U.S. patent application number 14/364972 was filed with the patent office on 2014-11-27 for mixtures of at least one dialkylphosphinic acid with at least one other dialkylphosphinic acid that is different therefrom, method for production thereof, and use thereof.
This patent application is currently assigned to CLARIANT FINANCE (BVI) LIMITED. The applicant listed for this patent is Harald Bauer, Frank Osterod, Fabian Schneider, Martin Sicken. Invention is credited to Harald Bauer, Frank Osterod, Fabian Schneider, Martin Sicken.
Application Number | 20140350149 14/364972 |
Document ID | / |
Family ID | 47428550 |
Filed Date | 2014-11-27 |
United States Patent
Application |
20140350149 |
Kind Code |
A1 |
Schneider; Fabian ; et
al. |
November 27, 2014 |
Mixtures Of At Least One Dialkylphosphinic Acid With At Least One
Other Dialkylphosphinic Acid That Is Different Therefrom, Method
For Production Thereof, And Use Thereof
Abstract
The invention relates to a mixture of at least one
dialkylphosphinic acid of the formula (I) ##STR00001## in which
R.sup.1, R.sup.2 are the same or different and are each
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl, C.sub.7-C.sub.18-alkylaryl, with at least
one different dialkylphosphinic acid of the formula (II)
##STR00002## in which R.sup.3, R.sup.4 are the same or different
and are each C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl and/or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2.
Inventors: |
Schneider; Fabian; (Koeln,
DE) ; Osterod; Frank; (Koeln, DE) ; Bauer;
Harald; (Kerpen, DE) ; Sicken; Martin; (Koeln,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Schneider; Fabian
Osterod; Frank
Bauer; Harald
Sicken; Martin |
Koeln
Koeln
Kerpen
Koeln |
|
DE
DE
DE
DE |
|
|
Assignee: |
CLARIANT FINANCE (BVI)
LIMITED
Tortola
VG
|
Family ID: |
47428550 |
Appl. No.: |
14/364972 |
Filed: |
December 13, 2012 |
PCT Filed: |
December 13, 2012 |
PCT NO: |
PCT/EP2012/005175 |
371 Date: |
June 12, 2014 |
Current U.S.
Class: |
524/133 ;
252/609 |
Current CPC
Class: |
C07F 9/301 20130101;
C08G 59/1488 20130101; C09K 21/12 20130101; C07F 9/30 20130101;
C08L 63/00 20130101; C08L 61/06 20130101 |
Class at
Publication: |
524/133 ;
252/609 |
International
Class: |
C09K 21/12 20060101
C09K021/12 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 21, 2011 |
DE |
10 2011 121 900.9 |
Claims
1. A mixture of at least one dialkylphosphinic acid of the formula
(I) ##STR00005## wherein R.sup.1, R.sup.2 are the same or different
and are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least
one different dialkylphosphinic acid of the formula (II)
##STR00006## wherein R.sup.3, R.sup.4 are the same or different and
are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2.
2. The mixture as claimed in claim 1, wherein R.sup.1 and R.sup.2
are the same or different and are methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,
n-hexyl, isohexyl or phenyl.
3. The mixture as claimed in claim 1, wherein R.sup.3 and R.sup.4
are the same or different and are methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl,
n-hexyl, isohexyl or phenyl, with the proviso that at least one of
the R.sup.3 and R.sup.4 radicals is different than R.sup.1 and
R.sup.2.
4. The mixture as claimed in claim 1, comprising 0.1 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 99.9 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
5. The mixture as claimed in claim 1, comprising 40 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 60 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
6. The mixture as claimed in claim 1, comprising 60 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 40 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
7. The mixture as claimed in claim 1, comprising 80 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 20 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
8. The mixture as claimed in claim 1, comprising 90 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 10 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
9. The mixture as claimed in claim 1, comprising 95 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 5 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
10. The mixture as claimed in claim 1, comprising 98 to 99.9% by
weight of the at least one dialkylphosphinic acid of the formula
(I) and 2 to 0.1% by weight of the at least one different
dialkylphosphinic acid of the formula (II).
11. The mixture as claimed in claim 1, wherein the at least one
dialkylphosphinic acid is diethylphosphinic acid,
ethylpropylphosphinic acid, ethylbutylphosphinic acid,
ethylpentylphosphinic acid, ethylhexylphosphinic acid,
dipropylphosphinic acid, propylbutylphosphinic acid,
propylpentylphosphinic acid, propylhexylphosphinic acid,
dibutylphosphinic acid, butylpentylphosphinic acid,
butylhexylphosphinic acid, dipentylphosphinic acid,
pentylhexylphosphinic acid dihexylphosphinic acid or mixtures
thereof.
12. The mixture as claimed in claim 1 wherein the at least one
dialkylphosphinic acid is diethylphosphinic acid, wherein the at
least one different dialkylphosphinic acid is butylethylphosphinic
acid and wherein the mixture comprises 98 to 99.9% by weight of
diethylphosphinic acid and 2 to 0.1% by weight of
butylethylphosphinic acid.
13. The mixture as claimed in claim 1, further comprising at least
one synergist, wherein the at least one synergist is a
nitrogen-containing compound, melem, melam, melon, melamine borate,
melamine cyanurate, melamine phosphate, dimelamine phosphate,
pentamelamine triphosphate, trimelamine diphosphate,
tetrakismelamine triphosphate, hexakismelamine pentaphosphate,
melamine diphosphate, melamine tetraphosphate, melamine
pyrophosphate, melamine polyphosphate, melam polyphosphate, melem
polyphosphate, melon polyphosphate or mixtures thereof; aluminum
compounds, aluminum hydroxide, halloysite, sapphire products,
boehmite, nanoboehmite; magnesium compounds, magnesium hydroxide;
tin compounds, tin oxides; antimony compounds, antimony oxides;
zinc compounds, zinc oxide, zinc hydroxide, zinc oxide hydrate,
zinc carbonate, zinc stannate, zinc hydroxystannate, zinc silicate,
zinc phosphate, zinc borophosphate, zinc borate, zinc molybdate or
mixtures thereof; silicon compounds, silicates, silicones or
mixtures thereof; phosphorus compounds, phosphinic acids and salts
thereof, phosphonic acids and salts thereof, phosphine oxides,
phosphazenes, piperazine (pyro)phosphates or mixtures thereof;
carbodiimides, piperazines, (poly)isocyanates, styrene-acrylic
polymers; carbonylbiscaprolactam or mixtures thereof; nitrogen
compounds selected from the group consisting of oligomeric esters
of tris(hydroxyethyl) isocyanurate with aromatic polycarboxylic
acids, or benzoguanamine, acetoguanamine, tris(hydroxyethyl)
isocyanurate, allantoin, glycoluril, cyanurates, cyanurate-epoxide
compounds, urea cyanurate, dicyanamide, guanidine, guanidine
phosphate, sulfate and mixtures thereof.
14. The mixture as claimed in claim 1, comprising 99 to 1% by
weight of the mixture of at least one dialkylphosphinic acid of the
formula (I) and at least one different dialkylphosphinic acid of
the formula (II) and 1 to 99% by weight of a synergist.
15. A process for preparing a mixture of at least one
dialkylphosphinic acid of the formula (I) ##STR00007## wherein
R.sup.1, R.sup.2 are the same or different and are
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least
one different dialkylphosphinic acid of the formula (II)
##STR00008## wherein R.sup.3, R.sup.4 are the same or different and
are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2, comprising the steps of
reacting a phosphorus source with an initiator and an olefin and
treating the alkylated phosphorus compound thus obtained with a
mineral acid and converting it, by concentration and workup, to a
mixture of at least one dialkylphosphinic acid of the formula (I)
and at least one different dialkylphosphinic acid of the formula
(II).
16. The process as claimed in claim 15, wherein the phosphorus
source is a phosphinic salt, the olefin is ethylene and the mineral
acid is sulfuric acid or hydrochloric acid, and the free-radical
initiator is 2,2'-azobis(2-amidinopropane) dihydrochloride,
2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride,
azobis(isobutyronitrile), 4,4'-azobis(4-cyanopentanoic acid) and/or
2,2'-azobis(2-methylbutyronitrile), hydrogen peroxide, ammonium
peroxodisulfate, potassium peroxodisulfate, dibenzoyl peroxide,
di-tert-butyl peroxide, peracetic acid, diisobutyryl peroxide,
cumene peroxyneodecanoate, tert-butyl peroxyneodecanoate,
tert-butyl peroxypivalate, tert-amyl peroxypivalate, dipropyl
peroxydicarbonate, dibutyl peroxydicarbonate, dimyristyl
peroxydicarbonate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl
peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexylcarbonate,
tert-butyl peroxyisobutyrate, 1,1-di(tert-butylperoxy)cyclohexane,
tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl
peroxydiethylacetate, tert-butyl peroxyisopropylcarbonate,
2,2-di(tert-butylperoxy)butane, tert-amyl hydroperoxide
and/er-2,5-dimethyl-2,5-di(tert-butylperoxy)hexane or mixtures
thereof.
17. The process as claimed in claim 15 further comprising reacting
sodium phosphinate with ethylene and then with dilute sulfuric
acid, concentrated, filtered and distilled, in order to obtain a
mixture of diethylphosphinic acid and butylethylphosphinic
acid.
18. The process as claimed in claim 15, wherein the reaction takes
place in a solvent and the solvent is an alcohol, acid or
water.
19. The process as claimed in claim 15, wherein the reaction
temperature is between 50 and 150.degree. C.
20. An intermediate for further syntheses, a binder, a crosslinker
or accelerator in the curing of epoxy resins, polyurethanes and
unsaturated polyester resins, a polymer stabilizer, a crop
protection composition, a sequestrant, a mineral oil additive, an
anticorrosive, a washing composition, a cleaning composition or an
electronic composition comprising a mixture of at least one
dialkylphosphinic acid of the formula (I) ##STR00009## wherein
R.sup.1, R.sup.2 are the same or different and are
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least
one different dialkylphosphinic acid of the formula (II)
##STR00010## wherein R.sup.3. R.sup.4 are the same or different and
are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2.
21. A flame retardant, as a flame retardant for clearcoats and
intumescent coatings, a flame retardant for wood and other
cellulosic products, a reactive and a nonreactive flame retardant
for polymers, a flame-retardant polymer molding a flame-retardant
for rendering polyester and pure and blended cellulose fabrics
flame-retardant by impregnation, or a synergist comprising a
mixture of at least one dialkylphosphinic acid of the formula (I)
##STR00011## wherein R.sup.1, R.sup.2 are the same or different and
are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with at least
one different dialkylphosphinic acid of the formula (II)
##STR00012## wherein R.sup.3, R.sup.4 are the same or different and
are C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2.
22. A flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber comprising
0.5 to 45% by weight of a mixture of at least one dialkylphosphinic
acid of the formula (I) ##STR00013## wherein R.sup.1, R.sup.2 are
the same or different and are C.sub.1-C.sub.18-alkyl,
C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or
C.sub.7-C.sub.18-alkylaryl, with at least one different
dialklophosphinic acid of the formula (II) ##STR00014## wherein
R.sup.3, R.sup.4 are the same or different and are
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2, 0.5 to 99.5% 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 a
reinforcing material, where the sum of the components is 100% by
weight.
23. A flame-retardant thermoplastic or thermoset polymer molding
composition or polymer molding, film, filament or fiber comprising
1 to 30% by weight of a mixture of at least one dialkylphosphinic
acid of the formula (I) ##STR00015## wherein R.sup.1, R.sup.2 are
the same or different and are C.sub.1-C.sub.18-alkyl.
C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl or
C.sub.7-C.sub.18-alkylaryl, with at least one different
dialkylphosphinic acid of the formula (II) ##STR00016## wherein
R.sup.3, R.sup.4 are the same or different and are
C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl,
C.sub.6-C.sub.18-aryl or C.sub.7-C.sub.18-alkylaryl, with the
proviso that at least one of the R.sup.3 and R.sup.4 radicals is
different than R.sup.1 and R.sup.2, 10 to 95% by weight of
thermoplastic or thermoset polymer or mixtures thereof, 2 to 30% by
weight of additives and 2 to 30% by weight of filler or a
reinforcing material, where the sum of the components is 100% by
weight.
Description
[0001] The present invention relates to mixtures of at least one
dialkylphosphinic acid with at least one other, different
dialkylphosphinic acid, to a process for preparation thereof and
use thereof.
[0002] In the production of printed circuit boards, which are being
used to an increasing degree in various devices, for example
computers, cameras, cellphones, LCD and TFT screens and other
electronic devices, different materials, especially polymers, are
being used. These include particularly thermosets, glass
fiber-reinforced thermosets and thermoplastics. Owing to their good
properties, epoxy resins are used particularly frequently.
[0003] According to the relevant standards (IPC-4101, Specification
for Base Materials for Rigid and Multilayer Printed Boards), these
printed circuit boards must be rendered flame-retardant.
[0004] The thermal expansion of printed circuit boards in the
course of production thereof is a problem. The conditions of
electronics manufacture for printed circuit boards require that
printed circuit boards withstand high thermal stresses without
damage or deformation. The application of conductor tracks
(lead-free soldering) to printed circuit boards is effected at
temperatures up to about 260.degree. C. It is therefore important
that printed circuit boards do not warp under thermal stress and
the products remain dimensionally stable.
[0005] Thermal expansion is significant particularly even in the
case of prepregs (short form of "preimpregnated fibers") and
laminates, since these constitute the initial forms or precursors
of printed circuit boards.
[0006] It is thus important to minimize the thermal expansion of
test specimens in order to obtain a good, dimensionally stable
product (finished printed circuit board).
[0007] It is an object of the present invention to modify polymers
for prepregs, printed circuit boards and laminates such that they
are subject only to very low thermal expansion--if any at all--and
dimensional stability is fulfilled.
[0008] This object is achieved by mixtures of at least one
dialkylphosphinic acid of the formula (I)
##STR00003## [0009] in which [0010] R.sup.1, R.sup.2 are the same
or different and are each C.sub.1-C.sub.18-alkyl,
C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl,
C.sub.7-C.sub.18-alkylaryl, [0011] with at least one different
dialkylphosphinic acid of the formula (II)
[0011] ##STR00004## [0012] in which [0013] R.sup.3, R.sup.4 are the
same or different and are each C.sub.1-C.sub.18-alkyl,
C.sub.2-C.sub.18-alkenyl, C.sub.6-C.sub.18-aryl and/or
C.sub.7-C.sub.18-alkylaryl, [0014] with the proviso that at least
one of the R.sup.3 and R.sup.4 radicals is different than R.sup.1
and R.sup.2.
[0015] Preferably, R.sup.1 and R.sup.2 are the same or different
and are each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or
phenyl.
[0016] Preferably, R.sup.3 and R.sup.4 are the same or different
and are each methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl and/or phenyl,
with the proviso that at least one of the R.sup.3 and R.sup.4
radicals is different than R.sup.1 and R.sup.2.
[0017] The mixtures preferably comprise 0.1 to 99.9% by weight of
dialkylphosphinic acid of the formula (I) and 99.9 to 0.1% by
weight of a different dialkylphosphinic acid of the formula
(II).
[0018] More preferred are mixtures comprising 40 to 99.9% by weight
of dialkylphosphinic acid of the formula (I) and 60 to 0.1% by
weight of a different dialkylphosphinic acid of the formula
(II).
[0019] Further preferred are mixtures comprising 60 to 99.9% by
weight of dialkylphosphinic acid of the formula (I) and 40 to 0.1%
by weight of a different dialkylphosphinic acid of the formula
(II).
[0020] Also preferred are mixtures comprising 80 to 99.9% by weight
of dialkylphosphinic acid of the formula (I) and 20 to 0.1% by
weight of a different dialkylphosphinic acid of the formula
(II).
[0021] Likewise preferred are mixtures comprising 90 to 99.9% by
weight of dialkylphosphinic acid of the formula (I) and 10 to 0.1%
by weight of a different dialkylphosphinic acid of the formula
(II).
[0022] Additionally preferred are mixtures comprising 95 to 99.9%
by weight of dialkylphosphinic acid of the formula (I) and 5 to
0.1% by weight of a different dialkylphosphinic acid of the formula
(II).
[0023] Particular preference is given, however, to mixtures
comprising 98 to 99.9% by weight of dialkylphosphinic acid of the
formula (I) and 2 to 0.1% by weight of a different
dialkylphosphinic acid of the formula (II).
[0024] The dialkylphosphinic acids are preferably diethylphosphinic
acid, ethylpropylphosphinic acid, ethylbutylphosphinic acid,
ethylpentylphosphinic acid, ethylhexylphosphinic acid,
dipropylphosphinic acid, propylbutylphosphinic acid,
propylpentylphosphinic acid, propylhexylphosphinic acid,
dibutylphosphinic acid, butylpentylphosphinic acid,
butylhexylphosphinic acid, dipentylphosphinic acid,
pentylhexylphosphinic acid and/or dihexylphosphinic acid.
[0025] Particular preference is given in accordance with the
invention to mixtures comprising 98 to 99.9% by weight of
diethylphosphinic acid and 2 to 0.1% by weight of
butylethylphosphinic acid.
[0026] The inventive mixtures preferably further comprise at least
one synergist, the synergist being a nitrogen-containing compound
such as melem, melam, melon, melamine borate, melamine cyanurate,
melamine phosphate, dimelamine phosphate, pentamelamine
triphosphate, trimelamine diphosphate, tetrakismelamine
triphosphate, hexakismelamine pentaphosphate, melamine diphosphate,
melamine tetraphosphate, melamine pyrophosphate, melamine
polyphosphate, melam polyphosphate, melem polyphosphate and/or
melon polyphosphate;
aluminum compounds such as aluminum hydroxide, halloysite, sapphire
products, boehmite, nanoboehmite; magnesium compounds such as
magnesium hydroxide; tin compounds such as tin oxides; antimony
compounds such as antimony oxides; zinc compounds such as zinc
oxide, zinc hydroxide, zinc oxide hydrate, zinc carbonate, zinc
stannate, zinc hydroxystannate, zinc silicate, zinc phosphate, zinc
borophosphate, zinc borate and/or zinc molybdate; silicon compounds
such as silicates and/or silicones; phosphorus compounds such as
phosphinic acids and salts thereof, phosphonic acids and salts
thereof and/or phosphine oxides, phosphazenes and/or piperazine
(pyro)phosphates; carbodiimides, piperazines, (poly)isocyanates,
styrene-acrylic polymers; and/or carbonylbiscaprolactam; nitrogen
compounds from the group of oligomeric esters of tris(hydroxyethyl)
isocyanurate with aromatic polycarboxylic acids, or benzoguanamine,
acetoguanamine, tris(hydroxyethyl) isocyanurate, allantoin,
glycoluril, cyanurates, cyanurate-epoxide compounds, urea
cyanurate, dicyanamide, guanidine, guanidine phosphate and/or
sulfate.
[0027] The mixtures preferably comprise 99 to 1% by weight of
mixtures of at least one dialkylphosphinic acid of the formula (I)
and one different dialkylphosphinic acid of the formula (II) as
claimed in at least one of claims 1 to 7 and 1 to 99% by weight of
synergist.
[0028] The invention also relates to a process for preparing the
mixtures as claimed in at least one of claims 1 to 12, which
comprises reacting a phosphorus source with an initiator and an
olefin and treating the alkylated phosphorus compound thus obtained
with a mineral acid and converting it, by concentration and workup,
to a mixture of at least one dialkylphosphinic acid of the formula
(I) and at least one different dialkylphosphinic acid of the
formula (II).
[0029] Preferably, the phosphorus source is a phosphinic salt, the
olefin is ethylene and the mineral acid is sulfuric acid or
hydrochloric acid, and the free-radical initiator is
2,2'-azobis(2-amidinopropane) dihydrochloride,
2,2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride,
azobis(isobutyronitrile), 4,4'-azobis(4-cyanopentanoic acid) and/or
2,2'-azobis(2-methylbutyronitrile) or hydrogen peroxide, ammonium
peroxodisulfate, potassium peroxodisulfate, dibenzoyl peroxide,
di-tert-butyl peroxide, peracetic acid, diisobutyryl peroxide,
cumene peroxyneodecanoate, tert-butyl peroxyneodecanoate,
tert-butyl peroxypivalate, tert-amyl peroxypivalate, dipropyl
peroxydicarbonate, dibutyl peroxydicarbonate, dimyristyl
peroxydicarbonate, dilauroyl peroxide, 1,1,3,3-tetramethylbutyl
peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexylcarbonate,
tert-butyl peroxyisobutyrate, 1,1-di(tert-butylperoxy)cyclohexane,
tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl
peroxydiethylacetate, tert-butyl peroxyisopropylcarbonate,
2,2-di(tert-butylperoxy)butane, tert-amyl hydroperoxide and/or
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.
[0030] The process is preferably executed in such a way that sodium
phosphinate is reacted with ethylene and then with dilute sulfuric
acid, concentrated, filtered and distilled, in order to obtain a
mixture of diethylphosphinic acid and butylethylphosphinic
acid.
[0031] Preferably, the reaction takes place in a solvent and the
solvent is an alcohol, acid or water.
[0032] The reaction temperature is preferably between 50 and
150.degree. C.
[0033] The invention also encompasses the use of mixtures as
claimed in at least one of claims 1 to 12 as an intermediate for
further syntheses, as a binder, as a crosslinker or accelerator in
the curing of epoxy resins, polyurethanes and 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 and in electronics
applications.
[0034] More particularly, the invention encompasses the use of
mixtures as claimed in at least one of claims 1 to 14 as a flame
retardant, especially as a flame retardant for clearcoats and
intumescent coatings, as a 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.
[0035] The invention also relates to a flame-retardant
thermoplastic or thermoset polymer molding composition and to
polymer moldings, films, filaments and fibers comprising 0.5 to 45%
by weight of mixtures as claimed in at least one of claims 1 to 14,
0.5 to 99.5% 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.
[0036] Finally, the invention also relates to a flame-retardant
thermoplastic or thermoset polymer molding composition and to
polymer moldings, films, filaments and fibers comprising 1 to 30%
by weight of mixtures as claimed in at least one of claims 1 to 14,
10 to 95% by weight of thermoplastic or thermoset polymer or
mixtures thereof, 2 to 30% by weight of additives and 2 to 30% by
weight of filler or reinforcing materials, where the sum of the
components is 100% by weight.
[0037] Mixtures of at least one dialkylphosphinic acid of the
formula (I) and at least one different dialkylphosphinic acid of
the formula (II) are claimed, with the proviso that at least one of
the R.sup.3 and R.sup.4 radicals is different than R.sup.1 and
R.sup.2. This means that either R.sup.3 or R.sup.4 is different
than R.sup.1 and R.sup.2 or else both are different, i.e. R.sup.3
and R.sup.4 are different than R.sup.1 and R.sup.2.
[0038] Preferably mixtures of at least one dialkylphosphinic acid
of the formula (I) and at least one different dialkylphosphinic
acid of the formula (II) are composed of dimethylphosphinic acid
and methylethylphosphinic acid, dimethylphosphinic acid and
methylpropylphosphinic acid, dimethylphosphinic acid and
methylbutylphosphinic acid, dimethylphosphinic acid and
methylpentylphosphinic acid, dimethylphosphinic acid and
methylhexylphosphinic acid, dimethylphosphinic acid and
ethylethylphosphinic acid, dimethylphosphinic acid and
ethylpropylphosphinic acid, dimethylphosphinic acid and
ethylbutylphosphinic acid, dimethylphosphinic acid and
ethylpentylphosphinic acid, dimethylphosphinic acid and
ethylhexylphosphinic acid, dimethylphosphinic acid and
propylpropylphosphinic acid, dimethylphosphinic acid and
propylbutylphosphinic acid, dimethylphosphinic acid and
propylpentylphosphinic acid, dimethylphosphinic acid and
propylhexylphosphinic acid, dimethylphosphinic acid and
butylbutylphosphinic acid, dimethylphosphinic acid and
butylpentylphosphinic acid, dimethylphosphinic acid and
butylhexylphosphinic acid, dimethylphosphinic acid and
pentylpentylphosphinic acid, dimethylphosphinic acid and
pentylhexylphosphinic acid, dimethylphosphinic acid and
hexylhexylphosphinic acid, diethylphosphinic acid and
methylethylphosphinic acid, diethylphosphinic acid and
methylpropylphosphinic acid, diethylphosphinic acid and
methylbutylphosphinic acid, diethylphosphinic acid and
methylpentylphosphinic acid, diethylphosphinic acid and
methylhexylphosphinic acid, diethylphosphinic acid and
ethylpropylphosphinic acid, diethylphosphinic acid and
ethylbutylphosphinic acid, diethylphosphinic acid and
ethylpentylphosphinic acid, diethylphosphinic acid and
ethylhexylphosphinic acid, diethylphosphinic acid and
propylpropylphosphinic acid, diethylphosphinic acid and
propylbutylphosphinic acid, diethylphosphinic acid and
propylpentylphosphinic acid, diethylphosphinic acid and
propylhexylphosphinic acid, diethylphosphinic acid and
butylbutylphosphinic acid, diethylphosphinic acid and
butylpentylphosphinic acid, diethylphosphinic acid and
butylhexylphosphinic acid, diethylphosphinic acid and
pentylpentylphosphinic acid, diethylphosphinic acid and
pentylhexylphosphinic acid, diethylphosphinic acid and
hexylhexylphosphinic acid, dipropylphosphinic acid and
methylethylphosphinic acid, dipropylphosphinic acid and
methylpropylphosphinic acid, dipropylphosphinic acid and
methylbutylphosphinic acid, dipropylphosphinic acid and
methylpentylphosphinic acid, dipropylphosphinic acid and
methylhexylphosphinic acid, dipropylphosphinic acid and
ethylpropylphosphinic acid, dipropylphosphinic acid and
ethylbutylphosphinic acid, dipropylphosphinic acid and
ethylpentylphosphinic acid, dipropylphosphinic acid and
ethylhexylphosphinic acid, dipropylphosphinic acid and
propylbutylphosphinic acid, dipropylphosphinic acid and
propylpentylphosphinic acid, dipropylphosphinic acid and
propylhexylphosphinic acid, dipropylphosphinic acid and
butylbutylphosphinic acid, dipropylphosphinic acid and
butylpentylphosphinic acid, dipropylphosphinic acid and
butylhexylphosphinic acid, dipropylphosphinic acid and
pentylpentylphosphinic acid, dipropylphosphinic acid and
pentylhexylphosphinic acid, dipropylphosphinic acid and
hexylhexylphosphinic acid, dibutylphosphinic acid and
methylethylphosphinic acid, dibutylphosphinic acid and
methylpropylphosphinic acid, dibutylphosphinic acid and
methylbutylphosphinic acid, dibutylphosphinic acid and
methylpentylphosphinic acid, dibutylphosphinic acid and
methylhexylphosphinic acid, dibutylphosphinic acid and
ethylpropylphosphinic acid, dibutylphosphinic acid and
ethylbutylphosphinic acid, dibutylphosphinic acid and
ethylpentylphosphinic acid, dibutylphosphinic acid and
ethylhexylphosphinic acid, dibutylphosphinic acid and
propylbutylphosphinic acid, dibutylphosphinic acid and
propylpentylphosphinic acid, dibutylphosphinic acid and
propylhexylphosphinic acid, dibutylphosphinic acid and
butylpentylphosphinic acid, dibutylphosphinic acid and
butylhexylphosphinic acid, dibutylphosphinic acid and
pentylpentylphosphinic acid, dibutylphosphinic acid and
pentylhexylphosphinic acid, dibutylphosphinic acid and
hexylhexylphosphinic acid, dipentylphosphinic acid and
methylethylphosphinic acid, dipentylphosphinic acid and
methylpropylphosphinic acid, dipentylphosphinic acid and
methylbutylphosphinic acid, dipentylphosphinic acid and
methylpentylphosphinic acid, dipentylphosphinic acid and
methylhexylphosphinic acid, dipentylphosphinic acid and
ethylpropylphosphinic acid, dipentylphosphinic acid and
ethylbutylphosphinic acid, dipentylphosphinic acid and
ethylpentylphosphinic acid, dipentylphosphinic acid and
ethylhexylphosphinic acid, dipentylphosphinic acid and
propylbutylphosphinic acid, dipentylphosphinic acid and
propylpentylphosphinic acid, dipentylphosphinic acid and
propylhexylphosphinic acid, dipentylphosphinic acid and
butylpentylphosphinic acid, dipentylphosphinic acid and
butylhexylphosphinic acid, dipentylphosphinic acid and
pentylhexylphosphinic acid, dipentylphosphinic acid and
hexylhexylphosphinic acid, dihexylphosphinic acid and
methylethylphosphinic acid, dihexylphosphinic acid and
methylpropylphosphinic acid, dihexylphosphinic acid and
methylbutylphosphinic acid, dihexylphosphinic acid and
methylpentylphosphinic acid, dihexylphosphinic acid and
methylhexylphosphinic acid, dihexylphosphinic acid and
ethylpropylphosphinic acid, dihexylphosphinic acid and
ethylbutylphosphinic acid, dihexylphosphinic acid and
ethylpentylphosphinic acid, dihexylphosphinic acid and
ethylhexylphosphinic acid, dihexylphosphinic acid and
propylbutylphosphinic acid, dihexylphosphinic acid and
propylpentylphosphinic acid, dihexylphosphinic acid and
propylhexylphosphinic acid, dihexylphosphinic acid and
butylpentylphosphinic acid, dihexylphosphinic acid and
butylhexylphosphinic acid, dihexylphosphinic acid and
pentylhexylphosphinic acid, methylethylphosphinic acid and
methylpropylphosphinic acid, methylethylphosphinic acid and
methylbutylphosphinic acid, methylethylphosphinic acid and
methylpentylphosphinic acid, methylethylphosphinic acid and
methylhexylphosphinic acid, methylethylphosphinic acid and
ethylpropylphosphinic acid, methylethylphosphinic acid and
ethylbutylphosphinic acid, methylethylphosphinic acid and
ethylpentylphosphinic acid, methylethylphosphinic acid and
ethylhexylphosphinic acid, methylethylphosphinic acid and
propylbutylphosphinic acid, methylethylphosphinic acid and
propylpentylphosphinic acid, methylethylphosphinic acid and
propylhexylphosphinic acid, methylethylphosphinic acid and
butylpentylphosphinic acid, methylethylphosphinic acid and
butylhexylphosphinic acid, methylethylphosphinic acid and
pentylhexylphosphinic acid, methylpropylphosphinic acid and
methylbutylphosphinic acid, methylpropylphosphinic acid and
methylpentylphosphinic acid, methylpropylphosphinic acid and
methylhexylphosphinic acid, methylpropylphosphinic acid and
ethylpropylphosphinic acid, methylpropylphosphinic acid and
ethylbutylphosphinic acid, methylpropylphosphinic acid and
ethylpentylphosphinic acid, methylpropylphosphinic acid and
ethylhexylphosphinic acid, methylpropylphosphinic acid and
propylbutylphosphinic acid, methylpropylphosphinic acid and
propylpentylphosphinic acid, methylpropylphosphinic acid and
propylhexylphosphinic acid, methylpropylphosphinic acid and
butylpentylphosphinic acid, methylpropylphosphinic acid and
butylhexylphosphinic acid, methylpropylphosphinic acid and
pentylhexylphosphinic acid, methylbutylphosphinic acid and
methylpentylphosphinic acid, methylbutylphosphinic acid and
methylhexylphosphinic acid, methylbutylphosphinic acid and
ethylpropylphosphinic acid, methylbutylphosphinic acid and
ethylbutylphosphinic acid, methylbutylphosphinic acid and
ethylpentylphosphinic acid, methylbutylphosphinic acid and
ethylhexylphosphinic acid, methylbutylphosphinic acid and
propylbutylphosphinic acid, methylbutylphosphinic acid and
propylpentylphosphinic acid, methylbutylphosphinic acid and
propylhexylphosphinic acid, methylbutylphosphinic acid and
butylpentylphosphinic acid, methylbutylphosphinic acid and
butylhexylphosphinic acid, methylbutylphosphinic acid and
pentylhexylphosphinic acid, methylpentylphosphinic acid and
methylhexylphosphinic acid, methylpentylphosphinic acid and
ethylpropylphosphinic acid, methylpentylphosphinic acid and
ethylbutylphosphinic acid, methylpentylphosphinic acid and
ethylpentylphosphinic acid, methylpentylphosphinic acid and
ethylhexylphosphinic acid, methylpentylphosphinic acid and
propylbutylphosphinic acid, methylpentylphosphinic acid and
propylpentylphosphinic acid, methylpentylphosphinic acid and
propylhexylphosphinic acid, methylpentylphosphinic acid and
butylpentylphosphinic acid, methylpentylphosphinic acid and
butylhexylphosphinic acid, methylpentylphosphinic acid and
pentylhexylphosphinic acid, methylhexylphosphinic acid and
ethylpropylphosphinic acid, methylhexylphosphinic acid and
ethylbutylphosphinic acid, methylhexylphosphinic acid and
ethylpentylphosphinic acid, methylhexylphosphinic acid and
ethylhexylphosphinic acid, methylhexylphosphinic acid and
propylbutylphosphinic acid, methylhexylphosphinic acid and
propylpentylphosphinic acid, methylhexylphosphinic acid and
propylhexylphosphinic acid, methylhexylphosphinic acid and
butylpentylphosphinic acid, methylhexylphosphinic acid and
butylhexylphosphinic acid, methylhexylphosphinic acid and
pentylhexylphosphinic acid, ethylpropylphosphinic acid and
ethylbutylphosphinic acid, ethylpropylphosphinic acid and
ethylpentylphosphinic acid, ethylpropylphosphinic acid and
ethylhexylphosphinic acid, ethylpropylphosphinic acid and
propylbutylphosphinic acid, ethylpropylphosphinic acid and
propylpentylphosphinic acid, ethylpropylphosphinic acid and
propylhexylphosphinic acid, ethylpropylphosphinic acid and
butylpentylphosphinic acid, ethylpropylphosphinic acid and
butylhexylphosphinic acid, ethylpropylphosphinic acid and
pentylhexylphosphinic acid, ethylbutylphosphinic acid and
ethylpropylphosphinic acid, ethylbutylphosphinic acid and
ethylpentylphosphinic acid, ethylbutylphosphinic acid and
ethylhexylphosphinic acid, ethylbutylphosphinic acid and
propylbutylphosphinic acid, ethylbutylphosphinic acid and
propylpentylphosphinic acid, ethylbutylphosphinic acid and
propylhexylphosphinic acid, ethylbutylphosphinic acid and
butylpropylphosphinic acid, ethylbutylphosphinic acid and
butylpentylphosphinic acid, ethylbutylphosphinic acid and
butylhexylphosphinic acid, ethylbutylphosphinic acid and
pentylethylphosphinic acid, ethylbutylphosphinic acid and
pentylpropylphosphinic acid, ethylbutylphosphinic acid and
pentylbutylphosphinic acid, ethylbutylphosphinic acid and
pentylhexylphosphinic acid, ethylpentylphosphinic acid and
ethylpropylphosphinic acid, ethylpentylphosphinic acid and
ethylbutylphosphinic acid, ethylpentylphosphinic acid and
ethylhexylphosphinic acid, ethylpentylphosphinic acid and
propylbutylphosphinic acid, ethylpentylphosphinic acid and
propylpentylphosphinic acid, ethylpentylphosphinic acid and
propylhexylphosphinic acid, ethylpentylphosphinic acid and
butylpropylphosphinic acid, ethylpentylphosphinic acid and
butylpentylphosphinic acid, ethylpentylphosphinic acid and
butylhexylphosphinic acid, ethylpentylphosphinic acid and
pentylpropylphosphinic acid, ethylpentylphosphinic acid and
pentylbutylphosphinic acid, ethylpentylphosphinic acid and
pentylhexylphosphinic acid, ethylhexylphosphinic acid and
ethylpropylphosphinic acid, ethylhexylphosphinic acid and
ethylbutylphosphinic acid, ethylhexylphosphinic acid and
ethylhexylphosphinic acid, ethylhexylphosphinic acid and
propylbutylphosphinic acid, ethylhexylphosphinic acid and
propylpentylphosphinic acid, ethylhexylphosphinic acid and
propylhexylphosphinic acid, ethylhexylphosphinic acid and
butylpropylphosphinic acid, ethylhexylphosphinic acid and
butylpentylphosphinic acid, ethylhexylphosphinic acid and
butylhexylphosphinic acid, ethylhexylphosphinic acid and
pentylpropylphosphinic acid, ethylhexylphosphinic acid and
pentylbutylphosphinic acid, ethylhexylphosphinic acid and
pentylhexylphosphinic acid, propylbutylphosphinic acid and
propylpentylphosphinic acid, propylbutylphosphinic acid and
propylhexylphosphinic acid, propylbutylphosphinic acid and
butylpentylphosphinic acid, propylbutylphosphinic acid and
butylhexylphosphinic acid, propylbutylphosphinic acid and
pentylpropylphosphinic acid, propylbutylphosphinic acid and
pentylbutylphosphinic acid, propylbutylphosphinic acid and
pentylhexylphosphinic acid, propylbutylphosphinic acid and
hexylbutylphosphinic acid, propylbutylphosphinic acid and
hexylpropylphosphinic acid, propylpentylphosphinic acid and
propylhexylphosphinic acid, propylpentylphosphinic acid and
butylpentylphosphinic acid, propylpentylphosphinic acid and
butylhexylphosphinic acid, propylpentylphosphinic acid and
pentylbutylphosphinic acid, propylpentylphosphinic acid and
pentylhexylphosphinic acid, propylhexylphosphinic acid and
butylhexylphosphinic acid, propylhexylphosphinic acid and
pentylbutylphosphinic acid, propylhexylphosphinic acid and
pentylhexylphosphinic acid, butylpentylphosphinic acid and
butylhexylphosphinic acid, butylpentylphosphinic acid and
pentylhexylphosphinic acid, butylpentylphosphinic acid and
hexylbutylphosphinic acid, butylpentylphosphinic acid and
hexylpentylphosphinic acid, butylhexylphosphinic acid and
pentylhexylphosphinic acid.
[0039] This list also includes all variations, for example n-,
iso-, tert- etc., i.e., for instance, tert-butylisopentylphosphinic
acid and isohexyl-n-pentylphosphinic acid and all other conceivable
mixtures.
[0040] In addition, multicomponent mixtures may also occur, for
example those of dimethylphosphinic acid and methylethylphosphinic
acid and methylpropylphosphinic acid, diethylphosphinic acid and
methylethylphosphinic acid and dipropylphosphinic acid etc.;
accordingly, four-component mixtures and mixtures with a higher
number of the aforementioned diphosphinic acids are also
possible.
[0041] Particular preference is given to mixtures of
dimethylphosphinic acid and butylethylphosphinic acid,
diethylphosphinic acid and butylethylphosphinic acid,
dipropylphosphinic acid and butylethylphosphinic acid,
dibutylphosphinic acid and butylethylphosphinic acid,
dimethylphosphinic acid and hexylethylphosphinic acid,
diethylphosphinic acid and hexylethylphosphinic acid.
[0042] The mixture preferably comprises 0.1 to 99.9% by weight of
diphosphinic acid of the formula (I) and 99.9 to 0.1% by weight of
butylalkylphosphinic acid of the formula (II).
[0043] The mixture more preferably comprises 99.9 to 50% by weight
of diphosphinic acid of the formula (I) and 0.1 to 50% by weight of
butylalkylphosphinic acid of the formula (II).
[0044] The mixture more preferably also comprises 80 to 99.5% by
weight of diphosphinic acid of the formula (I) and 0.5 to 20% by
weight of butylalkylphosphinic acid of the formula (II).
[0045] The mixture especially preferably comprises 95 to 99.9% by
weight of diphosphinic acid of the formula (I) and 0.1 to 5% by
weight of butylalkylphosphinic acid of the formula (II).
[0046] The preferred diphosphinic acid of the formula (I) is
diethylphosphinic acid, and the preferred butylalkylphosphinic acid
of the formula (II) is butylethylphosphinic acid.
[0047] The invention encompasses especially mixtures consisting of
98 to 99.9% by weight of diethylphosphinic acid and 2 to 0.1% by
weight of butylethylphosphinic acid.
[0048] As stated above, the mixture preferably further comprises at
least one synergist. The synergist is preferably at least one
expansion-neutral substance, which means that its dimensions do not
change under thermal or similar stress. Such changes can be
determined by means of the coefficient of thermal expansion. This
describes the changes in the dimensions of a substance in the event
of temperature changes.
[0049] The mixtures preferably comprise 65 to 1% by weight of the
mixture of at least one dialkylphosphinic acid of the formula (I)
and at least one dialkylphosphinic acid of the formula (II) as
claimed in at least one of claims 1 to 12 and 1 to 35% by weight of
synergist.
[0050] The mixtures preferably also comprise 80 to 95% by weight of
the mixture of at least one dialkylphosphinic acid of the formula
(I) and at least one dialkylphosphinic acid of the formula (II) as
claimed in at least one of claims 1 to 12 and 5 to 20% by weight of
synergist.
[0051] In the process according to the invention, the solvent used
is preferably acetic acid or water and the reaction temperature is
preferably 80 to 120.degree. C.
[0052] Preference is given to processing the inventive mixture of
at least one dialkylphosphinic acid of the formula (I) and at least
one different dialkylphosphinic acid of the formula (II) by mixing
it into a polymer system.
[0053] The mixing is effected by kneading, dispersing and/or
extruding.
[0054] Preference is given to using the inventive mixture of at
least one dialkylphosphinic acid of the formula (I) and at least
one different dialkylphosphinic acid of the formula (II) by
additive incorporation into a polymer system.
[0055] Particular preference is given to using the mixtures of at
least one dialkylphosphinic acid of the formula (I) and at least
one different dialkylphosphinic acid of the formula (II) by
reactive incorporation into a polymer system. Reactive
incorporation is characterized by a resulting permanent bond to the
polymer extrudates of the polymer system, as a result of which the
inventive mixture of at least one dialkylphosphinic acid of the
formula (I) and at least one different dialkylphosphinic acid of
the formula (II) cannot be leached out.
[0056] The inventive mixtures can be used with further flame
retardants and further synergists. The further flame retardants
include, for example, phosphorus compounds such as phosphinates,
phosphonates, phosphates, phosphonic acids, phosphinic acids,
phosphoric acids, phosphines, phosphine oxides, phosphorus oxides
and others.
[0057] Suitable polymer additives for flame-retardant polymer
molding compositions and polymer moldings are UV absorbers, light
stabilizers, lubricants, colorants, antistats, nucleating agents,
fillers, synergists, reinforcers and others.
[0058] The polymer systems preferably originate from the group of
the thermoplastic polymers such as polyamide, polyester or
polystyrene and/or thermoset polymers.
[0059] The thermoset polymers are more preferably epoxy resins.
[0060] The thermoset polymers are more preferably epoxy resins
which have been cured with phenols and/or dicyandiamide [more
generally: phenol derivatives (resols); alcohols and amines],
especially phenol derivatives and dicyandiamide.
[0061] The thermoset polymers are more preferably epoxy resins
which have been cured with phenols and/or dicyandiamide and/or a
catalyst.
[0062] The catalysts are preferably imidazole compounds.
[0063] The epoxy resins are preferably polyepoxide compounds.
[0064] The epoxy resins are preferably resins based on novolac
and/or bisphenol A.
[0065] 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.
[0066] 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.
[0067] 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.
[0068] The polymers are preferably polystyrene (Polystyrol.RTM.
143E (BASF), poly(p-methylstyrene), poly(alpha-methylstyrene).
[0069] 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.
[0070] 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 copolymers, and mixtures thereof, as known, for
example, as ABS, MBS, ASA or AES polymers.
[0071] 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., Sagex.RTM. and Telgopor.RTM..
[0072] 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.
[0073] 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.
[0074] 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.
[0075] The polymers are preferably homo- and copolymers of cyclic
ethers, such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bisglycidyl
ethers.
[0076] 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.
[0077] The polymers are preferably polyphenylene oxides and
sulfides and mixtures thereof with styrene polymers or
polyamides.
[0078] 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.
[0079] 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 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 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, polyamides or
copolyamides modified with EPDM (ethylene-propylene-diene rubber)
or ABS (acrylonitrile-butadiene-styrene); and polyamides condensed
during processing ("RIM polyamide systems").
[0080] The polymers are preferably polyureas, polyimides,
polyamidimides, polyetherimides, polyesterimides, polyhydantoins
and polybenzimidazoles.
[0081] 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.
[0082] The polymers are preferably polycarbonates and polyester
carbonates.
[0083] The polymers are preferably polysulfones, polyether sulfones
and polyether ketones.
[0084] 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.
[0085] The polymers are preferably drying and nondrying alkyd
resins.
[0086] 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.
[0087] The polymers are preferably crosslinkable acrylic resins
which derive from substituted acrylic esters, for example from
epoxy acrylates, urethane acrylates or polyester acrylates.
[0088] 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.
[0089] 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.
[0090] The polymers are preferably mixtures (polyblends) of the
above-mentioned 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).
[0091] The molding composition produced is preferably of
rectangular shape with a regular or irregular base, or of cubic
shape, cuboidal shape, cushion shape or prism shape.
[0092] The invention is illustrated by the examples which
follow.
[0093] Production, processing and testing of flame-retardant
polymer molding compositions and flame-retardant polymer
moldings
[0094] The flame-retardant components are mixed with the polymer
pellets and any additives and incorporated in a twin-screw extruder
(model: Leistritz LSM.RTM. 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.
[0095] 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. The
test specimens are tested for flame retardancy and classified using
the UL 94 test (Underwriter Laboratories).
[0096] 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: [0097] 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.
[0098] 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. [0099] V-2: cotton indicator ignited by
flaming drops, other criteria as for V-1.
[0100] Not classifiable (ncl): does not fulfill fire class V-2.
[0101] For some samples examined, the LOI was also measured. The
LOI (Limiting Oxygen Index) is determined to ISO 4589 and
corresponds to the lowest oxygen concentration in percent by volume
which just still supports the combustion of the polymer in a
mixture of oxygen and nitrogen. The higher the LOI the greater the
nonflammability of the material tested.
TABLE-US-00001 LOI 23 flammable LOI 24-28 limited flammability LOI
29-35 flame-retardant LOI >36 particularly flame-retardant
Chemicals and Abbreviations Used
[0102] Phenol novolac: Bakelite.RTM. PF 0790, from Hexion
Initiator: Vazo 67, from DuPont
EXAMPLE 1
[0103] According to EP-A-1544205, example 8, a diethylphosphinic
acid metal salt solution is obtained from sodium hypophosphite by
means of initiator and ethylene. Subsequent treatment of the
product solution with dilute sulfuric acid, concentration,
filtration and distillation at 184.degree. C. (1 mbar) give a yield
of 94% of a mixture of diethylphosphinic acid (99.9% by weight) and
butylethylphosphinic acid (0.01% by weight).
EXAMPLE 2
[0104] According to EP-A-1544205, example 8, a diethylphosphinic
acid metal salt solution is obtained from sodium hypophosphite by
means of initiator and ethylene. Treatment of the product solution
with dilute sulfuric acid, concentration, filtration and
distillation at 180-190.degree. C. (1 mbar) give a yield of 92% of
a mixture of diethylphosphinic acid (98% by weight) and
butylethylphosphinic acid (2% by weight).
EXAMPLE 3
[0105] Diethylphosphinic acid is obtained analogously to
EP-A-1544205, example 8, from sodium hypophosphite by means of
initiator and ethylene, and is purified by means of subsequent
distillation.
[0106] Butylethylphosphinic acid is synthesized by reaction of
ethylphosphinic acid with butene analogously to WO-A-2009/010188. A
mixture of diethylphosphinic acid and butylethylphosphinic acid in
a weight ratio of 90:10 is obtained by mixing the two pure
components.
EXAMPLE 4
[0107] In a manner corresponding to example 3, a mixture of
diethylphosphinic acid and butylethylphosphinic acid in a weight
ratio of 60:40 is obtained by mixing the two pure components.
EXAMPLE 5
[0108] In a manner corresponding to example 3, a mixture of
diethylphosphinic acid and butylethylphosphinic acid in a weight
ratio of 50:50 is obtained by mixing the two pure components.
[0109] General method for producing polymer moldings: [0110] a)
Preparation of phosphorus-modified epoxy resin [0111] A 2 l
five-neck flask apparatus is initially charged with 1000 g of the
epoxy resin (e.g. Beckopox EP 140). It is heated to 110.degree. C.
for one hour and volatile components are removed under reduced
pressure. Thereafter, the reaction mixture is inertized with
nitrogen and the temperature in the flask is increased to
170.degree. C. 118 g of the mixture of the phosphorus compounds
(selected from examples 1 to 5) are added in each case, while
stirring under flowing nitrogen, and an exothermic reaction is
observed. The resulting resin is yellow in color and free-flowing.
[0112] b) Production of epoxy resin specimens [0113] 100 parts of
the phosphorus-modified epoxy resin are mixed with one
corresponding OH equivalent of phenol novolac (hydroxide
equivalents 105 g/mol, melting point 85-95.degree. C.) and heated
to 150.degree. C. The mixture is stirred until a homogeneous
mixture has formed and is allowed to cool to 130.degree. C. Then
0.03 part 2-phenylimidazole is added and the mixture is stirred
once again for 5-10 min. Thereafter, the mixture is poured warm
into a dish and cured at 140.degree. C. for 2 h and at 200.degree.
C. for 2 h. [0114] c) Production of epoxy resin laminate [0115] 100
parts phosphorus-modified epoxy resin as per b) are added to 63
parts acetone and 27 parts Dowanol.RTM. PM, and the appropriate
amount of phenol resin is added. The mixture is left to stir for 30
min. and 2-phenylimidazole is added. Thereafter, the mixture is
filtered through a 400 .mu.m sieve in order to remove excess resin
particles. Then a woven glass fabric (7628 type, 203 g/m.sup.2) is
immersed into the solution until complete wetting of the fabric has
taken place. The wetted fabric is pulled out of the mixture and
excess resin is removed. Thereafter, the wetted fabric is initially
cured in stages in a drying cabinet for a brief period at
temperatures up to 165.degree. C. and then fully cured in a heated
press. The resin content of the cured laminates is 30-50%.
[0116] The thermal expansion of the molding produced, a laminate,
is determined to ASTM E831-06.
EXAMPLE 6
[0117] According to the general method for producing a polymer
molding, 100% of a bisphenol A resin is used to produce a
laminate.
EXAMPLE 7
[0118] Diethylphosphinic acid is obtained analogously to patent
EP-A-1544205, example 8, from sodium hypophosphite by means of
initiator and ethylene, and is purified by means of subsequent
distillation.
[0119] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of
diethylphosphinic acid is used to produce a molding.
EXAMPLE 8
[0120] Butylethylphosphinic acid is synthesized by reaction of
ethylphosphinic acid with butene analogously to
WO-A-2009/010188.
[0121] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of
butylethylphosphinic acid is used to produce a molding.
EXAMPLE 9
[0122] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of the inventive
mixture according to example 1 is used to produce a molding.
EXAMPLE 10
[0123] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of the inventive
mixture according to example 2 is used to produce a molding.
EXAMPLE 11
[0124] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of the inventive
mixture according to example 3 is used to produce a molding.
EXAMPLE 12
[0125] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of the inventive
mixture according to example 4 is used to produce a molding.
EXAMPLE 13
[0126] According to the general method for producing a polymer
molding, a composition composed to 90% by weight of bisphenol A
resin with hardener and catalyst and 10% by weight of the inventive
mixture according to example 5 is used to produce a molding.
[0127] The results are reproduced in the following table:
TABLE-US-00002 Mixture of Coefficient dialkylphosphinic acid of
thermal Composition of of the formula (I)/ expansion polymer
dialkylphosphinic acid 0.degree.-100.degree. system/mixture of the
formula (II) [ppm/.degree. C.] Example [% by wt./% by wt.] [% by
wt./% by wt.] Z X Y 6 100:0 69 20 7 7 90:10 100:0 70 21 8 8 90:10
0:100 71 20 7 9 90:10 99.9:0.1 65 18 5 10 90:10 98:2 63 17 5 11
90:10 90:10 60 16 5 12 90:10 60:40 58 14 4 13 90:10 50:50 56 13
4
[0128] Compared to the pure laminate (example 6), there is a
decrease in the values for the coefficient of thermal expansion of
the laminate comprising the inventive mixture of diethylphosphinic
acid and butylethylphosphinic acid; thermal expansion is thus very
low. An increase in the butylethylphosphinic acid content brings
about a further improvement. The inventive products lead to lower
expansion of the moldings produced and thus meet the demands on
dimensional stability.
* * * * *