polymer moldings,
films, filaments and fibers comprising 0.1 to 45% by weight of
mixtures of aluminum phosphite with sparingly soluble aluminum
salts and nitrogen-free extraneous ions as claimed in one or more
of claims 1 to 5, 55 to 99.9% by weight of thermoplastic or
thermoset polymer or mixtures thereof, 0 to 55% by weight of
additives and 0 to 55% by weight of filler or reinforcing
materials, where the sum of the components is 100% by weight.
[0032] The invention likewise relates to flame-retardant
thermoplastic or thermoset polymer molding compositions and polymer
moldings, films, filaments and fibers comprising 0.1 to 45% by
weight of a flame retardant mixture comprising 0.1 to 50% by weight
of mixtures of aluminum phosphite with sparingly soluble aluminum
salts and nitrogen-free extraneous ions as claimed in one or more
of claims 1 to 5 and 50 to 99.9% by weight of flame retardant, 55
to 99.9% by weight of thermoplastic or thermoset polymer or
mixtures thereof, 0 to 55% by weight of additives and 0 to 55% by
weight of filler or reinforcing materials, where the sum of the
components is 100% by weight.
[0033] The flame retardant in the aforementioned use preferably
comprises dialkylphosphinic acids and/or salts thereof and/or
condensation products of melamine and/or reaction products of
melamine with phosphoric acid and/or reaction products of
condensation products of melamine with polyphosphoric acid or
mixtures thereof; nitrogen-containing phosphates of the formulae
(NH.sub.4).sub.yH.sub.3-yPO.sub.4 and (NH.sub.4 PO.sub.3).sub.z,
where y is 1 to 3 and z is 1 to 10 000; benzoguanamine,
tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine,
melamine cyanurate, dicyandiamide and/or guanidine; magnesium
oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide,
tin oxide, aluminum hydroxide, boehmite, dihydrotalcite,
hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc
hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate,
basic zinc silicate and/or zinc stannate.
[0034] The flame retardant in the aforementioned use more
preferably comprises melam, melem, melon, dimelamine pyrophosphate,
melamine polyphosphate, melam polyphosphate, melon polyphosphate
and/or melem polyphosphate and/or mixed poly salts thereof and/or
ammonium hydrogenphosphate, ammonium dihydrogenphosphate and/or
ammonium polyphosphate.
[0035] The flame retardant in the aforementioned use preferably
also comprises aluminum hypophosphite, zinc hypophosphite, calcium
hypophosphite, sodium phosphite, monophenylphosphinic acid and
salts thereof, mixtures of dialkylphosphinic acids and salts
thereof and monoalkylphosphinic acids and salts thereof,
2-carboxyethylalkylphosphinic acid and salts thereof,
2-carboxyethylmethylphosphinic acid and salts thereof,
2-carboxyethylarylphosphinic acid and salts thereof,
2-carboxyethylphenylphosphinic acid and salts thereof,
oxa-10-phosphaphenanthrene (DOPO) and salts thereof and adducts
onto para-benzoquinone, or itaconic acid and salts thereof.
[0036] Preferably, x is also 0.01 to 0.1.
[0037] Inventive mixtures of aluminum phosphite and sparingly
soluble aluminum salts form as forced crystals in the course of
crystallization. The sparingly soluble aluminum salts preferably
form the core of the crystallized grains in the sense of core-shell
crystals. Aluminum phosphite forms the shell. The aluminum
phosphite preferably contains extraneous ions. The extraneous ions
are chemically bound into the aluminum phosphite and cannot be
removed by means of purification processes. They thus also differ
from pure physical mixtures, in which the aforementioned components
are present alongside one another and may be separable. This is not
the case for the inventive mixtures of aluminum phosphite with
sparingly soluble aluminum salts and nitrogen-free extraneous
ions.
[0038] Preferred extraneous ions are Na, K, Ca, Mg.
[0039] Preferred extraneous ions are also anions or oxo anions of
the elements of the seventh main group, such as chlorides, complex
chlorides, bromides, chlorates and perchlorates.
[0040] Preferred extraneous ions are anions or oxo anions of the
elements of the sixth main group, such as hydroxides, peroxides,
peroxide hydrates, sulfites, sulfates, sulfate hydrates,
hydrogensulfates, peroxosulfates and peroxodisulfates.
[0041] Preferred extraneous ions are anions or oxo anions of the
elements of the fifth main group, such as hydrogenphosphites,
phosphites, hypophosphite, phosphate, hydrogenphosphate and
dihydrogenphosphate.
[0042] Preferred extraneous ions are anions or oxo anions of the
elements of the fourth main group, such as carbonates,
percarbonates and stannates.
[0043] Preferred extraneous ions are anions or oxo anions of the
elements of the third main group, such as borates, perborates and
perborate hydrates.
[0044] Preferred extraneous ions, such as anions of carboxylic
acids, are formates, acetates, propionates, lactates, ascorbates
and tartrates.
[0045] The inventive mixtures of aluminum phosphite with sparingly
soluble aluminum salts and nitrogen-free extraneous ions preferably
have a particle size of 0.1 to 1000 .mu.m and a bulk density of 80
to 800 g/l, more preferably of 200 to 700 g/l.
[0046] The inventive mixtures of aluminum phosphite with sparingly
soluble aluminum salts and nitrogen-free extraneous ions preferably
have L color values of 85 to 99.9, more preferably of 90 to 98.
[0047] The inventive mixtures of aluminum phosphite with sparingly
soluble aluminum salts and nitrogen-free extraneous ions preferably
have a color values of -4 to +9, more preferably -2 to +6.
[0048] The inventive mixtures of aluminum phosphite with sparingly
soluble aluminum salts and nitrogen-free extraneous ions preferably
have b color values of -2 to +6, more preferably -1 to +3.
[0049] The color values are reported in the Hunter system (CIE-LAB
system, Commission Internationale d'Eclairage). L values range from
0 (black) to 100 (white), a values from -a (green) to +a (red), and
b values from -b (blue) to +b (yellow).
[0050] In the process according to the invention, an aluminum
source, preferably comprising sparingly soluble aluminum salts, as
described above, and a non-salt phosphorus source are crystallized
in the presence of an auxiliary acid. Optionally, the auxiliary
acid can be neutralized with nitrogen-free base.
[0051] Preferred non-salt phosphorus sources are phosphorous acid
or precursors which can form phosphite ions under the conditions of
the process, for example phosphorus trioxide (P.sub.2O.sub.6) which
can form phosphorous acid under hydrolysis, phosphorus trichloride,
or hypophosphite which can be converted to phosphite by
oxidation.
[0052] The process according to the invention avoids the use of
templates which pollute the wastewater or have to be removed in a
costly and inconvenient manner, or, when they remain in the
product, can worsen the thermal stability.
[0053] The process according to the invention also avoids the use
of readily soluble aluminum salts or phosphite salts; instead,
sparingly soluble aluminum salts and non-salt phosphorus sources
are used. A disadvantage here is actually inadequate conversion,
since the sparingly soluble aluminum phosphite crystallizes in the
form of a shell on the raw material and thus hinders the progress
of the reaction.
[0054] Surprisingly, the process according to the invention, in
contrast, enables the full conversion of all reactants by complete
or partial dissolution of the insoluble aluminum source. The
dissolved aluminum can be crystallized with the phosphorus source.
Partial dissolution is effected with catalytic or substoichiometric
amounts of auxiliary acid. As a result, a smaller amount of raw
materials (acid) is consumed and a smaller amount of wastes (salts)
is released than if the phosphorous acid were to be used in excess
in order to achieve the same effect.
[0055] Preferred auxiliary acids are acids and oxo acids of the
elements of main group 7 of the Periodic Table of the Elements, of
main group 6, of main group 5 or of main group 4, or carboxylic
acids.
[0056] Particularly suitable acids are hydrochloric acid,
hydrofluoric acid, chloric acid, perchloric acid, sulfuric acid,
sulfurous acid, nitrous acid, nitric acid, carbonic acid, formic
acid, acetic acid, propionic acid, lactic acid, ascorbic acid and
tartaric acid.
[0057] Preferably, the auxiliary acid itself is then neutralized
with substoichiometric amounts of base.
[0058] Preferred bases for this purpose are alkali metal and
alkaline earth metal hydroxides, for example sodium hydroxide
solution and potassium hydroxide solution of varying
concentrations, milk of lime, slaked lime and/or barium hydroxide
solution.
[0059] Preferred reaction conditions are temperatures of 0 to
300.degree. C., more preferably of 50 to 170.degree. C., and
reaction times of 10.sup.-7 to 10.sup.2 h. The pressure may vary
between 1 and 200 MPa (=0.00001 to 200 bar), preferably between 10
Pa and 10 MPa.
[0060] Preference is given to an energy input of 0.083 to 10
kW/m.sup.3, more preferably 0.33-1.65 kW/m.sup.3.
[0061] Preferred solvents are water, formic acid, acetic acid and
protic organic solvents, especially ethanol, methanol and
propanol.
[0062] A preferred reaction methodology is to initially charge the
aluminum source, phosphorus source and the auxiliary acid and,
after the crystallization, to meter in the nitrogen-free base.
[0063] A preferred reaction methodology is to initially charge the
aluminum source and the phosphorus source and to meter in the
auxiliary acid in the course of crystallization.
[0064] A preferred reaction methodology is to initially charge the
aluminum source and phosphorus source, to meter in auxiliary acid
in the course of crystallization, and to meter in nitrogen-free
base after the crystallization.
[0065] A preferred pH in the course of crystallization is 0 to 7,
more preferably 0.5 to 6 and most preferably 1 to 5. The pH used in
the course of crystallization may affect the thermal stability of
the inventive aluminum phosphite mixtures.
[0066] The reaction methodology determines the concentrations of
the reactants in the course of crystallization. This determines,
for example, particle sizes and thermal stability of the
products.
[0067] A preferred solids concentration is 2 to 30% by weight, more
preferably 5 to 15% by weight.
[0068] A preferred ratio of auxiliary acid to phosphorus source is
0.1 to 50 mol % per mole of phosphorus, more preferably 1 to 20 mol
%, most preferably 2 to 10 mol %.
[0069] A preferred ratio of nitrogen-free base to phosphorus source
is 0.1 to 70 mol % per mole of phosphorus, more preferably 1 to 40
mol %, most preferably 1 to 30 mol %.
[0070] A preferred ratio of phosphorus source to the aluminum
source is 3 mol/1 mol to 1 mol/3 mol, more preferably 2.5 mol/2 mol
to 3.5 mol/2 mol.
[0071] Preference is given to the use of mixtures of aluminum
phosphite with sparingly soluble aluminum salts and nitrogen-free
extraneous ions as a flame retardant synergist.
[0072] Preferred dialkylphosphinic acids or salts thereof are those
of the formula (II)
##STR00001## [0073] in which [0074] R.sup.1, R.sup.2 are the same
or different and are each linear or branched C.sub.1-C.sub.6-alkyl;
[0075] M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn,
Li, Na, K, H and/or a protonated nitrogen base; [0076] m is 1 to
4.
[0077] Preferred dialkylphosphinic salts are aluminum
trisdiethylphosphinate, aluminum trismethylethylphosphinate,
titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate,
titanyl bismethylethylphosphinate, titanium
tetrakismethylethylphosphinate, zinc bisdiethylphosphinate, zinc
bismethylethylphosphinate and mixtures thereof.
[0078] Suitable further flame retardants are also particular
nitrogen compounds (DE-A-196 14 424, DE-A-197 34 437 and DE-A-197
37 727). These are preferably those of the formulae (III) to (VIII)
or mixtures thereof
##STR00002## [0079] in which [0080] R.sup.5 to R.sup.7 are each
hydrogen, C.sub.1-C.sub.8-alkyl, C.sub.5-C.sub.16-cycloalkyl or
-alkylcycloalkyl, possibly substituted by a hydroxyl function or a
C.sub.1-C.sub.4-hydroxyalkyl function, C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.8-alkoxy, -acyl, -acyloxy, C.sub.6-C.sub.12-aryl or
-arylalkyl, --OR.sup.8 and --N(R.sup.8)R.sup.9, and also
N-alicyclically or N-aromatically, [0081] R.sup.8 is hydrogen,
C.sub.1-C.sub.8-alkyl, C.sub.5-C.sub.16-cycloalkyl or
-alkylcycloalkyl, possibly substituted by a hydroxyl function or a
C.sub.1-C.sub.4-hydroxyalkyl function, C.sub.2-C.sub.8-alkenyl,
C.sub.1-C.sub.8-alkoxy, -acyl, -acyloxy or C.sub.6-C.sub.12-aryl or
arylalkyl, [0082] R.sup.9 to R.sup.13 are the same groups as
R.sup.8, and also --O--R.sup.8, [0083] m and n are each
independently 1, 2, 3 or 4, [0084] X denotes acids which can form
adducts with triazine compounds (III); [0085] or oligomeric esters
of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic
acids.
[0086] The remaining moisture content of the inventive mixtures of
aluminum phosphite with sparingly soluble aluminum salts and
nitrogen-free extraneous ions is 0.01 to 9%, preferably 0.05 to
0.5%.
[0087] Preferred polymer additives for flame-retardant polymer
molding compositions and flame-retardant polymer moldings are UV
absorbers, light stabilizers, lubricants, colorants, antistats,
nucleating agents, reinforcing agents, fillers and/or
synergists.
[0088] The invention also relates to polymer moldings, films,
filaments and fibers comprising 1 to 50% by weight of the inventive
mixtures of aluminum phosphite with sparingly soluble aluminum
salts and nitrogen-free extraneous ions [0089] 50 to 99% by weight
of polystyrene-based polymer or mixtures thereof [0090] 0 to 60% by
weight of polymer additives [0091] 0 to 60% by weight of
filler.
[0092] Preference is given in accordance with the invention to the
use of the inventive flame-retardant polymer moldings as lamp
components such as lamp fittings and holders, plugs and multisocket
extensions, bobbins, housing for capacitors or contactors, and
circuit breakers, relay housing and reflectors.
[0093] The invention also relates to an intumescent flame-retardant
coating comprising 1 to 50% of the inventive mixtures of aluminum
phosphite with sparingly soluble aluminum salts and nitrogen-free
extraneous ions, and 50 to 99% by weight of ammonium polyphosphate,
binder, foam former, fillers, dialkylphosphinic acid salts and/or
polymer additives.
[0094] The polymers preferably originate from the group of the
thermoplastic polymers such as polyester, polystyrene or polyamide,
and/or the thermoset polymers.
[0095] The polymers are preferably polymers of mono- and diolefins,
for example polypropylene, polyisobutylene, polybutene-1,
poly-4-methylpentene-1, polyisoprene or polybutadiene, and addition
polymers of cycloolefins, for example of cyclopentene or
norbornene; and also polyethylene (which may optionally be
crosslinked), e.g. high-density polyethylene (HDPE), high-density
high-molar mass polyethylene (HDPE-HMW), high-density
ultrahigh-molar mass polyethylene (HDPE-UHMW), medium-density
polyethylene (MDPE), low-density polyethylene (LDPE), linear
low-density polyethylene (LLDPE), branched low-density polyethylene
(BLDPE), and mixtures thereof.
[0096] The polymers are preferably copolymers of mono- and
diolefins with one another or with other vinyl monomers, for
example ethylene-propylene copolymers, linear low-density
polyethylene (LLDPE) and mixtures thereof with low-density
polyethylene (LDPE), propylene-butene-1 copolymers,
propylene-isobutylene copolymers, ethylene-butene-1 copolymers,
ethylene-hexene copolymers, ethylene-methylpentene copolymers,
ethylene-heptene copolymers, ethylene-octene copolymers,
propylene-butadiene copolymers, isobutylene-isoprene copolymers,
ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate
copolymers, ethylene-vinyl acetate copolymers and copolymers
thereof with carbon monoxide, or ethylene-acrylic acid copolymers
and salts thereof (ionomers), and also terpolymers of ethylene with
propylene and a diene such as hexadiene, dicyclopentadiene or
ethylidenenorbornene; and also mixtures of such copolymers with one
another, e.g. polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid
copolymers, LLDPE/ethylene-vinyl acetate copolymers,
LLDPE/ethylene-acrylic acid copolymers and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0097] The polymers are preferably hydrocarbon resins (e.g.
C.sub.5-C.sub.9), including hydrogenated modifications thereof
(e.g. tackifier resins) and mixtures of polyalkylenes and
starch.
[0098] The polymers are preferably polystyrene (Polystyrene 143E
(BASF)), poly(p-methylstyrene), poly(alpha-methylstyrene).
[0099] The polymers are preferably copolymers of styrene or
alpha-methylstyrene with dienes or acrylic derivatives, for example
styrene-butadiene, styrene-acrylonitrile, styrene-alkyl
methacrylate, styrene-butadiene-alkyl acrylate and methacrylate,
styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate;
more impact-resistant mixtures of styrene copolymers and another
polymer, for example a polyacrylate, a diene polymer or an
ethylene-propylene-diene terpolymer; and block copolymers of
styrene, for example styrene-butadiene-styrene,
styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or
styrene-ethylene/propylene-styrene.
[0100] The polymers are preferably graft copolymers of styrene or
alpha-methylstyrene, for example styrene onto polybutadiene,
styrene onto polybutadiene-styrene or polybutadiene-acrylonitrile
copolymers, styrene and acrylonitrile (or methacrylonitrile) onto
polybutadiene; styrene, acrylonitrile and methyl methacrylate onto
polybutadiene; styrene and maleic anhydride onto polybutadiene;
styrene, acrylonitrile and maleic anhydride or maleimide onto
polybutadiene; styrene and maleimide onto polybutadiene, styrene
and alkyl acrylates or alkyl methacrylates onto polybutadiene,
styrene and acrylonitrile onto ethylene-propylene-diene
terpolymers, styrene and acrylonitrile onto polyalkyl acrylates or
polyalkyl methacrylates, styrene and acrylonitrile onto
acrylate-butadiene butadiene copolymers, and mixtures thereof, as
known, for example, as ABS, MBS, ASA or AES polymers.
[0101] The styrene polymers are preferably comparatively
coarse-pore foam such as EPS (expanded polystyrene), e.g. Styropor
(BASF) and/or foam with relatively fine pores such as XPS (extruded
rigid polystyrene foam), e.g. Styrodur.RTM. (BASF). Preference is
given to polystyrene foams, for example Austrotherm.RTM. XPS,
Styrofoam.RTM. (Dow Chemical), Floormate.RTM., Jackodur.RTM.,
Lustron.RTM., Roofmate.RTM., Styropor.RTM., Styrodur.RTM.,
Styrofoam.RTM., Sagex.degree. and Telgopor.RTM..
[0102] The polymers are preferably halogenated polymers, for
example polychloroprene, chlorine rubber, chlorinated and
brominated copolymer of isobutylene-isoprene (halobutyl rubber),
chlorinated or chlorosulfonated polyethylene, copolymers of
ethylene and chlorinated ethylene, epichlorohydrin homo- and
copolymers, especially polymers of halogenated vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride; and copolymers thereof, such as
vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or
vinylidene chloride-vinyl acetate.
[0103] The polymers are preferably polymers which derive from
alpha,beta-unsaturated acids and derivatives thereof, such as
polyacrylates and polymethacrylates, polymethyl methacrylates,
polyacrylamides and polyacrylonitriles impact-modified with butyl
acrylate, and copolymers of the monomers mentioned with one another
or with other unsaturated monomers, for example
acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate
copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers,
acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl
methacrylate-butadiene terpolymers.
[0104] The polymers are preferably polymers which derive from
unsaturated alcohols and amines or the acyl derivatives or acetals
thereof, such as polyvinyl alcohol, polyvinyl acetate, stearate,
benzoate or maleate, polyvinyl butyral, polyallyl phthalate,
polyallylmelamine; and copolymers thereof with olefins.
[0105] The polymers are preferably homo- and copolymers of cyclic
ethers, such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bisglycidyl
ethers.
[0106] The polymers are preferably polyacetals such as
polyoxymethylene, and those polyoxymethylenes which contain
comonomers, for example ethylene oxide; polyacetals which have been
modified with thermoplastic polyurethanes, acrylates or MBS.
[0107] The polymers are preferably polyphenylene oxides and
sulfides and mixtures thereof with styrene polymers or
polyamides.
[0108] The polymers are preferably polyurethanes which derive from
polyethers, polyesters and polybutadienes having both terminal
hydroxyl groups and aliphatic or aromatic polyisocyanates, and the
precursors thereof.
[0109] The polymers are preferably polyamides and copolyamides
which derive from diamines and dicarboxylic acids and/or from
aminocarboxylic acids or the corresponding lactams, such as nylon
2/12, nylon 4 (poly-4-aminobutyric acid, Nylon.RTM. 4, from
DuPont), nylon 4/6 (poly(tetramethyleneadipamide)), Nylon.RTM. 4/6,
from DuPont), nylon 6 (polycaprolactam, poly-6-aminohexanoic acid,
Nylon.RTM. 6, from DuPont, Akulon.RTM. K122, from DSM; Zytel.RTM.
7301, from DuPont; Durethan.RTM. B 29, from Bayer), nylon 6/6
((poly(N,N'-hexamethyleneadipamide), Nylon.RTM. 6/6 , from DuPont,
Zytel.RTM. 101, from DuPont; Durethan.RTM. A30, Durethan.RTM. AKV,
Durethan.RTM. AM, from Bayer; Ultramid.RTM. A3, from BASF), nylon
6/9 (poly(hexamethylenenonanamide), Nylon.RTM. 6/9, from DuPont),
nylon 6/10 (poly(hexamethylenesebacamide), Nylon.RTM. 6/10, from
DuPont), nylon 6/12 (poly(hexamethylenedodecanediamide), Nylon.RTM.
6/12, from DuPont), nylon 6/66
(poly(hexamethyleneadipamide-co-caprolactam), Nylon.RTM. 6/66, from
DuPont), nylon 7 (poly-7-aminoheptanoic acid, Nylon.RTM. 7, from
DuPont), nylon 7,7 (polyheptamethylenepimelamide, Nylon.RTM. 7,7,
from DuPont), nylon 8 (poly-8-aminooctanoic acid, Nylon.RTM. 8,
from DuPont), nylon 8,8 (polyoctamethylenesuberamide, Nylon.RTM.
8,8, from DuPont), nylon 9 (poly-9-aminononanoic acid, Nylon.RTM.
9, from DuPont), nylon 9,9 (polynonamethyleneazelamide, Nylon.RTM.
9,9, from DuPont), nylon 10 (poly-10-aminodecanoic acid, Nylon.RTM.
10, from DuPont), nylon 10,9 (poly(decamethyleneazelamide),
Nylon.RTM. 10,9, from DuPont), nylon 10,10
(polydecamethylenesebacamide, Nylon.RTM. 10,10, from DuPont), nylon
11 (poly-11-aminoundecanoic acid, Nylon.RTM. 11, from DuPont),
nylon 12 (polylauryllactam, Nylon.RTM. 12, from DuPont,
Grillamid.RTM. L20, from Ems Chemie), aromatic polyamides
proceeding from m-xylene, diamine and adipic acid; polyamides
prepared from hexamethylenediamine and iso- and/or terephthalic
acid (polyhexamethyleneisophthalamide,
polyhexamethyleneterephthalamide) and optionally an elastomer as a
modifier, e.g. poly-2,4,4-trimethylhexamethyleneterephthalamide or
poly-m-phenyleneisophthalamide; block copolymers of the
aforementioned polyamides with polyolefins, olefin copolymers,
ionomers or chemically bonded or grafted elastomers; or with
polyethers, for example with polyethylene glycol, polypropylene
glycol or polytetramethylene glycol. In addition,
ethylene-propylene-diene rubber-(EPDM-) or ABS-modified polyamides
or copolyamides, and polyamides condensed during processing ("RIM
polyamide systems").
[0110] The polymers are preferably polyureas, polyimides,
polyamidimides, polyetherimides, polyesterimides, polyhydantoins
and polybenzimidazoles.
[0111] The polymers are preferably polyesters which derive from
dicarboxylic acids and dialcohols and/or from hydroxycarboxylic
acids or the corresponding lactones, such as polyethylene
terephthalate, polybutylene terephthalate (Celanex.RTM. 2500,
Celanex.RTM. 2002, from Celanese; Ultradur.RTM., from BASF),
poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates,
and block polyether esters which derive from polyethers with
hydroxyl end groups; and also polyesters modified with
polycarbonates or MBS.
[0112] The polymers are preferably polycarbonates and polyester
carbonates.
[0113] The polymers are preferably polysulfones, polyether sulfones
and polyether ketones.
[0114] Preferably, the polymers are crosslinked polymers which
derive from aldehydes on the one hand, and phenols, urea or
melamine on the other hand, such as phenol-formaldehyde,
urea-formaldehyde and melamine-formaldehyde resins.
[0115] The polymers are preferably drying and nondrying alkyd
resins.
[0116] The polymers are preferably unsaturated polyester resins
which derive from copolyesters of saturated and unsaturated
dicarboxylic acids with polyhydric alcohols, and vinyl compounds as
crosslinking agents, and also the halogenated, flame-retardant
modifications thereof.
[0117] The polymers preferably comprise crosslinkable acrylic
resins which derive from substituted acrylic esters, for example
from epoxy acrylates, urethane acrylates or polyester
acrylates.
[0118] Preferably, the polymers are alkyd resins, polyester resins
and acrylate resins which have been crosslinked with melamine
resins, urea resins, isocyanates, isocyanurates, polyisocyanates or
epoxy resins.
[0119] The polymers are preferably crosslinked epoxy resins which
derive from aliphatic, cycloaliphatic, heterocyclic or aromatic
glycidyl compounds, for example products of bisphenol A diglycidyl
ethers, bisphenol F diglycidyl ethers, which are crosslinked by
means of customary hardeners, for example anhydrides or amines,
with or without accelerators.
[0120] The polymers are preferably mixtures (polyblends) of the
abovementioned polymers, for example PP/EPDM
(polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or
ABS (polyamide/ethylene-propylene-diene rubber or
acrylonitrile-butadiene-styrene), PVC/EVA (polyvinyl
chloride/ethylene-vinyl acetate), PVC/ABS (polyvinyl
chloride/acrylonitrile-butadiene-styrene), PVC/MBS (polyvinyl
chloride/methacrylate-butadiene-styrene), PC/ABS
(polycarbonate/acrylonitrile-butadiene-styrene), PBTP/ABS
(polybutylene terephthalate/acrylonitrile-butadiene-styrene),
PC/ASA (polycarbonate/acrylic ester-styrene-acrylonitrile), PC/PBT
(polycarbonate/polybutylene terephthalate), PVC/CPE (polyvinyl
chloride/chlorinated polyethylene), PVC/acrylate (polyvinyl
chloride/acrylate, POM/thermoplastic PUR
(polyoxymethylene/thermoplastic polyurethane), PC/thermoplastic PUR
(polycarbonate/thermoplastic polyurethane), POM/acrylate
(polyoxymethylene/acrylate), POM/MBS
(polyoxymethylene/methacrylate-butadiene-styrene), PPO/HIPS
(polyphenylene oxide/high-impact polystyrene), PPO/PA 6,6
(polyphenylene oxide/nylon 6,6) and copolymers, PA/HDPE
(polyamide/high-density polyethylene), PA/PP
(polyamide/polyethylene), PA/PPO (polyamide/polyphenylene oxide),
PBT/PC/ABS (polybutylene
terephthalate/polycarbonate/acrylonitrile-butadiene-styrene) and/or
PBT/PET/PC (polybutylene terephthalate/polyethylene
terephthalate/polycarbonate).
[0121] Suitable compounding units for production of polymer molding
compositions are single-shaft extruders or single-screw extruders,
for example from Berstorff GmbH, Hanover and/or from Leistritz,
Nuremberg, and multizone screw extruders with three-zone screws
and/or short compression screws, and twin-screw extruders, for
example from Coperion Werner & Pfleiderer GmbH & Co. KG,
Stuttgart (ZSK 25, ZSK30, ZSK 40, ZSK 58, ZSK MEGAcompounder 40,
50, 58, 70, 92, 119, 177, 250, 320, 350, 380) and/or from Berstorff
GmbH, Hanover, Leistritz Extrusionstechnik GmbH, Nuremberg.
[0122] Effective screw lengths (L) in the case of single-shaft
extruders or single-screw extruders are 20 to 40D, and in the case
of multizone screw extruders, for example, 25D with intake zone
(L=10D), transition zone (L=6D), ejection zone (L=9D); in the case
of twin-screw extruders 8 to 48D.
[0123] Suitable compounding units are also co-kneaders, for example
from Coperion Buss Compounding Systems, Pratteln, Switzerland, e.g.
MDK/E46-11D and/or laboratory kneaders (MDK 46 from Buss,
Switzerland with L=11D).
[0124] Usable compounding units are also compounders with a
contrarotatory twin screw, for example Compex 37 and 70 models from
Krauss-Maffei Berstorff, and ring extruders, for example from
3+Extruder GmbH, Laufen, with a ring of three to twelve small
screws which rotate about a static core, and/or planetary gear
extruders, for example from Entex, Bochum, and/or vented extruders
and/or cascade extruders and/or Maillefer screws.
[0125] Production, processing and testing of flame-retardant
polymer molding compositions and polymer moldings
[0126] The flame-retardant components were mixed with the polymer
pellets and any additives and incorporated in a twin-screw extruder
(model: Leistritz LSM 30/34) at temperatures of 230 to 260.degree.
C. (PBT-GR) or of 260 to 280.degree. C. (PA 66-GR). The homogenized
polymer strand was drawn off, cooled in a water bath and then
pelletized.
[0127] After sufficient drying, the molding compositions were
processed on an injection molding machine (model: Aarburg
Allrounder) at melt temperatures of 240 to 270.degree. C. (PBT-GR)
or of 260 to 290.degree. C. (PA 66-GR) to give test specimens.
[0128] Test specimens of each mixture were used to determine the UL
94 fire class (Underwriter Laboratories) on specimens of thickness
1.5 mm. The UL 94 fire classifications are as follows: [0129] V-0:
afterflame time never longer than 10 sec, total of afterflame times
for 10 flame applications not more than 50 sec, no flaming drops,
no complete consumption of the specimen, afterglow time for
specimens never longer than 30 sec after end of flame application
[0130] V-1: afterflame time never longer than 30 sec after end of
flame application, total of afterflame times for 10 flame
applications not more than 250 sec, afterglow time for specimens
never longer than 60 sec after end of flame application, other
criteria as for V-0 [0131] V-2: cotton indicator ignited by flaming
drops, other criteria as for V-1.
[0132] Not classifiable (ncl): does not fulfill fire class V-2.
Test of Thermal Stability and Phosphine Formation
[0133] An important criterion for the thermal stability of the
inventive mixtures of aluminum phosphite with sparingly soluble
aluminum salts and nitrogen-free extraneous ions is the temperature
at which decomposition occurs and toxic phosphine (PH.sub.3) is
formed. The release thereof in the course of production of
flame-retardant polymers must absolutely be avoided. For the
determination, a material sample is heated in a tubular oven under
flowing nitrogen (30 l/g), by raising the temperature stepwise. The
decomposition temperature has been attained when a Drager detection
tube can detect more than 1 ppm PH.sub.3 (short-term tube for
hydrogen phosphide).
Determination of the Content of Water of Crystallization (Residual
Moisture Content)
[0134] A specimen is heated to constant weight in a Nabertherm
muffle furnace heated to 300.degree. C. for 15 minutes. The mass of
the residue based on the starting weight, calculated in percent and
subtracted from 100, gives the weight loss.
[0135] The invention is illustrated by the examples which follow.
Further data (starting weights, conditions, yields and analyses)
can be found in tables 1 and 2.
Example 1
[0136] 674 g of aluminum hydroxide, 1511 g of 70% by weight
phosphorous acid, 361 g of 25% by weight sulfuric acid and 11 067 g
of demineralized water are initially charged in a 16 l
high-pressure stirred vessel from Pfaudler, heated to 150.degree.
C. and stirred for 3 h. The resulting suspension is discharged and
filtered at 80.degree. C. by means of a heatable Seitz pressure
filter and washed with demineralized water, redispersed and washed
once again, then dried at 220.degree. C. In a very high yield, an
inventive mixture of aluminum phosphite with sparingly soluble
aluminum salts and nitrogen-free extraneous ions is obtained with
very high thermal stability (PH.sub.3 formation from 360.degree.
C.).
Example 2
[0137] As in example 1, aluminum hydroxide, 70% by weight
phosphorous acid, 25% by weight sulfuric acid and 11 067 g of
demineralized water are initially charged, heated to 150.degree. C.
and stirred for 23 h, then 688 g of 25% by weight sodium hydroxide
solution are added and the mixture is stirred for 1 h. As in
example 1, the suspension is discharged, filtered, washed and
dried. In a very high yield, an inventive mixture of aluminum
phosphite with sparingly soluble aluminum salts and nitrogen-free
extraneous ions is obtained with very high thermal stability
(PH.sub.3 formation from 380.degree. C.).
Example 3
[0138] As in example 1, aluminum hydroxide, 70% by weight
phosphorous acid and demineralized water are initially charged,
heated to 120.degree. C. and stirred for 6 h. During the reaction
time, the pH of the solution is kept at pH=1 by metered addition of
1237 g of 25% by weight sulfuric acid. Shortly before the end of
the reaction, 1054 g of 25% by weight sodium hydroxide solution are
added. As in example 1, the suspension is discharged, filtered,
washed and dried. In a very high yield, an inventive mixture of
aluminum phosphite with sparingly soluble aluminum salts and
nitrogen-free extraneous ions is obtained with very high thermal
stability (PH.sub.3 formation from 380.degree. C.).
Example 4
[0139] As in example 1, aluminum hydroxide, 70% by weight
phosphorous acid and demineralized water are initially charged,
heated to 100.degree. C. and stirred for 24 h. During the reaction
time, the pH of the solution is kept at pH=1.5 by metered addition
of 361 g of 25% by weight sulfuric acid. As in example 1, the
suspension is discharged, filtered, washed and dried. In a very
high yield, an inventive mixture of aluminum phosphite with
sparingly soluble aluminum salts and nitrogen-free extraneous ions
is obtained with very high thermal stability (PH.sub.3 formation
from 380.degree. C.).
Example 5 (Comparative)
[0140] A noninventive, commercially available aluminum phosphite
shows a lower thermal stability in comparison (PH.sub.3 formation
from 320.degree. C.).
Flame-Retardant Polymer Molding Compositions and Polymer
Moldings
[0141] 50% by weight of nylon 6,6 polymer, 30% by weight of glass
fibers, 3.6% by weight of inventive mixture of aluminum phosphite
with sparingly soluble aluminum salts and nitrogen-free extraneous
ions according to example 3 and 16.4% by weight of Exolit.RTM.
OP1230 aluminum diethylphosphinate (from Clariant) are used in
accordance with the general methods specified to produce
flame-retardant polymer molding compositions and flame-retardant
polymer moldings in the form of UL-94 test specimens. The UL-94
test gives V-0 classification.
[0142] 50% by weight of polybutylene terephthalate polymer, 30% by
weight of glass fibers, 3.6% by weight of inventive mixture of
aluminum phosphite with sparingly soluble aluminum salts and
nitrogen-free extraneous ions according to example 3 and 16.4% by
weight of Exolit.RTM. OP1240 aluminum diethylphosphinate (from
Clariant) are used in accordance with the general methods specified
to produce flame-retardant polymer molding compositions and
flame-retardant polymer moldings in the form of UL-94 test
specimens. The UL-94 test gives V-0 classification.
TABLE-US-00001 TABLE 1 Starting weights and reaction conditions
Starting weights Conditions Phosphorous Aluminum Sulfuric Sodium
hydroxide Reaction Water acid hydroxide acid 25% solution 25%
Temperature time Example [g] [g] [g] [g] [g] [.degree. C.] [h] 1
11067 1511 674 361 -- 150 3 2 11067 1511 674 361 688 150 24 3 11067
1511 674 1237 1054 120 6 4 11067 1511 674 361 -- 100 24 5 aluminum
phosphite (comp.) Aluminum hydroxide: Hydral .RTM. 710, from
Caldic
TABLE-US-00002 TABLE 2 Analysis results, compositions of the
inventive products, test results Addn. of the aluminum phosphite
mixtures Weight loss Analyses aluminum aluminum (% by wt., PH.sub.3
aluminum phosphorus sodium sulfate phosphite hydroxide sodium
sulfate 300.degree. C.) formation Yield Example [%] [%] [%] [%] [%]
[%] [%] [%] [%] [.degree. C.] [%] 1 18.3 30.6 0.007 0.993 96.7 1.4
0.007 0.093 1.27 360 95.3 2 18.7 30.3 0.340 0.087 95.8 3.0 0.340
0.087 0.60 380 97.8 3 17.2 29.5 5.000 0.190 93.2 0.1 5.000 0.190
0.82 380 95.1 4 18.4 29.2 0.003 3.000 92.3 4.0 0.003 3.000 0.60 360
94.7 5 96.0 4.0 320 (comp.)
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