U.S. patent application number 13/302144 was filed with the patent office on 2012-03-15 for ethylene diphosphinic acids.
This patent application is currently assigned to CLARIANT FINANCE (BVI) LIMITED. Invention is credited to Harald BAUER, Werner KRAUSE, Peter STANIEK.
Application Number | 20120064790 13/302144 |
Document ID | / |
Family ID | 38948994 |
Filed Date | 2012-03-15 |
United States Patent
Application |
20120064790 |
Kind Code |
A1 |
BAUER; Harald ; et
al. |
March 15, 2012 |
Ethylene Diphosphinic Acids
Abstract
The invention relates to ethylene diphosphinic acids and salts
thereof of general formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A, in which
A, H and/or CR.sup.5R.sup.6--OH, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 are the same or different, and denote
independently from each other H, C.sub.1-C.sub.20 alkyl,
C.sub.6-C.sub.20 aryl and or C.sub.6-C.sub.20 aralkyl, and X
denotes H, an alkali metal, an element of the second main and
secondary group, an element of the third main and secondary group,
an element of the fourth main and secondary group, an element of
the fifth main and secondary group, an element of the sixth
secondary group, an element of the seventh secondary group, an
element of the eight secondary group and/or a nitrogen base. Also
disclosed are a method for producing same and the use thereof.
Inventors: |
BAUER; Harald; (Kerpen,
DE) ; KRAUSE; Werner; (Huerth, DE) ; STANIEK;
Peter; (Binzen, DE) |
Assignee: |
CLARIANT FINANCE (BVI)
LIMITED
Tortola
VG
|
Family ID: |
38948994 |
Appl. No.: |
13/302144 |
Filed: |
November 22, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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12444794 |
Apr 8, 2009 |
8084518 |
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13302144 |
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Current U.S.
Class: |
442/301 ;
526/319; 528/395; 528/398; 544/214; 556/174; 556/18; 562/20 |
Current CPC
Class: |
C02F 2103/10 20130101;
Y10T 442/2672 20150401; C02F 5/14 20130101; Y10T 442/3976 20150401;
C07F 9/305 20130101; C02F 2303/08 20130101; B27K 3/34 20130101;
C07F 9/485 20130101; B27K 2240/30 20130101; C08G 18/40 20130101;
C09K 21/12 20130101; C08K 5/5313 20130101; C02F 2103/16 20130101;
C08G 2101/00 20130101; C08G 18/388 20130101 |
Class at
Publication: |
442/301 ; 562/20;
556/174; 556/18; 544/214; 526/319; 528/398; 528/395 |
International
Class: |
D03D 15/00 20060101
D03D015/00; C07F 19/00 20060101 C07F019/00; C08G 79/14 20060101
C08G079/14; C08F 122/10 20060101 C08F122/10; C08G 79/04 20060101
C08G079/04; C07F 9/30 20060101 C07F009/30; C07F 9/6521 20060101
C07F009/6521 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 14, 2006 |
DE |
102006048698.6 |
Oct 6, 2011 |
EP |
PCT/EP2007/008692 |
Claims
1. An ethylenediphosphinic acid or salt thereof having the formula
(I) A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A (I)
where A is H and/or CR.sup.5R.sup.6--OH, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 are identical or different and are each,
independently of one another, H, C.sub.1-C.sub.20-alkyl,
C.sub.6-C.sub.20-aryl or C.sub.6-C.sub.20-aralkyl and X is H, an
alkali metal, an element of main or transition group 2, an element
of main or transition group 3, an element of main or transition
group 4, an element of main or transition group 5, an element of
transition group 6, an element of transition group 7, an element of
transition group 8 and/or a nitrogen base.
2. An ethylenediphosphinic acid or salt thereof as claimed in claim
1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 are
identical or different and are each, independently of one another,
H, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl, n-pentyl
or phenyl.
3. An ethylenediphosphinic acid or salt thereof as claimed in one
or more of claims 1 to 3, wherein A is H and X is Li, Na, K; Mg,
Ca, Zn, Sr; Al, Ce, La; Ge, Sn, Pb, Ti, Zr; Sb, Bi; Cr, Mo, W; Mn;
Fe, Co or Ni.
4. An ethylenediphosphinic acid or salt thereof as claimed in one
or more of claims 1 to 4, wherein A is H and X is H, Na, Al, Zn,
Ca, Mg, Ti or melamine.
5. A process (1) for preparing ethylenediphosphinic acids and salts
thereof having the formula (I)
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A (I) where
A is H and/or CR.sup.5R.sup.6--OH, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 are identical or different and are each,
independently of one another, H, C.sub.1-C.sub.20-alkyl,
C.sub.6-C.sub.20-aryl or C.sub.6-C.sub.20-aralkyl and X is H or an
alkali metal, wherein a) a monophosphinic acid adduct of the
formula (II) H--P(O)(OX)-A (II) is reacted with acetylene and b) if
desired, the resulting ethylenediphosphinic acid of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A is
separated off from by-products.
6. A process (2) for preparing ethylenebis(hydroxyalkylphosphinic
acid) salts or ethylenediphosphinic acid salts of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is an alkali metal, an element of main
group or transition group 2, an element of main or transition group
3, an element of main or transition group 4, an element of main or
transition group 5, an element of transition group 6, an element of
transition group 7, an element of transition group 8 and/or a
nitrogen base, wherein an ethylenebis(hydroxyalkylphosphinic acid)
or ethylenediphosphinic acid of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is H, is reacted in a solvent system with
a reactant I which is a compound of an alkali metal, of an element
of main or transition group 2, of an element of main or transition
group 3, of an element, of main or transition group 4, of an
element of main or transition group 5, of an element of transition
group 6, of an element of transition group 7, of an element of
transition group 8 and/or a nitrogen base.
7. A process (3) for preparing ethylenebis(hydroxyalkylphosphinic
acid) salts or ethylenediphosphinic acid salts of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is an element of main group or transition
group 2, an element of main or transition group 3, an element of
main or transition group 4, an element of main or transition group
5, an element of transition group 6, an element of transition group
7, an element of transition group 8 and/or a nitrogen base, wherein
ethylenebis(hydroxyalkylphosphinic acid) or ethylenediphosphinic
acid of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is an alkali metal, is reacted in a
solvent system with a reactant II to form another metal salt (not
an alkali metal salt).
8. The process as claimed in claim 7, wherein the reactant II is a
borate, carbonate, hydroxocarbonate, hydroxocarbonate hydrate,
mixed hydroxocarbonate, mixed hydroxocarbonate hydrate, phosphate,
sulfate, sulfiate hydrate, hydroxosulfate hydrate, mixed
hydroxosulfate hydrate, oxysulfate, acetate, nitrate, fluoride,
fluoride hydrate, chloride, chloride hydrate, oxychloride, bromide,
iodide, iodide hydrate, carboxylic acid derivative and/or
alkoxide.
9. A process (4) for preparing ethylenediphosphinic acid salts of
the type A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
as defined in claim 1 and A is H and X is H, an alkali metal, an
element of main or transition group 2, an element of main or
transition group 3, an element of main or transition group 4, an
element of main or transition group 5, an element of transition
group 6, an element of transition group 7, an element of transition
group 8 and/or a nitrogen base, wherein an
ethylenebis(hydroxyalkylphosphinic acid) of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A where
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and A is CR.sup.6R.sup.6--OH and X is H, an
alkali metal, an element of main or transition group 2, an element
of main or transition group 3, an element of main or transition
group 4, an element of main or transition group 5, an element of
transition group 6, an element of transition group 7, an element of
transition group 8 and/or a nitrogen base, is heated.
10. The process as claimed in claim 9, wherein heating is carried
out at from 20 to 300.degree. C., preferably from 50 to 200.degree.
C.
11. The process as claimed in claim 9 or 10, Wherein heating is
carried out in the presence of a protic acid which is a mineral
acid (hydrochloric acid, sulfuric acid, phosphoric acid),
carboxylic acid (formic acid, acetic acid, polymeric carboxylic
acid), sulfonic acid, phosphonic acid, organically crosslinked
carboxylic, sulfonic, phosphonic acid or a mixture thereof.
12. The use of ethylenediphosphinic acids as claimed in at least
one of claims 1 to 5 as flame retardants, in particular flame
retardants for clear coatings and intumescent coatings, flame
retardants for wood and other cellulose-containing products, as
reactive and/or nonreactive flame retardants for polymers, for
producing flame-retarded polymer molding compositions, for
producing flame-retardant polymer moldings and/or for the
flame-resistant treatment of polyesters and cellulose pure and
mixed woven fabrics by impregnation.
13. The use of ethylenediphosphinic acids as claimed in at least
one of claims 1 to 5 as binders for foundry compositions, mold
sands; as crosslinkers or accelerators in the curing of epoxy
resins, polyurethanes and unsaturated polyester resins; as polymer
stabilizers such as light stabilizers, free-radical scavengers
and/or heat stabilizers for woven cotton fabrics, polymer fibers,
plastics; as crop protection agents such as plant growth regulator,
as herbicide, pesticide or fungicide; as therapeutic agent or
additive in therapeutic agents for human beings and animals, e.g.
as enzyme modulator, for the simulation of tissue growth, as
sequestering agents, e.g. for the control of deposits in industrial
water piping systems, in mineral oil recovery and in metal
treatment agents; as mineral oil additive, e.g. as antioxidant and
for increasing the octane number; as corrosion inhibitor in laundry
detergent and cleaner applications, e.g. as decolorizing agent in
electronics applications, e.g. in polyelectrolytes for capacitors,
batteries and accumulators, and as free-radical scavengers in
photosensitive layers; as aldehyde scavengers; as formaldehyde
scavengers in adhesives, moldings, e.g. in building applications,
automobile, shipbuilding, aircraft and space flight industries, and
for electrical engineering, with it surprisingly having been found
that the phosphinic acids of the invention can be used for reducing
the liberation of aldehyde, and as acetaldehyde scavengers in
plastic beverage bottles.
14. A flame-retarded thermoplastic polymer molding composition
containing from 0.5 to 45% by weight of ethylenediphosphinic acid
as claimed in at least one of claims 1 to 5 and from 0.5 to 99.5%
by weight of thermoplastic polymer or mixtures thereof, with the
sum of the components being 100% by weight.
15. A flame-retarded thermoset composition containing from 0.1 to
45% by weight of ethylenediphosphinic acid as claimed in at least
one of claims 1 to 5, from 40 to 89.9% by weight of unsaturated
polyesters and from 10 to 60% by weight of vinyl monomers, with the
sum of the components being 100% by weight.
16. A flame-resistant epoxy resin containing from 0.5 to 50% by
weight of ethylenediphosphinic acid as claimed in at least one of
claims 1 to 5, from 5 to 99.5% by weight of an epoxy resin and from
0 to 20% by weight of a hardener, with the sum of the components
being 100% by weight.
Description
[0001] The invention relates to ethylenediphosphinic acids, a
process for preparing them and their use.
[0002] Ethylenediphosphinic acids are fundamentally known from the
prior art. Thus, DE-A-199 12 920 and WO-A-0 157 050 describe
phosphinic acids of the type
H--P(O)(OX)--[CH.sub.2CH.sub.2--P(O)(OX)].sub.nH where X is H,
metal or an alkyl group and n is greater than 1. These phosphinic
acids are oligomeric or polymeric. They are prepared by processes
which produce telomers but do not make it possible to obtain
phosphinic acids having a specific chain length.
[0003] It is therefore an object of the present invention to
provide ethylenediphosphinic acids which in each case have a
specific chain length and can thus be "tailored" to their
respective uses.
[0004] The invention accordingly provides ethylenediphosphinic
acids and salts thereof having the formula (I)
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A (I)
where A is H and/or CR.sup.5R.sup.6--OH, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 are identical or different and are each,
independently of one another, H, C.sub.1-C.sub.20-alkyl,
C.sub.5-C.sub.20-aryl or C.sub.5-C.sub.20-aralkyl and X is H, an
alkali metal, an element of main or transition group 2, an element
of main or transition group 3, an element of main or transition
group 4, an element of main or transition group 5, an element of
transition group 6, an element of transition group 7, an element of
transition group 8 and/or a nitrogen base.
[0005] Preference is given to R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6 being identical or different and each being,
independently of one another, H, methyl, ethyl, n-propyl, i-propyl,
n-butyl, tert-butyl, n-pentyl or phenyl.
[0006] Preference is given to A being H and X being Li, Na, K; Mg,
Ca, Zn, Sr; Al, Ce, La; Ge, Sn, Pb, Ti, Zr; Sb, Bi; Cr, Mo, W; Mn;
Fe, Co or Ni.
[0007] Particularly preference is given to A being H and X being H,
Na, Al, Zn, Ca, Mg, Ti or melamine.
[0008] The invention also provides a process (1) for preparing
ethylenediphosphinic acids and salts thereof having the formula
(I)
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A (I)
where A is H and/or CR.sup.6R.sup.6--OH, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6 are identical or different and are each,
independently of one another, H, C.sub.1-C.sub.20-alkyl,
C.sub.6-C.sub.20-aryl or C.sub.6-C.sub.20-aralkyl and X is H or an
alkali metal, wherein [0009] a) a monophosphinic acid adduct of the
formula (II)
[0009] H--P(O)(OX)-A (II) [0010] is reacted with acetylene and
[0011] b) if desired, the resulting ethylenediphosphinic acid of
the type A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
is separated off from by-products.
[0012] The invention also relates to a process (2) for preparing
ethylenebis(hydroxyalkylphosphinic acid) salts or
ethylenediphosphinic acid salts of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A, where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is an alkali metal, an element of main
group or transition group 2, an element of main or transition group
3, an element of main or transition group 4, an element of main or
transition group 5, an element of transition group 6, an element of
transition group 7, an element of transition group 8 and/or a
nitrogen base, wherein an ethylenebis(hydroxyalkylphosphinic acid)
or ethylenediphosphinic acid of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A, where A,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is H, is reacted in a solvent system with
a reactant I which is a compound of an alkali metal, of an element
of main or transition group 2, of an element of main or transition
group 3, of an element of main or transition group 4, of an element
of main or transition group 5, of an element of transition group 6,
of an element of transition group 7, of an element of transition
group 8 and/or a nitrogen base.
[0013] The invention also provides a process (3) for preparing
ethylenebis-(hydroxyalkylphosphinic acid) salts or
ethylenediphosphinic acid salts of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
where A, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6
are as defined in claim 1 and X is an element of main group or
transition group 2, an element of main or transition group 3, an
element of main or transition group 4, an element of main or
transition group 5, an element of transition group 6, an element of
transition group 7, an element of transition group 8 and/or a
nitrogen base, wherein ethylenebis(hydroxyalkylphosphinic acid) or
ethylenediphosphinic acid of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
where A, R.sup.1, R.sup.2, R.sup.3, R.sup.5 and R.sup.6 are as
defined in claim 1 and X is an alkali metal, is reacted in a
solvent system with a reactant II to form another metal salt (not
an alkali metal salt).
[0014] The reactant II is preferably a borate, carbonate,
hydroxocarbonate, hydroxocarbonate hydrate, mixed hydroxocarbonate,
mixed hydroxocarbonate hydrate, phosphate, sulfate, sulfate
hydrate, hydroxosulfate hydrate, mixed hydroxosulfate hydrate,
oxysulfate, acetate, nitrate, fluoride, fluoride hydrate, chloride,
chloride hydrate, oxychloride, bromide, iodide, iodide hydrate,
carboxylic acid derivative and/or alkoxide.
[0015] The invention also provides a process (4) for preparing
ethylenediphosphinic acid salts of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
as defined in claim 1 and A is H and X is H, an alkali metal, an
element of main or transition group 2, an element of main or
transition group 3, an element of main or transition group 4, an
element of main or transition group 5, an element of transition
group 6, an element of transition group 7, an element of transition
group 8 and/or a nitrogen base, wherein an
ethylenebis(hydroxyalkylphosphinic acid) of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 are
as defined in claim 1 and A is CR.sup.5R.sup.6--OH and X is H, an
alkali metal, an element of main or transition group 2, an element
of main or transition group 3, an element of main or transition
group 4, an element of main or transition group 5, an element of
transition group 6, an element of transition group 7, an element of
transition group 8 and/or a nitrogen base, is heated.
[0016] In the abovementioned process, the
ethylenebis(hydroxyalkylphosphinic acid) is preferably heated to
from 20 to 300.degree. C., particularly preferably from 50 to
200.degree. C.
[0017] Heating is preferably carried out in a protic acid which is
a mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid),
carboxylic acid (formic acid, acetic acid, polymeric carboxylic
acid), sulfonic acid, phosphonic acid, organically crosslinked
carboxylic, sulfonic, phosphonic acid or a mixture thereof.
[0018] The invention also provides for the use of
ethylenediphosphinic acids as claimed in at least one of claims 1
to 5 as flame retardants, in particular flame retardants for clear
coatings and intumescent coatings, flame retardants for wood and
other cellulose-containing products, as reactive and/or nonreactive
flame retardants for polymers, for producing flame-retarded polymer
molding compositions, for producing flame-retarded polymer moldings
and/or for the flame-resistant treatment of polyesters and
cellulose pure and mixed woven fabrics by impregnation.
[0019] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as binder, e.g. for
foundry compositions, mold sands.
[0020] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as crosslinker or
accelerator in the curing of epoxy resins, polyurethanes,
unsaturated polyester resins.
[0021] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as polymer
stabilizer, e.g. as light stabilizer, free-radical scavenger and/or
heat stabilizer for woven cotton fabrics, polymer fibers,
plastics.
[0022] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as crop protection
agent, e.g. as plant growth regulator, as herbicide, pesticide or
fungicide.
[0023] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as therapeutic agent
or additive in therapeutic agents for human beings and animals,
e.g. as enzyme modulator or for the stimulation of tissue
growth.
[0024] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as sequestering
agent, e.g. for the control of deposits in industrial water piping
systems, in mineral oil recovery and in metal treatment agents.
[0025] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as mineral oil
additive, e.g. as antioxidant and for increasing the octane
number.
[0026] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as corrosion
inhibitor.
[0027] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof in laundry detergent
and cleaner applications, e.g. as decolorizing agent.
[0028] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof in electronics
applications, e.g. in polyelectrolytes for capacitors, batteries
and accumulators, and as free-radical scavenger in photosensitive
layers.
[0029] Preference is given to the use of the inventive
ethylenediphosphinic acid and/or salt thereof as aldehyde
scavenger. It has surprisingly been found that the
ethylenediphosphinic acids of the invention can be used for
reducing the liberation of aldehyde. Preferred aldehydes are
formaldehyde and acetaldehyde.
[0030] Formaldehyde scavengers are preferably used in adhesives,
shaped bodies, e.g. in building applications, the automobile,
shipbuilding, aircraft and spaceflight industries, and for
electrical engineering, etc.
[0031] The invention also provides a flame-retardant thermoplastic
polymer molding composition containing from 0.5 to 45% by weight of
ethylenedi-phosphinic acid as claimed in at least one of claims 1
to 5 and from 0.5 to 99.5% by weight of thermoplastic polymer or
mixture thereof, with the sum of the components being 100% by
weight.
[0032] The invention also provides a flame-retardant thermoset
composition containing from 0.1 to 45% by weight of
ethylenediphosphinic acid as claimed in at least one of claims 1 to
5, from 40 to 89.9% by weight of unsaturated polyester and from 10
to 60% by weight of vinyl monomer, with the sum of the components
being 100% by weight.
[0033] The invention also provides an epoxy resin which has been
treated to make it flame resistant and contains from 0.5 to 50% by
weight of ethylenediphosphinic acid as claimed in at least one of
claims 1 to 5, from 5 to 99.5% by weight of an epoxy resin and from
0 to 20% by weight of a hardener, with the sum of the components
being 100% by weight.
[0034] Preferred ethylenediphosphinic acids correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is H, so
that when X is H, the resulting ethylenediphosphinic acid has the
formula
H--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--H;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--H;
and when X is aluminum, i.e. Al.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(OAl.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OAl.sub.1/3)--H;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
H--P(O)(OMeI)-CH.sub.2--CH.sub.2--P(O)(OMeI)-H.
[0035] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5, R.sup.6 are each H, so that
when X is H, the resulting ethylenediphosphinic acid has the
formula
HO--CH.sub.2--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--CH.sub.2--OH;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
HO--CH.sub.2--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--CH.sub.2--OH;
and when X is Al, i.e. Al.sub.m, the resulting ethylenediphosphinic
acid salt has the formula
HO--CH.sub.2--P(O)(OAl.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OAl.sub.1/3)---
CH.sub.2--OH;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
HO--CH.sub.2--P(O)(OMeI)-CH.sub.2--CH.sub.2--P(O)(OMeI)-CH.sub.2--OH.
[0036] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5 is CH.sub.3 and R.sup.6 is H, so
that when X is H, the resulting ethylenediphosphinic acid has the
formula
HO--CH(CH.sub.3)--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--CH(CH.sub.3)---
OH;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
HO--CH(CH.sub.3)--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--CH(CH.sub.3)-
--OH;
and when X is zinc, i.e. Zn.sub.1/2, the resulting
ethylenediphosphinic acid salt has the formula
HO--CH(CH.sub.3)--P(O)(OZn.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OZn.sub.1/-
2)--CH(CH.sub.3)--OH;
and when X is ammonium, i.e. NH.sub.4, the resulting
ethylenediphosphinic acid ammonium salt has the formula
HO--CH(CH.sub.3)--P(O)(ONH.sub.4)--CH.sub.2--CH.sub.2--P(O)(ONH.sub.4)---
CH(CH.sub.3)--OH.
[0037] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5 is phenyl and R.sup.6 is H, so
that when X is H, the resulting ethylenediphosphinic acid has the
formula
HO--CH(phenyl)-P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--CH(phenyl)-OH;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
HO--CH(phenyl)-P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--CH(phenyl)-OH;
and when X is titanium, i.e. Ti.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
HO--CH(phenyl)-P(O)(OTi.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OTi.sub.1/3)--
-CH(phenyl)-OH;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
HO--CH(phenyl)-P(O)(OMeI)-CH.sub.2--CH.sub.2--P(O)(OMeI)-CH(phenyl)-OH.
[0038] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5, R.sup.6 are each CH.sub.3, so
that when X is H, the resulting ethylenediphosphinic acid has the
formula
HO--C(CH.sub.3).sub.2--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--C(CH.sub.-
3).sub.2--OH;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--C(CH.su-
b.3).sub.2--OH;
and when X is magnesium, i.e. Mg.sub.1/2, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OMg.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OMg.s-
ub.1/2)--C(CH.sub.3).sub.2--OH;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OMeI)-CH.sub.2--CH.sub.2--P(O)(OMeI)-C(CH.su-
b.3).sub.2--OH.
[0039] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5 is CH.sub.3, R.sup.6 is
C.sub.2H.sub.5, so that when X is H, the resulting
ethylenediphosphinic acid has the formula
HO--C(CH.sub.3)(C.sub.2H.sub.5)--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--
-C(CH.sub.3)(C.sub.2H.sub.5)--OH;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3)(C.sub.2H.sub.5)--P(O)(OK)--CH.sub.2--CH.sub.2--P(O)(OK)--
-C(CH.sub.3)(C.sub.2H.sub.5)--OH;
and when X is aluminum, i.e. Al.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3)(C.sub.2H.sub.5)--P(O)(OAl.sub.1/3)--CH.sub.2--CH.sub.2---
P(O)(OAl.sub.1/3)--C(CH.sub.3)(C.sub.2H.sub.5)--OH;
and when X is ammonium, i.e. NH.sub.4, the resulting
ethylenediphosphinic acid ammonium salt has the formula
HO--C(CH.sub.3)(C.sub.2H.sub.5)--P(O)(ONH.sub.4)--CH.sub.2--CH.sub.2--P(-
O)(ONH.sub.4)--C(CH.sub.3)(C.sub.2H.sub.5)--OH.
[0040] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each H and A is
CR.sup.5R.sup.6--OH, where R.sup.5 is CH.sub.3, R.sup.6 is phenyl,
so that when X is H, the resulting ethylenediphosphinic acid has
the formula
HO--C(CH.sub.3)(phenyl)-P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--C(CH.sub-
.3)(phenyl)-OH;
and when X is an alkali metal, preferably Li, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3)(phenyl)-P(O)(OLD-CH.sub.2--CH.sub.2--P(O)(OLD-C(CH.sub.3-
)(phenyl)-OH;
and when X is zinc i.e. Zn.sub.1/2, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3)(phenyl)-P(O)(OZn.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OZn.-
sub.1/2)--C(CH.sub.3)(phenyl)-OH;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
HO--C(CH.sub.3)(phenyl)-P(O)(OMeI)-CH.sub.2--CH.sub.2--P(O)(OMeI)-C(CH.s-
ub.3)(phenyl)-OH.
[0041] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1 is methyl, R.sup.2, R.sup.3, R.sup.4 are each H and A
is H, so that when X is H, the resulting ethylenediphosphinic acid
has the formula
H--P(O)(OH)--CH(CH.sub.3)--CH.sub.2--P(O)(OH)--H;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(ONa)--C H(CH.sub.3)--CH.sub.2--P(O)(ONa)--H;
and when X is Al, i.e. Al.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(OAl.sub.1/3)--CH(CH.sub.3)--CH.sub.2--P(O)(OAl.sub.1/3)--H;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
H--P(O)(OMeI)-CH(CH.sub.3)--CH.sub.2--P(O)(OMeI)-H.
[0042] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1 is methyl, R.sup.2, R.sup.3, R.sup.4 are each H and A
is CR.sup.5R.sup.6--OH, where R.sup.5, R.sup.6 are each CH.sub.3,
so that when X is H, the resulting ethylenediphosphinic acid has
the formula
HO--C(CH.sub.3).sub.2--P(O)(OH)--CH(CH.sub.3)--CH.sub.2--P(O)(OH)--C(CH.-
sub.3).sub.2--OH;
and when X is an alkali metal, preferably K, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OK)--CH(CH.sub.3)--CH.sub.2--P(O)(OK)--C(CH.-
sub.3).sub.2--OH;
and when X is magnesium, i.e. Mg.sub.1/2, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OMg.sub.1/2)--CH(CH.sub.3)--CH.sub.2--P(O)(O-
Mg.sub.1/2)--C(CH.sub.3).sub.2--OH;
and when X is ammonium, i.e. NH.sub.4, the resulting
ethylenediphosphinic acid ammonium salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(ONH.sub.4)--CH(CH.sub.3)--CH.sub.2--P(O)(ONH-
.sub.4)--C(CH.sub.3).sub.2--OH.
[0043] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1 is phenyl, R.sup.2, R.sup.3, R.sup.4 are each H and A
is H, so that when X is H, the resulting ethylenediphosphinic acid
has the formula
H--P(O)(OH)--CH(phenyl)-CH.sub.2--P(O)(OH)--H;
and when X is an alkali metal, preferably Na, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(ONa)--CH(phenyl)-CH.sub.2--P(O)(ONa)--H;
and when X is Al, i.e. Al.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
H--P(O)(OAl.sub.1/3)--CH(phenyl)-CH.sub.2--P(O)(OAl.sub.1/3)--H;
and when X is melamine, i.e. MeI, the resulting
ethylenediphosphinic acid melamine salt has the formula
H--P(O)(OMeI)-CH(phenyl)-CH.sub.2--P(O)(OMeI)-H.
[0044] Preferred ethylenediphosphinic acids also correspond to the
formula
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A,
where R.sup.1 is phenyl, R.sup.2, R.sup.3, R.sup.4 are each H and A
is CR.sup.5R.sup.6--OH, where R.sup.5, R.sup.6 are each CH.sub.3,
so that when X is H, the resulting ethylenediphosphinic acid has
the formula
HO--C(CH.sub.3).sub.2--P(O)(OH)--CH(phenyl)-CH.sub.2--P(O)(OH)--C(CH.sub-
.3).sub.2--OH;
and when X is an alkali metal, preferably K, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OK)--CH(phenyl)-CH.sub.2--P(O)(OK)--C(CH.sub-
.3).sub.2--OH;
and when X is titanium, i.e. Ti.sub.1/3, the resulting
ethylenediphosphinic acid salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(OTi.sub.1/3)--CH(phenyl)-CH.sub.2--P(O)(OTi.-
sub.1/3)--C(CH.sub.3).sub.2--OH;
and when X is ammonium, i.e. NH.sub.4, the resulting
ethylenediphosphinic acid ammonium salt has the formula
HO--C(CH.sub.3).sub.2--P(O)(ONH.sub.4)--CH(phenyl)-CH.sub.2--P(O)(ONH.su-
b.4)--C(CH.sub.3).sub.2--OH.
[0045] Preferred nitrogen bases are ammonium, substituted ammonium,
ethylenediamine, hydroxylamine, urea, N-alicyclic compounds such as
pyrrolidine, piperidine, imidazolidine, piperazine, N-aromatic
compounds such as heteroaromatic ring compounds such as pyrrole,
pyridine, imidazole, pyrazine, substituted urea derivatives (e.g.
dimethylurea, N,N'-diphenylurea, benzylurea, acetyleneurea,
tetramethylurea), thiourea, guanidine, substituted guanidine
derivatives (e.g. alkylguanidine, arylguanidine,
diphenylguanidine), biguanide, melamine, substituted melamine
derivatives (e.g. ethylenedimelamine), condensation products of
melamine and more highly condensed compounds thereof, e.g. melem,
melam or melon, melamine-phenol systems, benzoguanamine,
acetoguanamine, urethanes, cyanamide, dicyandiamide, aniline,
sulfonamide, biuret, allantoin, tolyltriazole, benzotriazole,
2-amino-4-methylpyrimidine, hydantoin, substituted hydantoin
derivatives (e.g. 5,5-diphenylhydantoin), malonamide amidine,
ethylenebis-5-triazone, glycine anhydride and any mixtures
thereof.
[0046] Preferred alkali metals are sodium, potassium.
[0047] The reaction of the monophosphinic acid adduct with
acetylene in process (1) preferably takes place [0048] a) in the
presence of a solvent and a free-radical initiator, [0049] b) by
placing monophosphinic acid adduct and solvent in a reaction vessel
and secondly feeding in acetylene and initiator (if desired in a
solvent), [0050] c) by placing monophosphinic acid adduct,
acetylene and solvent in a reaction vessel and feeding in initiator
(if desired in a solvent), [0051] d) by placing monophosphinic acid
adduct, solvent and initiator in a reaction vessel and feeding in
acetylene (if desired in a solvent), [0052] e) by placing
monophosphinic acid adduct, acetylene, solvent and initiator in a
reaction vessel.
[0053] The product is preferably separated off in process (1) by
[0054] a) solid-liquid separation (e.g. filtration, centrifugation,
allowing to settle), [0055] b) liquid-liquid separation (e.g.
extraction, etc).
[0056] Preferred adducts for process (1) are those with aldehydes
and/or ketones.
[0057] Preferred aldehydes for process (1) are aliphatic aldehydes
(formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
valeraldehyde, caproaldehyde, acrolein, crotonaldehyde, propargyl
aldehyde) and/or aromatic aldehydes (benzaldehyde, p-tolualdehyde,
anisaldehyde or salicylaldehyde, vanillin).
[0058] Preferred ketones for process (1) are aliphatic ketones
(acetone, methyl ethyl ketone, chloroacetone, methyl vinyl ketone,
mesityl oxide, phorone) or aromatic ketones (acetophenone,
benzophenone).
[0059] Preferred aldehydes are aliphatic aldehydecarboxylic acids
(glyoxylic acid).
[0060] Preferred ketones are aliphatic ketocarboxylic acids
(pyruvic acid, acetoacetic acid, levulinic acid).
[0061] Preferred aldehydes are aliphatic hydroxyaldehydes
(glycolaldehyde, glyceraldehyde).
[0062] Preferred aldehydes are aliphatic hydroxyketones (acetol,
acetoin, dihydroxyacetone).
[0063] Preferred, aldehydes are aliphatic dialdehydes (glyoxal,
malonaldehyde, succinaldehyde).
[0064] Preferred aldehydes are ketoaldehydes (methylglyoxal).
[0065] Preferred ketones are diketones (diacetyl, acetylacetone,
acetonylacetone).
[0066] Suitable free-radical initiators for process (1) are in
principle all systems which generate free radicals. The addition
reaction of the olefin can be initiated by means of an anionic
initiator, a free-radical initiator or photochemically.
[0067] Particularly preferred free-radical initiators are peroxo
compounds such as peroxomonosulfuric acid, potassium persulfate
(potassium peroxomonosulfate), Caroat.TM., Oxo-ne.TM.,
peroxodisulfuric acid, potassium persulfate (potassium
peroxodisulfate), sodium persulfate (sodium peroxodisulfate),
ammonium persulfate (ammonium peroxodisulfate).
[0068] Particular preference is given to compounds which can form
peroxides in the solvent system, e.g. sodium peroxide, sodium
peroxide diperoxohydrate, sodium peroxide diperoxohydrate hydrate,
sodium peroxide dihydrate, sodium peroxide octahydrate, lithium
peroxide, lithium peroxide monoperoxohydrate trihydrate, calcium
peroxide, strontium peroxide, barium peroxide, magnesium peroxide,
zinc peroxide, potassium hyperoxide, potassium peroxide
diperoxohydrate, sodium peroxoborate tetrahydrate, sodium
peroxoborate trihydrate, sodium peroxoborate monohydrate, anhydrous
sodium peroxoborate, potassium peroxoborate peroxohydrate,
magnesium peroxoborate, calcium peroxoborate, barium peroxoborate,
strontium peroxoborate, potassium peroxoborate,
peroxomonophosphoric acid, peroxodiphosphoric acid, potassium
peroxodiphosphate, ammonium peroxodiphosphate, potassium ammonium
peroxodiphosphate (double salt), sodium carbonate peroxohydrate,
urea peroxohydrate, ammonium oxalate peroxide, barium peroxide
peroxohydrate, calcium hydrogen peroxide, calcium peroxide
peroxohydrate, ammonium triphosphate diperoxophosphate hydrate,
potassium fluoride peroxohydrate, potassium fluoride
triperoxohydrate, potassium fluoride diperoxohydrate, sodium
pyrophosphate diperoxohydrate, sodium pyrophosphate diperoxohydrate
octahydrate, potassium acetate peroxohydrate, sodium phosphate
peroxohydrate, sodium silicate peroxohydrate.
[0069] Particular preference is given to hydrogen peroxide,
performic acid, peracetic acid, benzoyl peroxide, di-t-butyl
peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, decanoyl
peroxide, lauryl peroxide, cumene hydroperoxide, pinene
hydroperoxide, p-methane hydroperoxide, t-butyl hydroperoxide,
acetylacetone peroxide, methyl ethyl ketone peroxide, succinic
peroxide, dicetyl peroxydicarbonate, t-butyl peroxyacetate, t-butyl
peroxymaleate, t-butyl peroxybenzoate, acetyl cyclohexylsulfonyl
peroxide.
[0070] Preference is given to using water-soluble azo compounds as
free-radical initiators.
[0071] Preference is also given to azo initiators such as
2-t-butylazo-2-cyanopropane, dimethyl azodiisobutyrate,
azobisisobutyronitrile, 2-t-butylazo-1-cyanocyclohexane,
1-t-amylazo-1-cyanocyclohexane. Preference is also given to alkyl
perketals such as 2,2-bis(t-butylperoxy)-butane, ethyl
3,3-bis(t-butylperoxy)butyrate,
1,1-di(t-butylperoxy)cyclo-hexane.
[0072] Particular preference is given to azo initiators such as
.RTM.VAZO 52, .RTM.VAZO 64 (AIBN), .RTM.VAZO 67, .RTM.VAZO 88,
.RTM.VAZO 44, .RTM.VAZO 56, .RTM.VAZO 68 from Dupont-Biesteritz,
V-70 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), V-65
2,2'-azobis(2,4-dimethylvaleronitrile), V-601 dimethyl
2,2'-azobis(2-methylpropionate), V-59
2,2'-azobis(2-methylbutyronitrile), V-40, VF-096
1,1'-azobis(cyclohexane-1-carbonitrile), V-30
1-[(cyano-1-methylethyl)azo]formamide, VAm-110
2,2'-azobis(N-butyl-2-methylpropionamide), Am-111
2,2'-azobis(N-cyclohexyl-2-methylpropionamide), VA-041
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride,
VA-044 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride,
VA-046B 2,2'-azobis[2-(2-imidazolin-2-yl)propane disulfate
dihydrate, V-50 2,2'-azobis(2-amidinopropane) hydrochloride, VA-057
2,2'-azobis-[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate,
VA-058
2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane]dihydrochl-
oride, VA-060
2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochlori-
de, VA-061, 2,2'-azobis[2-(2-imidazolin-2-yl)propane], VA-080
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e, VA-085 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide,
VA-086 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] from
Wako Chemicals.
[0073] The preparation in process (1) can be carried out using a
solvent. Solvents which are suitable according to the invention are
preferably water, alcohols such as methanol, ethanol, isopropanol,
n-propanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol,
isoamyl alcohol, t-amyl alcohol, n-hexanol, n-octanol, isooctanol,
n-tridecanol, benzyl alcohol, etc. Preference is also given to
glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, diethylene glycol, etc; aliphatic
hydro-carbons such as pentane, hexane, heptane, octane and
petroleum ether, petroleum benzene, kerosene, petroleum, paraffin
oil, etc; aromatic hydrocarbons such as benzene, toluene, xylene,
mesitylene, ethylbenzene, diethylbenzene, etc; halogenated
hydrocarbons such as methylene chloride, chloroform,
1,2-dichloroethane, chlorobenzene, carbon tetrachloride,
tetrabromoethylene, etc; alicyclic hydrocarbons such as
cyclopentane, cyclohexane and methylcyclohexane, etc; ethers such
as anisole (methyl phenyl ether), t-butyl methyl ether, dibenzyl
ether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether,
tetrahydrofuran, triisopropyl ether, etc; glycol ethers such as
diethylene glycol diethyl ether, diethylene glycol dimethyl ether
(diglyme), diethylene glycol monobutyl ether, diethylene glycol
monomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene
glycol monobutyl ether, triethylene glycol dimethyl ether
(triglyme), triethylene glycol monomethyl ether, etc; ketones such
as acetone, diisobutyl ketone, methyl n-propyl ketone; methyl ethyl
ketone, methyl isobutyl ketone, etc; esters such as methyl formate,
methyl acetate, ethyl acetate, n-propyl acetate and n-butyl
acetate, etc; carboxylic acids such as formic acid, acetic acid,
propionic acid, butyric acid, etc. One or more of these compounds
can be used either or alone or in combination.
[0074] According to the invention, preference is given to a weight
ratio of solvent to monophosphinic acid adduct in process (1) of
from 100:1 to 1:100, particularly preferably from 10:1 to 1:10.
[0075] According to the invention, preference is given to a molar
ratio of initiator to monophosphinic acid adduct in process (1) of
from 1:1 to 1:1000, particularly preferably from 1:2 to 1:100.
[0076] According to the invention, preference is given to a molar
ratio of acetylene to monophosphinic acid adduct in process (1) of
from 100:1 to 1:100, particularly preferably from 5:1 to 1:5.
[0077] According to the invention, preference is given to a
reaction time of from 0.1 to 100 h, particularly from 1 to 10 h, in
process (1).
[0078] According to the invention, the phosphinic acid of the type
HO--CR.sup.5R.sup.6--P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-
--CR.sup.5R.sup.6OH is preferably purified.
[0079] Preferred purification methods in process (1) are [0080] a)
recrystallization from a solvent according to the invention and
solid-liquid separation, [0081] b) digestion with a solvent
according to the invention and solid-liquid separation.
[0082] The preferred radio of solvent to phosphinic acid of the
type
HO--CR.sup.5R.sup.6--P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-
--CR.sup.5R.sup.6OH for the preferred purification method in
process (1) is from 1000:1 to 4:1, particularly preferably from
100:1 to 1:1.
[0083] The preferred temperature for the purification process in
process (1) is from 20 to 200.degree. C., particularly preferably
from 50 to 150.degree. C.
[0084] The preferred pressure for the purification process in
process (1) is from 10 to 100 000 000 Pa.
[0085] Preference is given to a purity after process (1) of greater
than 90%, particularly preferably greater than 95%.
[0086] The invention also provides processes for preparing
ethylenebis(hydroxyalkylphosphinic acid) salts and
ethylenediphosphinic acid salts, in which the acids are converted
into aluminum salts or the alkali metal salts are converted into
aluminum salts.
[0087] According to the invention, preference is given to a process
(2) in which an ethylenebis(hydroxyalkylphosphinic acid) or
ethylenediphosphinic acid according to the invention in which X is
H is reacted in a suitable solvent system with a reactant A.
[0088] In a process (3), the inventive salt of the
ethylenebis(hydroxyalkylphosphinic acid) or ethylenediphosphinic
acid according to the invention in which X is an alkali metal can
preferably be converted in a suitable solvent into another metal
salt by addition of another component B.
[0089] The reaction of the phosphinic acid according to the
invention with component A in process (2) is preferably carried out
at a solids content of the salts of phosphinic acids according to
the invention of from 0.1 to 70% by weight, preferably from 5 to
40% by weight.
[0090] The reaction in process (2) is preferably carried out at a
temperature of from -20 to +500.degree. C., particularly preferably
from 70 to 160.degree. C.
[0091] The ratio of component A to phosphorus (of the phosphinic
acid according to the invention) in process (2) is preferably from
0.8 to 3 ion equivalents (mole per charge on the cation),
particularly preferably from 1 to 2.
[0092] The molar ratio of solvent to phosphorus (of the phosphinic
acid according to the invention) in process (2) is preferably from
2 to 1000, particularly preferably from 4 to 100.
[0093] A solvent system which is preferred according to the
invention in process (2) has a dissociation constant pKa of from 10
to 30.
[0094] A component A which is preferred according to the invention
in process (2) is a salt of an element of main group 1, preferably
an alkali metal hydroxide, alkali metal oxide hydroxide, alkali
metal hydroxide carbonate, alkali metal alkoxide, particularly
preferably lithium hydroxide, sodium hydroxide, potassium
hydroxide, sodium methoxide, sodium ethoxide, sodium n-propoxide,
sodium i-propoxide, sodium n-butoxide, sodium i-butoxide, sodium
tert-butoxide, sodium amylate, sodium glycolate.
[0095] A component A which is preferred according to the invention
in process (2) is a salt of an element of main group 1, preferably
an element of main group or transition group 2, preferably an
alkaline earth metal hydroxide, alkaline earth metal oxide
hydroxide, alkaline earth metal hydroxide carbonate, particularly
preferably magnesium hydroxide (.RTM.Magnifin H5, Albermarle),
hydrotalcite (Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.nH.sub.2O),
dihydrotalcite, magnesium carbonate or magnesium calcium carbonate,
calcium hydroxide, basic zinc carbonate, zinc hydroxide carbonate,
basic zinc carbonate hydrate, zinc hydroxide or a mixed zinc oxide
hydroxide (standard zinc oxide, e.g. from Grillo, activated zinc
oxide, e.g. from Rheinchemie, zincite, calamine), zinc
hydroxystannate.
[0096] A component A which is preferred according to the invention
in process (2) is a salt of an element of main or transition group
3, preferably aluminum hydroxide, cerium hydroxide, lanthanum
hydroxide, aluminum alkoxide, cerium alkoxide, lanthanum alkoxide,
aluminum hydroxide or mixed aluminum oxide hydroxide,
dihydroxyaluminum sodium carbonate NaAl(OH).sub.2CO.sub.3 and/or a
polyaluminum hydroxy compound which preferably has an aluminum
content of from 9 to 40% by weight.
[0097] A component A which is preferred according to the invention
in process (2) is a salt of an element of main or transition group
4, preferably zinc hydroxide, lead hydroxide, titanium oxide
hydroxide, zirconium oxide hydroxide, tin alkoxide, titanium
alkoxide, zirconium alkoxide.
[0098] Titanium alkoxides which are preferred according to the
invention are titanium(IV) n-propoxide, .RTM.Tilcom NPT,
.RTM.Vertec NPT), titanium(IV) n-butoxide, titanium chloride
triisopropoxide, titanium(IV) ethoxide, titanium(IV)
2-ethylhexyloxide (.RTM.Tilcom EHT, .RTM.Vertetec EHT).
[0099] A tin alkoxide which is preferred according to the invention
is tin(IV) tert-butoxide.
[0100] A zinc alkoxide which is preferred according to the
invention is zirconium(IV) tert-butoxide.
[0101] Components B which are preferred according to the invention
in process (3) are borates, carbonates, hydroxocarbonates,
hydroxocarbonate hydrates, mixed hydroxocarbonates, mixed
hydroxocarbonate hydrates, phosphates, sulfates, sulfate hydrates,
hydroxosulfate hydrates, mixed hydroxosulfate hydrates,
oxysulfates, acetates, nitrates, fluorides, fluoride hydrates,
chloride, chloride hydrates, oxychlorides, bromides, iodides,
iodide hydrates, carboxylic acid derivatives and/or alkoxides of an
element of main group 1, of main group or transition group 2,
preferably Mg, Ca, Zn, of main group or transition group 3,
preferably Al, Ce, La.
[0102] Components B which are preferred according to the invention
in process (3) are aluminum chloride, aluminum nitrate, aluminum
sulfate, titanium sulfate, zinc nitrate, zinc sulfate and zinc
chloride.
[0103] The reaction in process (3) is preferably carried out in a
stirred vessel, mixer and/or kneader.
[0104] The reaction in process (3) is preferably carried out with
an energy input of from 0.083 to 1.65 kW/m.sup.3, particularly
preferably 0.33-1.65 kW/m.sup.3.
[0105] The salts of phosphinic acids according to the invention are
preferably separated off from the reaction mixture in process (3)
by filtration and/or centrifugation.
[0106] The salts of phosphinic acids according to the invention are
preferably separated off in process (3) by means of pressure
filters, vacuum filters, stirred filters, pressure candle filters,
axial plate filters, circular plate filters, centrifugal disc
filters, chamber/frame filter presses, automatic chamber filter
presses, vacuum drum cell filters, vacuum disc cell filters, vacuum
internal cell filters, vacuum flat cell filters, rotary pressure
filters, vacuum belt filters.
[0107] The filtration pressure in process (3) is preferably from
0.5 Pa to 6 MPa.
[0108] The filtration temperature in process (3) is preferably from
0 to 400.degree. C.
[0109] The specific filtration throughput in process (3) is
preferably from 10 to 200
[0110] The residual moisture content of the filtercake in process
(3) is preferably from 5 to 60%.
[0111] The salts of ethylenebis(hydroxyalkylphosphinic acid) or
ethylenediphosphinic acid according to the invention obtained in
process (3) are preferably separated off by means of solid bowl
centrifuges such as overflow centrifuges, peeler centrifuges,
chamber centrifuges, screw discharge centrifuges, plate
centrifuges, tube centrifuges, screen centrifuges such as
suspension and oscillatory centrifuges, screen screw centrifuges,
screen peeler centrifuges or pusher centrifuges.
[0112] The acceleration ratio in process (3) is preferably from 300
to 15 000.
[0113] The suspension throughput in process (3) is preferably from
2 to 400 m.sup.3*H.sup.-1.
[0114] The solids throughput in process (3) is preferably from 5 to
80 t*h.sup.-1.
[0115] The residual moisture content of the cake in process (3) is
preferably from 5 to 60%.
[0116] The salts of phosphinic acids according to the invention are
preferably dried in process (3).
[0117] Apparatuses which are, according to the invention, suitable
for drying in process (3) are chamber dryers, channel dryers, belt
dryers (air velocity=2-3 m/s), plate dryers (temperature: 20 to
400.degree. C.), drum dryers (100-250.degree. C. hot gas
temperature), paddle dryers (50-300.degree. C. temperature), flow
dryers (10-60 m/s air velocity, 50-300.degree. C. exhaust air
temperature), fluidized-bed dryers (0.2-0.5 m/s air velocity,
50-300.degree. C. exhaust air temperature), roller dryers, tube
dryers (20 to 200.degree. C. temperature), paddle dryers, vacuum
drying ovens (20 to 300.degree. C. temperature, 0.001-0.016 MPa
pressure), vacuum roller dryers (20 to 300.degree. C. temperature,
0.004-0.014 MPa pressure), vacuum paddle dryers (20 to 300.degree.
C. temperature, 0.003-0.02 MPa pressure), vacuum cone dryers (20 to
300.degree. C. temperature, 0.003-0.02 MPa pressure).
[0118] The invention also provides a process (4) for the formation
of inventive ethylenediphosphinic acid of the type
H--P(O)(OH)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OH)--H from
inventive ethylenebis(hydroxyalkylphosphinic acid) of the type
HO--CR.sup.5R.sup.6--P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-
--CR.sup.5R.sup.6OH.
[0119] An embodiment according to the invention of process (4) is
heating the inventive ethylenebis(hydroxyalkylphosphinic acid) of
the type
HO--CR.sup.5R.sup.6--P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-
--CR.sup.5R.sup.6OH.
[0120] The preferred temperature for the formation process in
process (4) is from 20 to 300.degree. C., particularly preferably
from 50 to 200.degree. C.
[0121] The preferred pressure for the formation process in process
(4) is from 10 to 100 000 000 Pa.
[0122] Preference is given to a molar ratio of protic acid to
inventive ethylenebis(hydroxyalkylphosphinic acid) of the type
HO--CR.sup.5R.sup.6--P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-
--CR.sup.5R.sup.6OH in process (4) of from 100:1 to 1:100,
particularly preferably from 10:1 to 1:10.
[0123] The protic acid is preferably removed in process (4). The
removal is preferably effected by distillation, extraction and/or
crystallization.
[0124] The preferred temperature for the removal of the protic acid
in process (4) is from 20 to 300.degree. C., particularly
preferably from 50 to 200.degree. C.
[0125] The preferred pressure for the removal of the protic acid in
process (4) is from 10 to 10.sup.8 Pa.
[0126] According to the invention, the heating in process (4) is
preferably carried out in the presence of a solvent.
[0127] The preferred temperature for separating off the solvent in
process (4) is from 20 to 300.degree. C., particularly preferably
from 50 to 200.degree. C.
[0128] The preferred pressure for separating of the solvent in
process (4) is from 10 to 10.sup.8 Pa.
[0129] The ethylenebis(hydroxyalkylphosphinic acid) according to
the invention is preferably used for preparing the
ethylenediphosphonic acid with elimination of the end groups (this
is possible as acids/alkali metal salts/AI salts, etc).
[0130] Here, preference is given to using the inventive phosphinic
acid and/or salt thereof of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
and derivatives thereof where R.sup.1, R.sup.2, R.sup.3, R.sup.4
are each H, C.sub.1-C.sub.20-alkyl, aryl (preferably phenyl) and/or
aralkyl, A is CR.sup.1R.sup.2OH, X is H, alkali metal, Al, Zn, Ca;
Mg, Ti, nitrogen base (preferably NH.sub.4, ethylenediamine,
melamine, etc) for preparing the inventive phosphinic acid and/or
salt thereof of the type
A-P(O)(OX)--CR.sup.1R.sup.2--CR.sup.3R.sup.4--P(O)(OX)-A
and derivatives thereof where R.sup.1, R.sup.2, R.sup.3, R.sup.4
are each H, C.sub.1-C.sub.20-alkyl, aryl (preferably phenyl) and/or
aralkyl, A is H, X is H, alkali metal, Al, Zn, Ca, Mg, Ti, nitrogen
base (preferably NH.sub.4, ethylenediamine, melamine, etc).
[0131] Preference is given to using the inventive phosphinic acid
and/or salt thereof for producing flame-retarded polymer molding
compositions.
[0132] The flame-retarded polymer molding composition preferably
contains from 0.5 to 45% by weight of inventive phosphinic acid
and/or salt thereof, from 0.5 to 95% by weight of polymer or
mixtures thereof, from 0.5 to 55% by weight of additives, from 0.5
to 55% by weight of filler or reinforcing materials, with the sum
of the components being 100% by weight.
[0133] The flame-retarded polymer molding composition preferably
contains from 10 to 40% by weight of inventive phosphinic acid
and/or salt thereof, from 10 to 80% by weight of polymer or
mixtures thereof, from 2 to 40% by weight of additives, from 2 to
0.40% by weight of filler or reinforcing materials, with the sum of
the components being 100% by weight.
[0134] In a process for producing flame-retarded polymer molding
compositions, the inventive phosphinic acid and/or salt thereof is
mixed with the polymer pellets and possibly additives and
compounded on a twin-screw extruder (ZSK 25 WLE, 14.5 kg/h, 200
rpm, L/D: 4) at temperatures of 170.degree. C. (polystyrene), about
270.degree. C. (PET, polyethylene terephthalate) from 230 to
260.degree. C. (polybutylene terephthalate, PBT), 260.degree. C.
(PA6) or from 260 to 280.degree. C. (PA 66). The homogenized
polymer strand is taken off, cooled in a water bath, subsequently
pelletized and dried to a residual moisture content of from 0.05 to
5% by weight, preferably from 0.1 to 1% by weight.
[0135] In a process for producing a flame-retarded polymer molding
composition, 1000 parts by weight of dimethyl terephthalate and 720
parts by weight of ethylene glycol and from 35 to 700 parts by
weight of a phosphinic acid according to the invention are
polymerized. If desired, the polymerization can be carried out in
the presence of zinc acetate. If desired, the flame-retarded
polymer molding composition can be spun to produce fibers.
[0136] The polymer is preferably a thermoplastic or thermoset
polymer.
[0137] The thermoplastic polymers are preferably polymers of
monoolefins and diolefins, for example polypropylene,
polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene,
polyisoprene or polybutadiene and also polymers of cycloolefins,
e.g. of cyclopentene or norbornene; also polyethylene (which may,
if appropriate, be crosslinked), e.g. high density polyethylene
(HDPE), high molecular weight high density polyethylene (HMWHDPE),
ultrahigh molecular weight high density polyethylene (UHMWHDPE),
medium density polyethylene (MDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), branched low
density polyethylene (BLDPE), and mixtures thereof.
[0138] The thermoplastic polymers are preferably copolymers of
monoolefins and diolefins with one another or with other vinyl
monomers, e.g. ethylene-propylene copolymers, linear low density
polyethylene (LLDPE) and mixtures thereof with low density
polyethylene (LDPE), propylene-1-butene copolymers,
propylene-isobutylene copolymers, ethylene-1-butene 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; 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 such as polyamides.
[0139] 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.
[0140] The thermoplastic polymers are preferably polystyrene,
poly(p-methyl-styrene) and/or poly(alpha-methylstyrene).
[0141] The thermoplastic polymers are preferably copolymers of
styrene or alpha-methylstyrene with dienes or acrylic derivatives,
e.g. styrene-butadiene, styrene-acrylonitrile, styrene-alkyl
methacrylate, styrene-butadiene-alkyl acrylate or methacrylate,
styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate;
high-impact mixtures of styrene copolymers and another polymer,
e.g. a polyacrylate, a diene polymer or an ethylene-propylene-diene
terpolymer; and also block copolymers of styrene, e.g.
styrene-butadiene-styrene, styrene-isoprene-styrene,
styrene-ethylene/butylene-styrene or
styrene-ethylene/propylene-styrene.
[0142] The thermoplastic polymers are preferably graft copolymers
of styrene or alpha-methylstyrene, e.g. styrene on polybutadiene,
styrene on polybutadiene-styrene or polybutadiene-acrylonitrile
copolymers, styrene and acrylonitrile (or methacrylonitrile) on
polybutadiene; styrene, acrylonitrile and methyl methacrylate on
polybutadiene; styrene and maleic anhydride on polybutadiene;
styrene, acrylonitrile and maleic anhydride or maleimide on
polybutadiene; styrene and maleimide on polybutadiene, styrene and
alkyl acrylates or alkyl methacrylates on polybutadiene, styrene
and acrylonitrile on ethylene-propylene-diene terpolymers, styrene
and acrylonitrile on polyalkyl acrylates or polyalkyl
methacrylates, styrene and acrylonitrile on acrylate-butadiene
copolymers, and also mixtures thereof, as are known as, for
example, ABS, MBS, ASA or AES polymers.
[0143] The thermoplastic polymers are preferably halogen-containing
polymers such as polychloroprene, chlorinated rubber, chlorinated
and brominated copolymer of isobutylene-isoprene (halobutyl
rubber), chlorinated or chlorosulfonated polyethylene, copolymers
of ethylene and chlorinated ethylene, epichlorohydrin homopolymers
and copolymers, in particular polymers of halogen-containing vinyl
compounds, e.g. polyvinyl chloride, polyvinylidene chloride,
polyvinyl fluoride, polyvinylidene fluoride; and also copolymers
thereof, e.g. vinyl chloride-vinylidene chloride, vinyl
chloride-vinylacetate or vinylidene chloride-vinyl acetate.
[0144] The thermoplastic polymers are preferably polymers derived
from alpha, beta-unsaturated acids and derivatives thereof, e.g.
polyacrylates and polymethacrylates, butyl acrylate-impact-modified
polymethyl meth-acrylates, polyacrylamides and polyacrylonitriles
and copolymers of the abovementioned monomers with one another or
with other unsaturated monomers, e.g. acrylonitrile-butadiene
copolymers, acrylonitrile-alkyl acrylate copolymers,
acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl
halide copolymers or acrylonitrile-alkyl methacrylate-butadiene
terpolymers.
[0145] The thermoplastic polymers are preferably polymers derived
from unsaturated alcohols and amines or acyl derivatives or acetals
thereof, e.g. polyvinyl alcohol, polyvinyl acetate, stearate,
benzoate, maleate, polyvinyl butyral, polyallyl phthalate,
polyallyl melamine; and also copolymers thereof with olefins.
[0146] The thermoplastic polymers are preferably homopolymers and
copolymers of cyclic ethers, e.g. polyalkylene glycols,
polyethylene oxide, polypropylene oxide or copolymers thereof with
bisglycidyl ethers.
[0147] The polymers are preferably thermoplastic polyacetals such
as polyoxymethylene or polyoxymethylenes containing comonomers,
e.g. ethylene oxide; polyacetals modified with thermoplastic
polyurethanes, acrylates or MBS.
[0148] The thermoplastic polymers are preferably polyphenylene
oxides and sulfides and mixtures thereof with styrene polymers or
polyamides.
[0149] The thermoplastic polymers are preferably polyurethanes
derived from polyethers, polyesters and polybutadienes having
terminal hydroxyl groups and aliphatic or aromatic polyisocyanates,
and also intermediates derived therefrom.
[0150] The thermoplastic polymers are preferably polyamides and
copolyamides derived from diamines and dicarboxylic acids and/or
from aminocarboxylic acids or the corresponding lactams, e.g.
polyamide 4, polyamide 6 (.RTM.Akulon K122, DSM; .RTM.Zytel 7301,
from DuPont; .RTM.Durethan B 29, from Bayer), polyamide 6/6
(.RTM.Zytel 101, from DuPont; .RTM.Durethan A30, .RTM.Durethan AKV,
.RTM.Durethan AM, from Bayer; .RTM.Ultramid A3, from BASF) 6/10,
6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12 (.RTM.Grillamid
L20, from Ems Chemie), aromatic polyamides derived from m-xylene,
diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic and/or terephthalic acid and,
if appropriate, an elastomer as modifier, e.g.
poly-2,4,4-trimethylhexamethyleneterephthalamide or
poly-m-phenyleneisophthalamide; block copolymers of the
above-mentioned polyamides with polyolefins, olefin copolymers,
ionomers or chemically bounded or grafted elastomers; or with
polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene glycol; also polyamides or copolyamides modified
with EPDM or ABS; and also polyamides which have been condensed
during processing ("RIM polyamide systems").
[0151] The polymers are preferably polyureas, polyimides, polyamide
imides, polyetherimides, polyesterimides, polyhydantoins and
polybenzimidazoles.
[0152] The thermoplastic polymers are preferably polyesters derived
from dicarboxylic acids and dialcohols and/or from
hydroxycarboxylic acids or the corresponding lactones, e.g.
polyethylene terephthalate, polybutylene terephthalate
(.RTM.Celanex 2500, .RTM.Celanex 2002, from Celanese;
.RTM.Ultradur, from BASF), poly-1,4-dimethylolcyclohexane
terephthalate, polyhydroxy-benzoates, and also block polyether
esters derived from polyethers having hydroxyl end groups; also
polyesters modified with polycarbonates or MBS.
[0153] The thermoplastic polymers are preferably polycarbonates and
polyester carbonates, polysulfones, polyether sulfones and
polyether ketones.
[0154] The polymers are preferably mixtures (polyblends) of the
above-mentioned polymers, e.g. PP/EPDM, polyamide/EPDM or ABS,
PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT,
PVC/CPE, PCV/acrylates, POM/thermoplastic PUR, PC/thermoplastic
PUR, POM/acrylate: POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,
PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
[0155] Preference is given to using the inventive phosphinic acid
and/or salt thereof for producing flame-retardant polymer moldings,
films, threads and fibers.
[0156] The flame-retarded polymer moldings, films, threads and
fibers preferably contain from 0.5 to 45% by weight of inventive
phosphinic acid and/or salt thereof, from 0.5 to 95% by weight of
thermoplastic polymer or mixtures thereof.
[0157] The flame-retardant polymer moldings, films, threads and
fibers preferably contain from 0.5 to 45% by weight of inventive
phosphinic acid and/or salt thereof, from 0.5 to 95% by weight of
thermoplastic polymer or mixtures thereof, from 0.5 to 55% by
weight of additives, from 0.5 to 55% by weight of filler or
reinforcing materials.
[0158] Finally, the invention also provides a process for producing
flame-retarded polymer moldings, wherein flame-retarded polymer
molding compositions according to the invention are processed by
injection molding (e.g. injection-molding machine (model: Aarburg
Allrounder) and pressing, foam injection molding, gas internal
pressure injection molding, blow molding, tape casting,
calendering, lamination or coating at relatively high temperatures
to produce flame-retarded polymer moldings.
[0159] In the process for producing flame-retarded polymer
moldings, the flame-retarded molding composition according to the
invention is processed at melt temperatures according to the
invention to produce polymer moldings.
[0160] Melt temperatures which are preferred according to the
invention are from 200 to 250.degree. C. in the case of
polystyrene, from 200 to 300.degree. C. in the case of
polypropylene, from 250 to 290.degree. C. in the case of
polyethylene terephthalate (PET), from 230 to 270.degree. C. in the
case of polybutylene terephthalate (PBT), from 260 to 290.degree.
C. in the case of polyamide 6 (PA 6), from 260 to 290.degree. C. in
the case of polyamide 6.6 (PA 6.6) and from 280 to 320.degree. C.
in the case of polycarbonate.
[0161] A flame-resistant thermoset composition according to the
invention comprises from 0.1 to 45% by weight of phosphinic acid
according to the invention, from 40 to 90% by weight of unsaturated
polyester, from 10 to 60% by weight of vinyl monomer.
[0162] The thermoset polymers are preferably unsaturated polyester
resins derived from copolyesters of saturated and unsaturated
dicarboxylic acids or anhydrides thereof with polyhydric alcohols
and also vinyl compounds as crosslinkers. UP resins are cured by
free-radical polymerization using initiators (e.g. peroxides) and
accelerators.
[0163] Preferred unsaturated dicarboxylic acids and derivatives for
preparing the polyesters are maleic anhydride and fumaric acid.
[0164] Preferred saturated dicarboxylic acids are phthalic acid,
isophthalic acid, terephthalic acid, tetrahydrophthalic acid,
adipic acid.
[0165] Preferred diols are 1,2-propanediol, ethylene glycol,
diethylene glycol and neopentyl glycol, ethoxylated or propoxylated
bisphenol A.
[0166] A preferred vinyl compound for crosslinking is styrene.
[0167] Preferred hardener systems are peroxides and metal
coinitiators, e.g. hydroperoxides and cobalt octanoate and/or
benzoyl peroxide and aromatic amines and/or UV sensitizers and
photosensitizers, e.g. benzoin ethers.
[0168] Preferred hydroperoxides are di-tert-butyl peroxide,
tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl
per-2-ethylhexanoate, tert-butyl permaleate, tert-butyl
perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl
peroxide, p-chlorobenzoyl peroxide or dicyclohexyl
peroxydicarbonate.
[0169] Preference is given to using initiators in amounts of from
0.1 to 20% by weight, preferably from 0.2 to 15% by weight, based
on the mass of all comonomers.
[0170] Preferred metal coinitiators are cobalt, manganese, iron,
vanadium, nickel or lead compounds. Preference is given to using
metal coinitiators in amounts of from 0.05 to 1% by weight, based
on the mass of all comonomers.
[0171] Preferred aromatic amines are dimethylaniline,
dimethylamino-p-toluene, diethylaniline, phenyldiethanolamines.
[0172] A process for producing flame-retarded copolymers is carried
out by copolymerizing (A) at least one ethylenically unsaturated
dicarboxylic anhydride derived from at least one
C.sub.4-C.sub.8-dicarboxylic acid, (B) at least one vinylaromatic
compound and (C) polyol and then reacting the product with (D)
phosphinic acid according to the invention.
[0173] A process for producing flame-retarded thermoset
compositions is carried out by mixing a thermoset resin with a
flame retardant component comprising phosphinic acid according to
the invention and wet pressing the resulting mixture at pressures
of from 3 to 10 bar and temperatures of from 20 to 60.degree. C.
(cold pressing).
[0174] Another process for producing flame-resistant thermoset
compositions is carried out by mixing a thermoset resin with
phosphinic acid according to the invention and wet pressing the
resulting mixture at pressures of from 3 to 10 bar and temperatures
of from 80 to 150.degree. C. (warm or hot pressing).
[0175] The polymers are preferably crosslinked epoxy resins derived
from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl
compounds, e.g. products of bisphenol A diglycidyl ethers,
bisphenol F diglycidyl ethers, which are crosslinked by means of
customary hardeners and/or accelerators.
[0176] Glycidyl compounds which can be used according to the
invention are bisphenol A diglycidyl esters, bisphenol F diglycidyl
esters, polyglycidyl esters of phenol-formaldehyde resins and
cresol-formaldehyde resins, polyglycidyl esters of phthalic,
isophthalic and terephthalic acid and of trimellitic acid,
N-glycidyl compounds of aromatic amines and heterocyclic nitrogen
bases and also diglycidyl and polyglycidyl compounds of polyhydric
aliphatic alcohols.
[0177] Suitable hardeners are polyamines such as
diethylenetriamine, triethylene-tetramine, aminoethylpiperazine,
isophoronediamine, polyamidoamine, diaminodiphenylmethane,
diaminodiphenol sulfones, dicyandiamide.
[0178] Suitable hardeners are polybasic acids or anhydrides
thereof, e.g. phthalic anhydride, maleic anhydride,
tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride,
hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.
[0179] Suitable hardeners are phenols such as phenol Novolak resin,
cresol Novolak resin, cyclopentadiene-phenol adduct resin,
phenol-aralkyl resin, cresol-aralkyl resin, naphthol-aralkyl resin,
bisphenol-modified phenol-aralkyl resin, phenol-trimethylolmethane
resin, tetraphenylolethane resin, naphthol Novolak resin,
naphthol-phenol cocondensate resin, naphthol-cresol cocondensate
resin, bisphenol-modified phenolic resin and
amino-triazine-modified phenolic resin.
[0180] These hardeners can be used either alone or in combination
with one another.
[0181] Catalysts or accelerators according to the invention for
crosslinking in polymerization are tertiary amines,
benzyldimethylamine, N-alkylpyridines, imidazole,
1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methyl-imidazole,
2-ethyl-4-methylimidazole, 2-phenylimidazole,
2-heptadecylimidazole, metal salts of organic, acids, Lewis acids
and amine complex salts.
[0182] Epoxy resins are suitable for the embedding of electric or
electronic components and for steeping and impregnation processes.
In electrical engineering, the epoxy resins used are predominantly
provided with flame retardants and used for circuit boards and
insulators.
[0183] The polymers are preferably crosslinked polymers derived
from aldehydes and phenols, urea or melamine, e.g.
phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde
resins.
[0184] The polymers are preferably crosslinkable acrylic resins
derived from substituted acrylic esters, e.g. from epoxy acrylates,
urethane acrylates or polyester acrylates.
[0185] The polymers are preferably alkyd resins, polyester resins
and acrylate resins crosslinked by means of melamine resins, urea
resins, isocyanates, isocyanurates, polyisocyanates or epoxy
resins.
[0186] A flame-retarded polyurethane molding composition can be
produced by reacting from 0.1 to 50 parts by weight of phosphinic
acid according to the invention with from 30 to 65 parts by weight
of polyisocyanate and from 30 to 65 parts by weight of polyol.
[0187] In a process for producing a flame-retarded polyurethane
molding composition, from 170 to 70 parts by weight, preferably
from 130 to 80 parts by weight, of polyisocyanates according to the
invention are reacted with 100 parts by weight of polyol according
to the invention, from 0.1 to 50 parts by weight of phosphinic acid
according to the invention and from 0.1 to 4 parts by weight,
particularly preferably from 1 to 2 parts by weight, of catalyst
according to the invention and, if desired, foamed by means of from
0.1 to 1.8 parts by weight, preferably from 0.3 to 1.6 parts by
weight, of blowing agent.
[0188] Preferred polyols are alkene oxide adducts of ethylene
glycol, 1,2-propanediol, bisphenol A, trimethylolpropane, glycerol,
pentaerythritol, sorbitol, sugar, degraded starch, ethylenediamine,
diaminotoluene and/or aniline, which serve as starter. The
oxyalkylating agents which are preferred according to the invention
preferably contain from 2 to 4 carbon atoms and are particularly
preferably ethylene oxide and propylene oxide.
[0189] Preferred polyester polyols are obtained by polycondensation
of a polyalcohol such as ethylene glycol, diethylene glycol,
propylene glycol, 1,4-butanediol, 1,5-pentanediol,
methylpentanediol, 1,6-hexanediol, trimethylolpropane, glycerol,
pentaerythritol, diglycerol, glucose and/or sorbitol with a dibasic
acid such as oxalic acid, malonic acid, succinic acid, tartaric
acid, adipic acid, sebacic acid, maleic acid, fumaric acid,
phthalic acid, terephthalic acid. These polyester polyols can be
used either alone or in combination.
[0190] Suitable polyisocyanates are aromatic, alicyclic or
aliphatic polyisocyanates having no fewer than two isocyanate
groups and mixtures thereof. Preference is given to aromatic
polyisocyanates such as tolylene diisocyanate, methylenedi(phenyl
isocyanate), naphthylene diisocyanate, xylylene diisocyanate,
tris(4-isocyanatophenyl)methane and poly-methylenepolyphenylene
diisocyanates; alicyclic polyisocyanates are methylenedi(phenyl
isocyanate), tolylene diisocyanate; and aliphatic polyisocyanates
are hexamethylene diisocyanate, isophorone diisocyanate, dimeryl
diisocyanate,
1,1-methylenebis(4-isocyanatocyclohexane)-4,4'-diisocyanatodicyclohexylme-
thane isomer mixture, 1,4-cyclohexyl diisocyanate, (R)Desmodur
grades (Bayer) and lysine diisocyanate and mixtures thereof.
[0191] Suitable polyisocyanates are modified products obtained by
reaction of polyisocyanate with polyol, urea, carbodiimide and/or
biuret.
[0192] Suitable catalysts are strong bases, alkali metal salts of
carboxylic acids or aliphatic tertiary amines. Preference is given
to quaternary ammonium hydroxides, alkali metal hydroxide or
alkoxide, sodium or potassium acetate, potassium octoate, sodium
benzoate, 1,4-diazabicyclo[2.2.2]-octane,
N,N,N',N'-tetramethylhexannethylenediamine,
N,N,N',N'-tetra-methylpropylenediamine,
N,N,N',N',N''-pentamethyldiethylenetriamine,
N,N'-di-(C.sub.1-C.sub.2)-alkylpiperazine,
trimethylaminoethylpiperazine, N,N-dimethylcyclohexylamine,
N,N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine,
trimethylamine, triethylamine, tributylamine, triethylenediamine,
bis(dimethylaminoalkyl)piperazine,
N,N,N',N'-tetramethylethylenediamine, N,N-diethylbenzylamine,
bis(N,N-diethylaminoethyl) adipate,
N,N,N',N'-tetramethyl-1,3-butanediamine,
N,N-diethyl[beta]phenylethylamine, 1,2-dimethylimidazole,
2-methylimidazole etc.
[0193] The weight ratio of polyisocyanates to polyol is preferably
170:70, more preferably 130:80, based on 100 parts by weight of the
polyol.
[0194] The weight ratio of catalyst is preferably from 0.1 to 4
parts by weight, particularly preferably from 1 to 2 parts by
weight, per 100 parts by weight of the polyol.
[0195] Preferred blowing agents are water, hydrocarbon,
chlorofluorocarbon, fluorinated hydrocarbon, etc.
[0196] The amount of any blowing agent used is from 0.1 to 1.8
parts by weight, preferably from 0.3 to 1.6 parts by weight,
preferably from 0.8 to 1.6 parts by weight, per 100 parts by weight
of the polyol.
[0197] The decomposition temperature is determined by standard
thermo-gravimetric methods. The decomposition temperature is
defined here as the temperature at which a weight loss of 2%
occurs.
Chemicals Used
[0198] HMPPA: 1-Hydroxy-1-methylethylphosphinic acid,
H--P(O)(OH)C(CH.sub.3).sub.2OH [0199] Wako V 65 B:
2,2'-Azobis-2,4-dimethylvaleronitrile [0200] Waco V50:
2,2'-Azobis-2-amidinopropane hydrochloride [0201] VAZO 52:
2,2'-Azobisisopropylbutyronitrile [0202] VAZO 67:
2,2'-Azobismethylbutyronitrile [0203] VAZO 64: AIBN
2,2'-azobisisobutyronitrile [0204] EBHA:
Ethylenebis(1-hydroxy-1-methylethylphosphinic acid),
HO--C(CH.sub.3).sub.2--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--C(CH.sub.3-
).sub.2--OH [0205] EBHNa: Disodium
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--C(CH.sub-
.3).sub.2--OH [0206] EBHAl: Aluminum
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(OAl.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OAl.su-
b.1/3)--C(CH.sub.3).sub.2--OH [0207] EBHZn: Zinc
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(OZn.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OZn.su-
b.1/2)--C(CH.sub.3).sub.2--OH [0208] EBHCa: Calcium
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(OCa.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OCa.su-
b.1/2)--C(CH.sub.3).sub.2--OH [0209] EBHMg: Magnesium
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(OMg.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OMg.su-
b.1/2)--C(CH.sub.3).sub.2--OH [0210] EBHFe: Iron
ethylenebis(1-hydroxy-1-methylethylphosphinate),
HO--C(CH.sub.3).sub.2--P(O)(OFe.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OFe.su-
b.1/3)--C(CH.sub.3).sub.2--OH [0211] EBPA: Ethylenebisphosphinic
acid, H--P(O)(OH)--CH.sub.2--CH.sub.2--P(O)(OH)--H [0212] EBPNa:
Disodium ethylenebisphosphinate,
H--P(O)(ONa)--CH.sub.2--CH.sub.2--P(O)(ONa)--H [0213] EBPAI:
Aluminum ethylenebisphosphinate,
H--P(O)(OAl.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OAl.sub.1/3)--H
[0214] EBPZn: Zinc ethylenebisphosphinate,
H--P(O)(OZn.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OZn.sub.1/2)--H
[0215] EBPCa: Calcium ethylenebisphosphinate,
H--P(O)(OCa.sub.1/2)--CH.sub.2--CH.sub.2--P(O)(OCa.sub.1/2)--H
[0216] EBPFe: Iron ethylenebisphosphinate,
H--P(O)(OFe.sub.1/3)--CH.sub.2--CH.sub.2--P(O)(OFe.sub.1/3)--H
[0217] EBPMeI: Melamine ethylenebisphosphinate,
H--P(O)(OC.sub.3H.sub.6N.sub.6)--CH.sub.2--CH.sub.2--P(O)(OC.sub.3H.sub.6-
N.sub.6)--H [0218] Polystyrene: Polystyrol 143 E, from BASF [0219]
PA 6.6: .RTM.Ultramid A3, from BASF [0220] MPP: .RTM.Melapur
200/70, from Ciba SC [0221] Glass fibers 1: VPPG 3540, from PPG
Industries, Inc [0222] Glass fibers 2: .RTM.Vetrotex EC 10983, from
Saint. Gobain
EXAMPLES
Preparation of Concentrated Hypophosphorous Acid (HPA,
H.sub.3PO.sub.2)
[0223] Concentrated HPA can be prepared according to the prior
art.
[0224] Commercially available 50% aqueous hypophosphorous acid is
concentrated by evaporation to constant weight on a rotary
evaporator under a water pump vacuum and a temperature which does
not exceed 40.degree. C. [0225] 1-Hydroxy-1-methylethylphosphinic
acid (HMPPA) [0226] 1-Hydroxy-1-methylethylphosphinic acid is
prepared according to the prior art from concentrated HPA and
isolated as a pale yellow oil to white resin in a yield of 96%.
[0227] Method of preparing
ethylenebis(1-hydroxy-1-methylethylphosphinic acid) HMPPA and amyl
alcohol were placed in a two liter five-neck flask provided with
stirrer, thermometer, low-temperature condenser, initiator
metering, frit for introduction of acetylene and blanketing with
nitrogen and homogenized. The reaction mixture was heated. The
stirrer speed was 460 rpm. After the reaction temperature had been
reached, the initiator was metered in as 10% strength solution in
the appropriate solvent by means of a pump. Acetylene was
introduced at 5-61/h. The product precipitates during the reaction
and, after the reaction is complete, is filtered off on a suction
filter and washed twice with acetone. The powder was dried at
120.degree. C. in a drying oven. Typical purity: 93.6%
(.sup.31P-NMR). The product is X-ray crystalline. The following
reflections (CuK.sub.alpha 1 radiation 1.54056 Ang) are observed:
rel. intensity/d: 20.2, 7.78620; 62.9, 5.63264; 100.0, 5.33438;
27.5, 4.91046; 47.2%, 4.49822 Ang. The hydroxyl group number is 290
mg KOH/g.
[0228] The product can, if desired, be digested with ethanol (25%
strength dispersion) to purify it further. The yields in this step
are 80-90% and lead to purities of about 99.2% (.sup.31P-NMR).
Example 1
[0229] 345 g of 1-hydroxy-1-methylethylphosphinic acid and 29.8 g
of Wako V65 B initiator in a total of 803 g of amyl alcohol at
80.degree. C. for 11 hours give 210 g of product.
Example 2
[0230] 345 g of 1-hydroxy-1-methylethylphosphinic acid and 18.3 g
of VAZO 52 initiator in a total of 803 g of amyl alcohol at
50.degree. C. for 11 hours give 141 g of product.
Example 3
[0231] 345 g of 1-hydroxy-1-methylethylphosphinic acid and 19.7 g
of AIBN initiator in a total of 803 g of amyl alcohol at
120.degree. C. for 8 hours give 240 g of product.
Example 4
[0232] 345 g of 1-hydroxy-1-methylethylphosphinic acid and 6.9 g of
Wako V65 B initiator in a total of 803 g of amyl alcohol at
80.degree. C. for 32 hours give 187 g of product.
Example 5
[0233] 345 g of 1-hydroxy-1-methylethylphosphinic acid and 29.8 g
of Wako V65 B initiator in a total of 350 g of amyl alcohol at
80.degree. C. for 11 hours give 259 g of product.
Example 6
Disodium ethylenebis(1-hydroxy-1-methylethylphosphinate)
[0234] 141 g of demineralized water are placed in a 1 l glass
beaker and firstly 40 g of NaOH pellets and then 137.1 g of EBHA
are carefully added while stirring. 318 g of a 50% strength by
weight solution of EBHNa are obtained.
[0235] General method of preparing
ethylenebis(1-hydroxy-1-methylethylphosphinate) salts and
ethylenebisphosphinate salts
[0236] Either the demineralized water is placed in a two liter or
four liter six-neck flask (provided with stirrer, thermometer,
stopper, inlet tube and reflux condenser) and the metal salt is
dissolved with heating to the precipitation temperature or the
finished metal salt solution is placed in the flask and heated to
the precipitation temperature. The calculated amount of EBHNa
solution is pumped in via an inlet tube by means of a pump over the
prescribed time. The preselected precipitation temperature is
maintained and the mixture is stirred at a preselected stirrer
speed. The solid product is filtered off hot on a suction filter,
then dispersed by means of demineralized water at 90.degree. C.
(five times the amount of the theoretical yield) and again filtered
off hot on a suction filter. The solid is dried at 100.degree. C.
and 30 mbar in a drying oven for 15 hours.
Example 7
Aluminum ethylenebis(1-hydroxy-1-methylethylphosphinate)
[0237] Using the general method for preparing the metal
ethylenebis(1-hydroxy-1-methylethylphosphinates), 318 g of EBHNa
solution are reacted with 209 g of aluminum sulfate solution at
90.degree. C. and 750 rpm stirrer speed for 2 hours. 132 g of solid
product are obtained. The product is X-ray crystalline. The
following reflections (CuK.sub.alpha 1 radiation 1.54056 Ang) are
observed: rel. intensity/d: 65.6, 11.03554; 100.0, 10.55511; 30.2,
8.91804; 33.4%, 8.74638 Ang. The analytical data are shown in table
2.
Example 8
Zinc ethylenebis(1-hydroxy-1-methylethylphosphinate)
[0238] Using the general method for preparing the metal
ethylenebis(1-hydroxy-1-methylethylphosphinates), 318 g of EBHNa
solution are reacted with 144 g of zinc sulfate heptahydrate
dissolved in 1240 g of demineralized water at 90.degree. C. and 250
rpm stirrer speed for 2 hours. 135 g of solid product are obtained.
The product is X-ray crystalline. The following reflections
(CuK.sub.alpha 1 radiation 1.54056 Ang) are observed: rel.
intensity/d: 100.0, 11.09087; 35.7, 10.67607; 29.4, 5.26978; 40.3%,
4.91046 Ang. The analytical data are shown in table 2.
Example 9
Magnesium ethylenebis(1-hydroxy-1-methylethylphosphinate)
[0239] Using the general method for preparing the metal
ethylenebis(1-hydroxy-1-methylethylphosphinates), 318 g of EBHNa
solution are reacted with 102 g of magnesium chloride hexahydrate
dissolved in 568 g of demineralized water at 50.degree. C. and 750
rpm stirrer speed for 2 hours. 111 g of solid product are obtained.
The product is X-ray crystalline. The following reflections
(CuK.sub.alpha 1 radiation 1.54056 Ang) are observed: rel.
intensity/d: 100.0%, 11.23166 Ang. The analytical data are shown in
table 2.
Example 10
Iron ethylenebis(1-hydroxy-1-methylethylphosphinate)
[0240] Using the general method for preparing the metal
ethylenebis(1-hydroxy-1-methylethylphosphinates), 318 g of EBHNa
solution are reacted with 67 g of iron sulfate dissolved in 2710 g
of demineralized water at 90.degree. C. and 750 rpm stirrer speed
for 8 hours. 139 g of solid product are obtained. The analytical
data are shown in table 2.
Example 11
Method of Preparing Ethylenebisphosphinic Acid by Elimination of
Acetone from ethylenebis(1-hydroxy-1-methylethylphosphinic
acid)
[0241] 274 g of EBHA are weighed into a four-neck flask provided
with distillation rectangle, dripping funnel and thermometer and
admixed with 4 mol of hydrochloric acid (37% strength). The
apparatus is made inert by means of nitrogen. The mixture is heated
to the boiling point of the hydrochloric acid on an oil bath and
the solution is boiled under reflux temperature (at the top:
105-108.degree. C.). The temperature at the top decreases with time
due to the elimination of acetone. Distillate is drained off every
now and again until the temperature at the top remains constant at
108.degree. C. (constantly replenished with 37% strength
hydrochloric acid by means of a dropping funnel). When the boiling
temperature is constant, the remaining hydrochloric acid is
distilled off at 1 mbar and max. 110.degree. C. on a rotary
evaporator.
Example 12
Disodium ethylenebisphosphinate
[0242] 83 g of demineralized water are placed in a 1 l glass beaker
while stirring and firstly 40 g of NaOH pellets and then 79 g of
EBPA are added carefully. 202 g of a 50% strength by weight
solution of EBPNa are obtained.
Example 13
Aluminum ethylenebisphosphinate
[0243] Using the general method for preparing the metal
ethylenebisphosphinates, 202 g of EBPNa solution are reacted with
209 g of aluminum sulfate solution at 90.degree. C. and 750 rpm
stirrer speed for 2 hours. 71 g of solid product are obtained. The
analytical data are shown in table 3.
Example 14
Zinc ethylenebisphosphinate
[0244] Using the general method for preparing the metal
ethylenebisphosphinates, 202 g of EBPNa solution are reacted with
144 g of zinc sulfate heptahydrate dissolved in 770 g, of
demineralized water at 100.degree. C. and 1500 rpm stirrer speed
for 1 hour. 95 g of solid product are obtained. The product is
X-ray crystalline. The following reflections (CuK.sub.alpha 1
radiation 1.54056 Ang) are observed: rel. intensity/d: 39.2,
7.82398; 37.2, 6.52943; 100.0, 3.90381; 63.3%, 3.22809 Ang. The
analytical data are shown in table 3.
Example 15
Calcium ethylenebisphosphinate
[0245] Using the general method for preparing the metal
ethylenebisphosphinates, 202 g of EBPNa solution are reacted with
74 g of calcium chloride dihydrate dissolved in 380 g of
demineralized water at 90.degree. C. and 750 rpm stirrer speed for
2 hours. 58 g of solid product are obtained. The analytical data
are shown in table 3.
Example 16
Iron Ethylenebisphosphinate
[0246] Using the general method for preparing the metal
ethylenebisphosphinates, 202 g of EBPNa solution are reacted with
67 g of iron sulfate dissolved in 2720 g of demineralized water at
90.degree. C. and 750 rpm stirrer speed for 2 hours. 90 g of solid
product are obtained. The analytical data are shown in table 3.
Example 17
Dimelamine ethylenebisphosphinate
[0247] 79 g of EBPA and 126 g of melamine are dissolved in hot
ethylene glycol. On cooling 148 g of solid product precipitates.
The product is X-ray crystalline. The following reflections
(CuK.sub.alpha 1 radiation 1.54056 Ang) are observed: rel.
intensity/d: 39.0, 5.71392; 40.2, 3.95093; 100.0%, 3.43265 Ang. The
analytical data are shown in table 3.
Example 18
Comparison
[0248] Using the general method, a mixture of 70% by weight of
polystyrene and 30% by weight of calcium hypophosphite is
compounded at 170.degree. C. on a twin-screw extruder to give a
polymer molding composition. Ignition occurs during processing as a
result of decomposition of the flame retardant.
Example 19
[0249] Using the general method, a mixture of 70% by weight of
polystyrene and 30% by weight of product from example 12 is
compounded at 170.degree. C. on a twin-screw extruder to give a
polymer molding composition. After drying, the molding compositions
are processed at 200-250.degree. C. on an injection molding machine
to produce polymer moldings and a UL-94 classification of V-0 is
determined.
Example 20
[0250] Using the general method, a mixture of 70% by weight of
polystyrene and 30% by weight of product from example 13 is
compounded at 170.degree. C. on a twin-screw extruder to give a
polymer molding composition. After drying, the molding compositions
are processed at 200-250.degree. C. on an injection molding machine
to produce polymer moldings and a UL-94 classification of V-0 is
determined.
Example 21
[0251] Using the general method, a mixture of 70% by weight of
polystyrene and 30% by weight of product from example 14 are
compounded at 170.degree. C. on a twin-screw extruder to give a
flame-retarded polymer molding composition. After drying, the
flame-retarded molding composition is processed at 200-250.degree.
C. on an injection molding machine to produce flame-retarded
polymer moldings and a UL-94 classification of V-0 is
determined.
Example 22
[0252] Using the general method, a mixture of 70% by weight of
polystyrene and 30% by weight of product from example 15 are
compounded at 170.degree. C. on a twin-screw extruder to give a
flame-retarded polymer molding composition. After drying, the
flame-retarded molding composition is processed at 200-250.degree.
C. on an injection molding machine to produce flame-retarded
polymer moldings and a UL-94 classification of V-0 is
determined.
Example 23
[0253] Using the general method, a mixture of 50% by weight of PA
6.6, 12.5% by weight of product from example 12, 12.5% by weight of
MPP and 25% by weight of glass fibers are compounded at
260-280.degree. C. on a twin-screw extruder to give a
flame-retarded polymer molding composition. After drying, the
flame-retarded molding composition is processed at 260-290.degree.
C. on an injection molding machine to produce flame-retarded
polymer moldings and a UL-94 classification of V-1 is
determined.
Example 24
[0254] Using the general method, a mixture of 50% by weight of PBT,
12.5% by weight of product from example 13, 12.5% by weight of MPP
and 25% by weight of glass fibers are compounded at 230-260.degree.
C. on a twin-screw extruder to give a flame-retarded polymer
molding composition. After drying, the flame-retarded molding
composition is processed at 230-270.degree. C. on an injection
molding machine to produce flame-retarded polymer moldings and a
UL-94 classification of V-1 is determined.
Example 25 (Comparison)
[0255] An adhesive composition is produced from 82% of Airflex 920
(Air Products and Chemicals Inc), 1% of Tego antifoam (East Falls
Corp.), 15% of AP 422 (Clariant GmbH) and 2% of Alcogum 296W (ALCO
Chemical). 100 g of this composition are weighed into a 250 ml
wide-neck screw-top bottle and stored at 60.degree. C. for 8 hours.
The gas space after storage was examined by means of formaldehyde
test strips from Drager Sicherheitstechnik GmbH (type 0.2/a). After
pumping ten times, a formaldehyde concentration of greater than 50
ppm is read off.
Example 26
[0256] An adhesive composition is produced from 80% of Airflex 920
(Air Products and Chemicals Inc), 1% of Tego antifoam (East Falls
Corp.), 15% of AP 422 (Clariant GmbH), 2% of Alcogum 296W (ALCO
Chemical) and 2% of the product from example 11. The product is
tested as described in example 25. A formaldehyde concentration of
about 10 ppm is read off. The adhesive is particularly suitable for
building applications.
TABLE-US-00001 TABLE 1 Preparation of
ethylenebis(1-hydroxy-2-methylethylphosphinic acid) HPA adduct
Initiator Solvent Actylene T Product DT .degree. C., 31P-NMR
Example g Type g Type g g .degree. C. th g % 2% WL ppm 1 345 Wako
V65 B 29.8 AmOH 803 64 80 11 210 55 167 54.8 2 345 VAZO 52 18.3
AmOH 803 64 50 11 141 37 3 345 AIBN 19.7 OctOH 803 64 120 8 240 63
4 345 Wako V65 B 6.9 AmOH 803 64 80 32 187 49 5 345 Wako V65 B 29.8
AmOH 350 64 80 11 259 68 WL = Weight loss DT = Decomposition
temperature
TABLE-US-00002 TABLE 2 Preparation of
ethylenebis(1-hydroxy-1-methyethylphosphinate) salts Stirrer DT
31P- Starting material A Starting material B Solvent T speed
Product .degree. C. 2% NMR P content Example g g g th .degree. C.
rpm g WL ppm exp % th % 6 EBHA 137 NaOH 40 H.sub.2O 141 0.5 30 300
318 -- 46 -- -- 7 EBHNa 318 Al.sub.2(SO.sub.4).sub.3 soln 209
H.sub.2O 0 2 90 750 132 248 46 20.6 21.4 4.3% Al 8 EBHNa 318
ZnSO.sub.4 7aq 144 H.sub.2O 1240 2 90 250 135 283 46 17.9 18.4 9
EBHNa 318 MgCl.sub.2 6aq 102 H.sub.2O 568 2 50 750 111 260 46 19.8
20.9 10 EBHNa 318 Fe.sub.2(SO.sub.4).sub.3 67 H.sub.2O 2710 8 90
750 139 262 46 19.5 20
TABLE-US-00003 TABLE 3 Preparation of ethylenebisphosphinate salts
Stirrer 31P- Starting material A Starting material B Solvent T
speed Product DT .degree. C. NMR P content Example g g g th
.degree. C. rpm g 2% WL ppm exp % th % 12 EBPA 79 NaOH 40 H.sub.2O
83 0.5 30 300 202 -- 31 -- -- 13 EBPNa 202 Al.sub.2(SO.sub.4).sub.3
soln 209 H.sub.2O 0 2 90 750 71 >600 31 33.2 35.6 4.3% Al 14
EBPNa 202 ZnSO.sub.4 7aq 144 H.sub.2O 770 1 100 1500 95 >1000 31
27.7 28.0 15 EBPNa 202 CaCl.sub.2 2aq 74 H.sub.2O 380 2 90 750 58
>600 31 30.0 31.6 16 EBPNa 202 Fe.sub.2(SO.sub.4).sub.3 67
H.sub.2O 2720 2 90 750 90 >600 31 29.9 32.1 17 EBPA 79 Melamine
126 Ethylene 3900 2 100 750 148 279 31 14.9 15.1 glycol
TABLE-US-00004 TABLE 4 Flame-retarded polymer molding compositions
and flame resistance tests on flame-retarded polymer moldings
Examples 18 19 20 21 22 Polystyrene [% by weight] 70 70 70 70 70
Calcium hypophosphite [% by weight] 30 Product from example 13 [%
by weight] 30 Product from example 14 [% by weight] 30 Product from
example 15 [% by weight] 30 Product from example 16 [% by weight]
30 UL-94 classification Ignition during V-0 V-0 V-0 V-0 (1.5 mm)
processing
TABLE-US-00005 TABLE 5 Flame-retarded polymer molding compositions
and flame resistance tests on flame-retarded polymer moldings
Examples 23 24 [% by weight] [% by weight] PA 6.6 50 PBT 50 Glass
fibers 1 25 Glass fibers 2 25 Product from example 13 12.5 Product
from example 14 12.5 MPP 12.5 -- MC -- 12.5 UL-94 class V-1 V-1
* * * * *