Note: Descriptions are shown in the official language in which they were submitted.
A-19902/A/CGM 448
' ~14~2~~
Enhancement of the storage stability of or ag nic phos~hites and~hosphonites
The invention relates to a process for stabilising organic phosphites and
phosphonites
against hydrolysis by addition of amines and acid-binding metal salts, to
compositions
comprising these three components, and to the use of amines together with acid-
binding
metal salts as hydrolysis stabilisers for phosphites and phosphonites.
Organic phosphites and phosphonites are widely used as heat stabilisers for
synthetic
polymers.
The preparation, storage and use of phosphites and phosphonites is, however,
impeded by
the fact that these compounds hydrolise very easily. A particular problem is
the storage of
the material at high atmospheric humidity.
Different methods have been proposed to provide products having enhanced
stability to
hydrolysis. Besides processes for the preparation of purer products and
methods of
purifiying the compounds, such methods are in particular the addition of
special stabilisers
which on the one hand reduce the tendency of the products to hydrolyse and
which, on the
other hand, do not have any negative effects in the subsequent use of the
phosphites or
phosphonites in organic polymers.
The last mentioned methods embrace the addition of amines as hydrolysis
stabilisers as is
disclosed, inter alia, in US-A-3 553 298. Further publications relating to the
stabilisation
of phosphites with amines are US-A-3 787 537, US-A-5 342 978, EP-A-168 721 and
EP-A-167 969. It is recommended in particular to use tertiary alkanolamines
and
alkylamines, pyridines and anilines; typical examples are triethylamine,
diethanolamine,
triethanolamine, di- and triisopropanolamine (TIPA),
tetraisopropanolethylenediamine,
aniline, phenylenediamine and hexamethylenetetramine. The amines are generally
used in
amounts of up to c. 5% by weight (based on the phosphite to be stabilised).
The
incorporation of the amine is carried out by dry milling or by dissolution in,
or mixing
with, the phosphite melt and subsequent crystallisation.
The isolated use of acid-binding metal salts as hydrolysis stabiliser for
phosphites has also
been disclosed (CA-A-2 097 674, US-A-5 208 362).
In spite of the known methods discussed above for enhancing the stability to
hydrolysis of
CA 02146203 2004-04-05
29276-355
2
organic phosphates and phosphonites there is still a need
for further improvement.
It has now been found that the combined addition
of amines and acid-binding metal salts surprisingly enhances
the stability to hydrolysis of organic phosphates and
phosphonites. Accordingly, the invention relates to a
composition comprising
(a) 25 to 99% by weight of an organic phosphate or
phosphonite,
(b) 0.01 to 50o by weight of organic amine, and
(c) 0.01 to 25o by weight of acid-binding metal salt, each
based on the total weight of the composition.
According to one aspect of the present invention,
there is provided a process for stabilising an organic
phosphate or phosphonite or a mixture of organic phosphates
or phosphonites against hydrolysis, which comprises adding
as stabiliser, (b) an organic amine and as stabiliser (c) an
acid-binding metal salt, so that the stabilized phosphate or
phosphonite comprises 0.01 to 50o by weight of the organic
amine component (b) and 0.01 to 25o by weight of the acid
binding metal salt (c), in each case based on the total
weight.
According to another aspect of the present
invention, there is provided a composition comprising
(a) 25 to 99o by weight of organic phosphate or phosphonite,
(b) 0.01 to 50o by weight of organic amine, and (c) 0.01 to
250 of acid-binding metal salt, each based on the total
weight of the composition, and wherein, besides components
(a), (b) and (c), the composition is free of organic
polymers as further components.
CA 02146203 2004-04-05
29276-355
2a
The phosphates and phosphonites stabilised
according to this invention are distinguished by their
excellent stability to hydrolysis and have good storage
stability even at high humidity.
A particularly interesting composition comprises
(a) 25 to 99o by weight of organic phosphate or phosphonite,
(b) 0.1 to 50o by weight of organic amine, and
(c) 0.5 to 25o by weight of acid-binding metal salt, each
based on the total weight of the composition.
The content of phosphate and/or phosphonite in the
stabilised composition is often 40 to 99o by weight,
preferably 70 to 99o by weight and, most preferably 80 to
99o by weight.
The organic phosphate or phosphonite stabilised
according to this invention usually contains 0.01 to 25o by
weight of component (b). The stabilised phosphate or
phosphonite preferably comprises an amine (component [b]) in
an amount of 0.01 to 20o by weight, preferably of 0.05 to
15o by weight and, most preferably, of 0.1 to loo by weight,
in each case based on the total weight of the composition.
Component (c) is usually in the novel composition
in an amount of 0.05 to 15o by weight, preferably of 0.1 to
10o by weight and, most preferably, of 0.1 to 5o by weight.
Accordingly, a preferred composition comprises 40
to 99o by weight of component (a), 0.01 to 25o by weight of
component (b) and 0.05 to 15o by weight of component (c), in
each case based on the total weight of the composition.
-3-
It is preferred that, in addition to components (a), (b) and (c) the novel
compositions do
not comprise organic polymers as further components, for example those having
a
molecular weight higher than 5000. Preferred compositions comprise, in
addition to
components (a), (b) and (c), no further main components, or possibly 1 or 2
further main
components which can also be used as stabilisers, e.g. as antioxidants, heat
stabilisers or
light stabilisers for synthetic polymers. Among these composition, those
compositions
which comprise no further main components are particularly preferred.
Further main components will be understood in this context as meaning those
additives
which are mixed with the novel composition and which constitute no impurities
such as
those resulting from the synthesis or from the storage or partial degradation
of one of
components (a) to (c).
Each of components (a) to (c) can be a single compound or a mixture of
compounds. In
the case of a compound mixture, the amounts stated indicate the total amount
of the
compounds used for each component.
Phosphites or organic phosphites are taken to mean compounds of formula
P(OR)3,
wherein the substitutents R are hydrocarbon radicals which may contain hetero
atoms, and
furthermore at most 2 of the 3 substitutents R may be hydrogen atoms. Hetero
atoms are
all atoms except carbon atoms and hydrogen atoms, preferably N, O, F, Si, P,
S, Cl, Br, Sn
and I.
Phosphonites are esters of phosphonous acid of formula P(OR)2R, wherein R has
the
meanings indicated above, or may be halogen.
The phosphite or phosphonite of component (a) is preferably a solid at
20°C and is usually
a crystalline solid.
The acid-binding metal salts used as component (c) in the novel compositions
are usually
carbonates, bicarbonates, carboxylates, oxides, hydroxides, phosphites,
borates or
corresponding mixed crystals, in particular of the metals lithium, sodium,
potassium,
copper, zinc, magnesium, calcium, strontium, barium, aluminium and/or
zirconium, as
well as hydrotalcites or zeolites. It is also possible to use several
different acid-binding
metal salts.
~1~~~~~~
-4-
Suitable acid-binding metal salts for use according to this invention are
naturally occuring
minerals as well as synthetically produced compounds. The metals can be
partially
interchanged. Said metals are crystalline, partially crystalline or amorphous,
or can be
obtained in the form of a dried gel.
The compounds of component {c) are expediently used in powdered form. The
crystallites
in the powder preferably have a high specific surface. Said high specific
surface can be
achieved by corresponding fine graining and/or a porous structure of the
crystallites, as is
the case e.g. with zeolites which may be used according to this invention.
Preferred acid-binding metal salts are those containing no or strongly
combined water of
crystallisation, such as compounds that do not release any water when heated
to 150°C, in
particular to 200°C, under normal pressure in the air.
Compounds of the series of the hydrotalcites can be represented by the general
formula IX
M2+1-R,M3+z~(OH)2'(A°-)x ' pH20
in (~)~
wherein
M2+ = Mg, Ca, Sr, Ba, Zn, Pb, Sn and/or Ni,
M3+ = Al, B or Bi,
A° is an anion of valency n,
n is a number from 1 to 4,
x is a number from 0 to 0.5,
p is a number from 0 to 2, and .
A = OH', CY, Br-,1-, C104 , HC03-, CH3C00-, C6HSC00-, CO32-, SO4z-,
00-
~00-, (CHOHCOO 2- CHOH CH OHCOO'. C H 2- 2-
)2 . ( )4 2 2 4(C00)2 , {CHZCOO)2 ,
CH3CHOHC00-, SiO32-, Si044-, Fe(CN)63-, Fe(CN)64-, 8033-, PO33- Or HP042-
Other hydrotalcites which may conveniently be used in the process described
above are
compounds of the general formula IXa,
MX+Al2(OH)2x+6nz(A° )2'PH20 {IXa),
~14~~0~
-5-
and M2+ in this formula IXa is at least one metal of the series consisting of
Mg and Zn,
preferably Mg; A°- is an anion, typically of the series consisting of
CO 2-, C ~00~ ,
3
OH- and S2-, and the anion has the valency n; p is a positive integer,
preferably from 0.5 to
5; and x and z are positive integers, x preferably being from 2 to 6 and z
being smaller
than 2.
Preferred compounds are those of the series of the hydrotalcites of the
general formula IX,
M2+1-~ ,Ms+x ~(0H)2 ~(A°-)x~ ~ pH20 ( )
° 1X
wherein M2+ is Ca, Mg or a solid solution of Mg and Zn; A°' is CO32-,
BO33- or PO33-; x is
a number from 0 to 0.5, and p is a number from 0 to 2. Of these metal salts,
those wherein
M3+ is an aluminium ion, are particularly preferred.
The use of basic hydrotalcites is preferred.
Very particularly preferred are hydrotalcites having the empirical formulae:
A1203-6Mg0-C02-12H20, (IXb)
MP,a.s~2(OHO3~C03-3.SH20, (IXc)
4MgO-A12O3~COZ~9HZO, (IXd)
4Mg0-A1203-C02-6H20, (IXe)
Zn0-3Mg0-A1203-C02-8-9H20 or (IXf)
Zn0-3Mg0-A1203-C02-5-6H20 . (IXg)
In the practice of this invention it is also possible to use zeolites of the
general formula (X)
M~°L(A102)R(SiO2)y~~WH2O (X),
2I4fi~(~~
-6-
wherein n is the charge of the cation M, and M is an element of the first or
second main
group, in particular Na, K, Mg and/or Ca,
y : x is a number from 0.8 to 1.2, and
w is a number from 0.5 to 10.
Basic zeolites are preferred.
Typical examples of suitable zeolites are compounds of the following empirical
formulae:
Nal2((AlO2)12(S1O2)12~' 12H20
Ca4.sNa3((~02y2(Si02)W30H20
KgNa3((A102)12(Si02)1~~27H20
Basic metal salts, for example basic hydrotalcites or zeolites, will be taken
to mean those
compounds which induce a pH higher than 7 in water.
The carbonates, bicarbonates, hydroxides, phosphites and borates for use
according to this
invention are preferably magnesium carbonate, zirconium carbonate and calcium
carbonate; sodium bicarbonate and potassium bicarbonate; magnesium hydroxide,
calcium
hydroxide, copper hydroxide, zinc hydroxide and aluminium hydroxide; secondary
and
tertiary sodium phosphite and potassium phosphite; and sodium borate and
calcium borate.
It is also possible to use metal oxides in the practice of this invention.
Oxides of divalent
metals are preferred. Particularly preferred oxides are those of the metals of
the second
main or subsidiary group, in particular zinc oxide, calcium oxide and
magnesium oxide.
Typical examples of metal carboxylates are the metal salts of saturated,
unsaturated or
hydroxylated aliphatic carboxylic acids. Particularly suitable are the salts
of
monocarboxylic acids of 6 to 20 carbon atoms, e.g. hexanoic acid, heptanoic
acid,
octanoic acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, myristic
acid, palmitic
acid, stearic acid, 12-oxystearic acid, oleic acid, linoleic acid or ricinolic
acid, as well as
the salts of dicarboxylic acids of 2 to 8 carbon atoms, such as oxalic acid,
malonic acid,
succinic acid, glutaric acid, adipic acid, pimelic acid, subaric acid, azelaic
acid, sebacic
acid, malefic acid, fumaric acid or tartaric acid. As salts of tricarboxylic
acid, citrates also
21462~~~
merit mention.
The metal salts of aromatic carboxylic acids, e.g. substituted benzoates or
phthalates, are
also of interest.
Metals of the series Ba, Sr, Ca, Mg and Zn are preferred. Preferred metal
carboxylates are
typically calcium stearate or zinc stearate and zinc oleate or calcium oleate.
The novel composition preferably comprises as amine (b) a sterically hindered
amine or
an amine of formula I
X'
(I),
X3~NwX2
wherein Xi and X2 are each independently of the other H, Cl-C2oalkyl, C4-
C2oalkyl which
is interrupted by -O- and optionally substituted by -OH, and wherein one or
more than one
ether group and, optionally, hydroxyl group, may be present, or are C2-
C2ohydroxyalkyl,
and X3 is C2-C2oalkyl, C4-C2oalkyl which is interrupted by -O- and optionally
substituted
by hydroxy, -(CH2)m NX1X2, or C2-C2ohydroxyalkyl; or wherein X2 arid X3 taken
together are C4-Cgalkylene, or C3-Cl2alkylene which is interrupted by -O- or -
NXl-, for
example -(CH2)m , -C2H4-O-C2H4- or -C2H4-NXl-C2H4-, wherein m is an integer
from 4
to 6, and X1 and X2 have the meanings indicated above; or an aromatic amine of
formula
Ia
4'
X
D
b
N~ ~ X 4 (Ia),
~D
X
wherein D is a nitrogen atom or a group -CXS-, and X4, X4~, X4~~ and XS are
each
independently of one another hydrogen or Cl-C4alkyl.
The sterically hindered amine is usually a cyclic sterically hindered amine,
more
particularly a compound of the series of the drivatives of
polyalkylpiperidines or
polyalkylpiperazines, comprising at least one group of formula II or III
_g_
CH3 G~
G-CH G2
- N (B)
G-CH2
CH3
CH3 G~
G-CH~,~ G2
- N~---~N
(III)
G-CH2
CH3
wherein G is hydrogen or methyl; and G1 and G2 are hydrogen, methyl or, taken
together,
are =O. The polyalkylpiperidine groups of formula II or III are preferably
bonded in
4-position to one or two polar substituents or to a polar spiro ring
system.
The use of a sterically hindered amine is preferred.
X1, XZ and X3 each embrace, inter alia, ethyl, propyl, butyl, pentyl, hexyl,
heptyl, octyl,
nonyl, decyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl,
hydroxyhexyl,
hydroxyheptyl, hydroxyoctyl, hydroxynonyl or hydroxydecyl.
X1, XZ and X3 are preferably identical.
The amine of formula I or Ia may typically be a tertiary amine, more
preferably a
tri-C2-C4alkanolamine such as triisopropanol amine {= amine A), or an aromatic
amine
such as trimethyltriazine, typically 1,3,5-trimethyl-2,4,6-triazine (= amine
Z), or also a
secondary amine such as dibutylamine, 2,2,6,6-tetramethylpiperidine (= amine
X), 4-
hydroxy-2,2,6,6-tetramethylpiperidine (H'TMP; = amine Y) or piperazine.
An important process is that wherein the amine is a tertiary amine of formula
I or Ia or a
cyclic sterically hindered amine containing at least one group of formula II
or III, wherein
G is hydrogen and G1 and G2 are hydrogen or, taken together, are a substituent
=O.
The use of derivatives of 2,2,6,6-tetramethylpiperidine in the novel process
is particularly
preferred.
2I~~~~~
-9-
The use of the classes of polyalkylpiperidines described hereinafter under (a)
to (h) and
carrying at least one group of formula II or III as indicated above, is of
particular interest:
(a) compounds of formula IV
GCH2 CHs G~
G "N O G ~2
(N),
GCH2 CH3 0
wherein n is a number from 1 to 4, G and G1 are each independently of the
other hydrogen
or methyl,
Gtt is hydrogen, oxyl, hydroxyl, C1-Clgalkyl, C3-Cgalkenyl, C3-Cgalkynyl, C~-
Cl2aralkyl,
C1-Ct8alkoxy, CS-Cgcycloalkoxy, C~-Cgphenylalkoxy, C1-Cgalkanoyl, C3-
Csalkenoyl,
C1-Clsalkanoyloxy, benzyloxy, glycidyl or a group -CH2CH(OH)-Z, wherein Z is
hydrogen, methyl or phenyl, and G11 is preferably H, C1-C4alkyl, allyl,
benzyl, acetyl or
acryloyl, and
G12, if n = l, is hydrogen, Ct-Ctgalkyl which may be interrupted by one or
more than one
oxygen atom, cyanoethyl, benzyl, glycidyl, a monovalent radical of an
aliphatic,
cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid,
carbaminic acid or
phosphorus-containing acid, or a monovalent silyl radical, preferably a
radical of an
aliphatic carboxylic acid of 2 to 18 carbon atoms, of a cycloaliphatic
carboxylic acid of 7
to 15 carbon atoms, of a a,Li-unsaturated carboxylic acid of 3 to 5 carbon
atoms, or of an
aromatic carboxylic acid of 7 to 15 carbon atoms, and the carboxylic acid may
be in each
case substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3
groups
-COOZ12, wherein Z12 is H, C1-CZOalkyl, C3-Cl2alkenyl, CS-C~cycloalkyl, phenyl
or
benzyl,
if n = 2, is C2-Cl2alkylene, C4-Cl2alkenylene, xylylene, a divalent radical of
an aliphatic,
cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or
phosphorus-containing acid, or a divalent silyl radical, preferably a radical
of an aliphatic
dicarboxylic acid of 2 to 36 carbon atoms, of a cycloaliphatic or aromatic
dicarboxylic
acid of 8 to 14 carbon atoms or of an aliphatic, cycloaliphadc or aromatic
dicarbamic acid
of 8 to 14 carbon atoms, and the dicarboxylic acid may be in each case
substituted in the
aliphatic, cycloaliphatic or aromatic moiety by 1 or 2 groups -COOZ12,
if n = 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic
tricarboxylic acid,
which radical can be substituted in the aliphatic, cycloaliphatic or aromatic
moiety by
- 10-
-COOZ12, or is a trivalent radical of an aromatic tricarbamic acid or of a
phosphorus-
containing acid, or is a trivalent sylil radical, and
if n = 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic
tetracarboxylic
acid.
The indicated carboxylic acid radicals in each case comprise radicals of
formula (-CO)nR,
in which the meaning of n is as indicated above and the meaning of R follows
from the
given definition.
C1-Cl2Alky1 substituents are typically methyl, ethyl, n-propyl, n-butyl, sec-
butyl,
tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-
dodecyl.
G11 or G12 defined as C1-Clgalkyl may typically be the groups indicated above
and, in
addition, e.g. n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
G1 l defined as C3-Cgalkenyl may be, for example, 1-propenyl, allyl,
methallyl, 2-butenyl,
2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.
Gll defined as C3-Cgalkynyl is preferably propargyl.
Gll defined as C~-Cl2aralkyl is preferably phenethyl, more particularly
benzyl.
Gll defined as Cl-Cgalkanoyl is typically formyl, propionyl, butyryl,
octanoyl, but
preferably acetyl and, as C3-Csalkenoyl, is preferably acryloyl.
G12 defined as a monovalent radical of a carboxylic acid is typically the
radical of acetic
acid, hexanoic acid, stearic acid, acrylic acid, methacrylic acid, benzoic
acid or
13(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid.
G12 defined as a monovalent silyl radical is typically a radical of formula
-(C~H2~)-Si(Z')2Z", wherein j is an integer from 2 to 5, and Z' and Z" are
each
independently of the other C1-C4alkyl or Ci-C4alkoxy.
G12 defined as a divalent radical of a dicarboxylic acid is typically the
radical of malonic
acid, succinic acid, glutaric acid, adipic acid, subaric acid, sebacic acid,
malefic acid,
itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid,
butyl(3,5-di-tert-
butyl-4-hydroxybenzyl)malonic acid or bicycloheptenedicarboxylic acid.
G12 defined as a trivalent radical of a tricarboxylic acid is typically the
radical of
21~62Q~
-11-
trimellitic acid, citric acid or nitrilotriacetic acid.
G12 defined as a tetravalent radical of a tetracarboxylic acid is typically
the tetravalent
radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
G12 defined as a divalent radical of a dicarbamic acid is typically a
hexamethylene-
dicarbamic acid radical or a 2,4-toluylenedicarbamic acid radical.
Preferred compounds are those of formula IV, wherein G is hydrogen, G11 is
hydrogen or
methyl, n is 2, and G12 is the diacyl radical of an aliphatic dicarboxylic
acid of 4 to 12
carbon atoms.
Illustrative examples of polyalkylpiperidine compounds of this class are:
1 ) 4-hydroxy-2,2,6,6-tetramethylpiperidine
2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine
5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
7} 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
8) 1,2,2,6,6-pentamethylpiperidine-4-yl-li(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate
9) bis(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleinate
10) bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate
11) bis(2,2,6,6-tetramethylpiperidin-4-yl)glutarate
12) bis(2,2,6,6-tetramethylpiperidiri-4-yl)adipate
13) bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate
14) bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate
15) bis(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)sebacate
16) bis(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate
17) 1-hydroxy-4-Li-cyanoethyloxy-2,2,6,6-tetramethylpiperidine
18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate
19} the tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of trimellitic acid
20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
21) the bis(2,2,6,6-tetramethylpiperidin-4-yl) ester of diethylmalonic acid
22) the bis(1,2,2,6,6-pentamethylpiperidin-4-yl) ester of dibutylmalonic acid
21~6~~~
- 12-
23) the bis(1,2,2,6,6-pentamethylpiperidin-4-yl) ester of butyl(3,5-di-tert-
butyl-4-hydroxy-
benzyl)malonic acid
24) bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
25) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate
26) hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethyl-piperidine)
27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethyl-
piperidine)
28) dimethyl-bis(2,2,6,6-tetramethylpiperidin-4-oxy)silane
29} phenyl-tris(2,2,6,6-tetramethylpiperidin-4-oxy)silane
30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphite
31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)phosphate
32) phenyl-[bis(1,2,2,6,6-pentamethylpiperidin-4-yl)]phosphonate
33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine
34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
35) 4-hydroxy-N(2-hydroxypropyl}-2,2,6,6-tetramethylpiperidine
36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
(b) compounds of formula (V)
Gas
GCH2 CH3 G' I
G"N N G'4 (V),
GCH2 NCH
3
wherein n is 1 or 2, and G, Gt and Gll have the meaning given in (a),
Gi3 is hydrogen, C1-Cl2alkyl, C2-CShydroxyalkyl, CS-C?cycloalkyl, C~-
Cgaralkyl,
C2-Clgalkanoyl, C3-Csalkenoyl, benzoyl or a group of formula
GCH2 CH3 G'
G» N
GCH2 CH3
and
G14, if n = 1, is hydrogen, C1-Clgalkyl, C3-Cgalkenyl, CS-C~cycloalkyl; C1-
C4alkyl which
2~.452~~
-13-
is substituted by a hydroxy, cyano, alkoxycarbonyl or carbamide group;
glycidyl; a group
of formula -CHZ-CH(OH)-Z or of formula -CONH-Z, wherein Z is hydrogen, methyl
or
phenyl;
if n = 2, is CZ-Cl2alkylene, C6-Cl2arylene, xylylene, a -CH2-CH(OH)-CH2- group
or a
group -CHZ-CH(OH)-CH2-O-D-O-, wherein D is CZ-Cloalkylene, C6-Clsarylene,
C6-Cl2cycloalkylene; or, provided that G13 is not alkanoyl, alkenoyl or
benzoyl, G14 may
also be 1-oxo-C2-Cl2alkylene, a divalent radical of an aliphatic,
cycloaliphatic or aromatic
dicarboxylic acid or dicarbamic acid, or also the group -CO-; or
if n = 1, G13 and G14, taken together, may be the divalent radical of an
aliphatic,
cycloaliphatic or aromatic 1,2-dicarboxylic acid or 1,3-dicarboxylic acid.
C1-Cl2Alky1 subsdtuents or C1-Clgalkyl substituents have the meaning indicated
under
(a).
CS-C~Cycloalkyl substituents are preferably cyclohexyl.
G13 defined as C~-Cgaralkyl is preferably phenylethyl or, more particularly,
benzyl. G13
defined as C2-Cshydroxyalkyl is preferably 2-hydroxyethyl or 2-hydroxypropyl.
G13 defined as C2-Clgalkanoyl is typically propionyl, butyryl, octanoyl,
dodecanoyl,
hexadecanoyl, octadecanoyl, but preferably acetyl and, as C3-Csalkenoyl, is
preferably
acryloyl.
G14 defined as C2-Cgalkenyl is typically allyl, methallyl, 2-butenyl, 2-
pentenyl, 2-hexenyl
or 2-octenyl.
G14 defined as C1-C4alkyl which is substituted by a hydroxy, cyano,
alkoxycarbonyl or
carbamide group may typically be 2-hydroxyethyl, 2-hydroxypropyl, 2-
cyanoethyl,
methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or
2-(dimethylaminocarbonyl)ethyl.
C2-Cl2Alkylene substituents are typically ethylene, propylene, 2,2-
dimethylpropylene,
tetramethylene, hexamethylene, octamethylene, decamethylene or
dodecamethylene.
C6-CiSArylene substituents are typically o-, m- or p-phenylene, 1,4-
naphthylene or
4,4'-diphenylene.
21~'~203
- 14-
C6-Cl2Cycloalkylene is preferably cyclohexylene.
Preferred compounds are those of formula V, wherein n is 1 or 2, G is
hydrogen, Gl l is
hydrogen or methyl, G13 is hydrogen, C1-Cl2alkyl or a group of formula
GCH2 CH3 G t
G» N
GCH2 CH3
and, if n = 1, G14 is hydrogen or Cl-Cl2alkyl and, if n = 2, is C2-Cgalkylene
or
1-oxo-C2-Cgalkylene. '
Illustrative examples of polyalkylpiperidine compounds of this class are:
37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diamine
38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacetamide
39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine
40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine
41) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipamide
42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-
hydroxypropylene-
1,3-diamine
43) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine
44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)succindiamide
45) the bis(2,2,6,6-tetramethylpiperidin-4-yl) ester of N-(2,2,6,6-
tetramethylpiperidin-
4-yl)-13-aminodipropionic acid
46) the compound of formula
21~~2~3
-15-
CH3 CH3 i aHs
CH3 - N~ N - CH2 CH(OH)- CH2 O
CH3 CH3
CH3-C-CH3
CH3 CH3 /
CH3 - N~ N - CH2 CH(OH)- CH2- O
I
CH3 CH3 C4H9
47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine
48) 4-(3-methyl-4-hydroxy-5-tert-butylbenzoic acid amido)-2,2,6,6-
tetramethylpiperidine
49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine
(c) compounds of formula (VI)
GCH2 CH3 G'
O
G > > N/~~ G ~ s
(VI),
GCH2 CH3 O
n
wherein n is 1 or 2, and G, Gl and Gil have the meaning indicated under (a),
and Gls, if n
= 1, is CZ-Cgalkylene, C2-Cghydroxyalkylene or C4-C22acyloxyalkylene; if n =
2, is the
group (-CH2)2C(CHZ-)2~
Gls defined as C2-Cgalkylene or C2-Cghydroxyalkylene is typically ethylene,
1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-
hydroxymethylpropylene.
G15 defined as C4-C22acyloxyalkylene is typically 2-ethyl-2-
acetoxymethylpropylene.
Illustrative examples of polyalkylpiperidine compounds of this class are:
50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
-
- 16-
51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane
52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane
53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-
dioxaspiro[5.5]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-
dioxaspiro[5.5]-
undecane
SS) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-
(1",3"-dioxane)-
2"-spiro-4"'-(2"',2"',6"',6"'-tetramethylpiperidine);
(d) compounds of formulae VIIA, VIIB and VIIC, preferably compounds of formula
VBC,
~G ~s
GCH2 CH3 G
N-C=O
G'-' ~ ( (VIIA),
C-N G"
GCH2 CH3 II
O n
GCH2 CH3 G'
O-C-T2
G "N~~ I (VIIB),
N-C=O
GCH2 CH3 H
GCH2 CH3 G'
O-C-T2
G1'N C-N G1' (VIIC),
GCH2 CH3 ~~
O n
wherein n is 1 or 2, and G, G1 and G11 have the meaning indicated in (a},
G16 is hydrogen, C1-Cl2alkyl, allyl, benzyl, glycidyl or CZ-C6alkoxyalkyl, and
Gl', if
n = l, is hydrogen, C1-Cl2alkyl, C3-CSalkenyl, C~-C9aralkyl, CS-C~cycloalkyl,
C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-Clcaryl, glycidyl, or a group of
formula
-(CH2)p-COO-Q or of formula -(CH2)p-O-CO-Q, wherein p is 1 or 2, and Q is Ci-
C4alkyl
or phenyl; if n = 2, is CZ-Cl2alkylene, C4-Cl2alkenylene, C6-Cl2arylene, a
group
-CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2-, wherein D is C2-Cloalkylene,
C6-Clsarylene, C6-Cl2cycloalkylene, or a group
-CH2CH(OZ')CHZ-(OCHZ-CH(OZ.')CHZ)2- , wherein Z' is hydrogen, C1-Cl8alkyl,
allyl,
benzyl, C2-C l2alkanoyl or benzoyl,
2.4620
17-
T1 and T2 are each independently of the other hydrogen, C1-Clgalkyl or C6-
Cloaryl or
C~-C9aralkyl each of which may be substituted by halogen or C1-C4alkyl, or T1
and T2,
together with the linking carbon atom, form a CS-Cl4cycloalkane ring.
Substituents C1-Cl2alkyl are typically methyl, ethyl, n-propyl, n-butyl, sec-
butyl,
tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-
dodecyl.
Substituents defined as C1-Clgalkyl may typically be the groups indicated
above and also
e.g. n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Substituents C2-C6alkoxyalkyl are typically methoxymethyl, ethoxymethyl,
propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl,
tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
G1' defined as C3-Csalkenyl is typically 1-propenyl, allyl, methallyl, 2-
butenyl or
2-pentenyl.
Gl~, Tl and T2 defined as C~-C9aralkyl are preferably phenethyl or, more
particularly,
benzyl. If Tl and T2, together with the carbon atom, form a cycloalkane ring,
then said
ring may typically be a cyclopentane, cyclohexane, cyclooctane or
cyclododecane ring.
Gl~ defined as C2-C4hydroxyalkyl is typically 2-hydroxyethyl, 2-hydroxypropyl,
2-hydroxybutyl or 4-hydroxybutyl.
G1', Ti and T2 defined as C6-Cloatyl is preferably phenyl, a- or Li-naphthyl,
each of which
may be substituted by halogen or C1-C4alkyl.
Gl~ defined as C2-Cl2alkylene is typically ethylene, propylene, 2,2-
dimethylpropylene,
tetramethylene, hexamethylene, octamethylene, decamethylene or
dodecamethylene.
G1' defined as C4-Cl2alkenylene is preferably 2-butenylene, 2-pentenylene or
3-hexenylene.
Gig defined as C6-Cl2arylene is typically o-, m- or p-phenylene, 1,4-
naphthylene or
4,4'-diphenylene.
21~62(l~
-1g -
Z' defined as C2-Cl2alkanoyl is typically propionyl, butyryl, octanoyl,
dodecanoyl, but is
preferably acetyl.
D defined as C2-Cloalkylene, C6-Clsarylene or C6-Cl2cycloalkylene is as
defined under
(b).
Illustrative examples of polyalkylpiperidine compounds of this class are:
56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione
59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione
60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione
61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4.5]decane
62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4.5]decane
63) 2,2,4,4-tetramethyl-7-oxa-3,20=diaza-21-oxo-dispiro[5.1.11.2]heneicosane
64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro-[4.5]decane
and, preferably:
65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5] decane-2,4-
dione
or the compounds of the following formulae:
- 19-
M
U
Z I Z U Z U
U Z U
M \= Z
U U U
U
U =O U O
I = Z
U -Z U
O I U I U U -Z
N z II
O
U ~M
M Z
O U U
Z
U = U
Z
U N
O
U-Z. U
oI
N
t0
N
V
O ~ O = O
N V N N
U U -Z U
U -Z U ~ ~U
O I N N N
U U U
U -Z
U =O Z Z
Z U =O
Z U =O = = O U =O
U U
U U ~ (~ U
Z
M Z M U
I Z Z U ~ U
U I U Z I Z
Z Z U Z U Z
U U J
N
-20-
(e) compounds of formula VIII, which are likewise preferred,
G'8
N' \ N
(VIII),
Gi N
n
wherein n is 1 or 2, and G1g is a group of one of formula
G~CH CH3 CH2G G2 G~ CH3 CH2G
» »
-E- (A)X CH N-G or -E- (A~N~-G
~CH2G ~~CH~3 CH2G
3
wherein G and Gll are as defined in (a), and Gl and G2 are hydrogen, methyl
or, taken
together, are a substituent =O ,
E is -O- or -NG13-, A is C2-C6alkylene or -(CH2)3-O-, and x is either O or 1,
G13 is hydrogen, Cl-Cl2alkyl, C2-Cshydroxyalkyl or CS-C~cycloalkyl,
G19 is identical to Glg or is one of the groups -NG21G22, -OG23, -NHCH20G23 or
-N(CH2OG23)2,
G2°, if n = 1, is identical to G1g or G19, and, if n = 2, is a group -E-
B-E-, wherein B is
C2-Cg alkylene or C2-Cgalkylene which is interrupted by 1 or 2 groups -
N(G2i)_,
G21 is Ci-Cl2alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl, or a group of
formula
GCH2 CH3 G
Gig N
GCH2 CH3
G22 is C1-C12-alkyl, cyclohexyl, benzyl, C1-C4-hydroxyalkyl, and G23 is
hydrogen,
C1-Cl2alkyl or phenyl, or G21 and G22, taken together, are C4-Csalkylene or
21!~62~
-21-
-CH2CH2
C4-Csoxaalkylene, typically
/'
-CH2CH2
-CH2CH2
or a group of formula N-G"
-CH2CH2
or G21 is a group of formula
HsC CHs
C4H9 N
G~~N N
N' /N
HsC CH ~3
C4H9 - N
H3C ~ CH3
H3C N CH3
G"
C1-Cl2Alky1 substituents are typically methyl, ethyl, n-propyl, n-butyl, sec-
butyl,
tent-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-
dodecyl.
C1-C4Hydroxyalkyl substituents are typically 2-hydroxyethyl, 2-hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
A defined as C2-C6alkylene is typically ethylene, propylene, 2,2-
dimethylpropylene,
tetramethylene or hexamethylene.
G21 and G22 together defined as C4-CSalkylene or oxaalkylene are typically
tetramethylene, pentamethylene or 3-oxapentamethylene.
Illustrative examples of polyalkylpiperidine compounds of this class are
compounds of the
following formulae:
~~~s~o~
-22-
CH3
H3C N CH3
H3C ~CH3
70) N - Calls
N' ' N
(CH3CH2)2N N N(CH2CH3)2
aHs)2
H3C CH3 H3C CH3
N~ N
71) C2Hs -N N-~NJ-N N-C2H5
C2Hs C2Hs
HsC CHs HsC CHs
R H3C CH3
72) N ~N wherein R = -NH-CH2CH2CH2-O N - CH3
'N' \ H C CH
R R 3 3
H3C CH3
CH2 CH2 NH
NH H3C CH3
73) H3C CH
s N ~ N HsC CHa
HN CH2- CH2 NH~ N J- NH- CH2- CH2 NH
HsC \CH3 H3C ~CH3
2146~~~
-23-
H3C CH3 H3C CH3
Calls N N Calls
HN N -~ ~NHCH2CH2N-CH2CH2NH~ ~~ N NH
H3C CH3 N Y N . N Y N H3C CH3
HsCa - N N ~ N N - Calls
HsC N~ CHs N HsC ' \CH3
74) H3C H CH3 H3C H CH3
HsCa ' /Calls
N N
H C CH3 H3C CH3
3
H C N . CH3 H3C H CH3
s H
R R
75) R-NH-(CH2)g-N-(CH2)2-~-(CH2)3-NH-R
HsC CHs
N iaHs
wherein R = ~ ~ N NH
NYN
H3C CH3
Calls - N
H3C I 'CH3
H3C H CH3
R R
76) R-NH-(CH2)3-N-(CH2)2-~-(CH2)3-NH-R (amine J)
21462fl3
-24-
HsC CHs
Calls
N ~ \
wherein R = ~ ~ N N - CH3
N \ 'N
H3C CH3
Calls _ N
H3C I 'CH3
H3C i CH3
CH3
CH3 R R CHs
77) R-NvCH2)3-N'C~"'~2)2-N'~CH2)3-~-R
HsC CHs
N ~aHs
wherein R = ~ ~ N N - CH3
N'\ 'N
H3C CH3
C4Hs - N
H3C CH3
H3C i CH3
CH3
C8H» -N
C8H» -N N 3 3
7g) C8H» -N~N~NH CH
2)3-
H3C ~ CH3
H3C H CH3
HsC CHs
NH
H C CH
21~~203
-25-
CH2CH20H
H3C N CH3
H3C ~CH3
79) N - Calls
~ H3C
H C CH N' \ N CH
3 3 ~ 3
HO-CH2CH2-N N N N N-CH2CH2 OH
1 I
H3C CH3 Calls Calls H3C CH3
CH2-CH=CH2
H3C N CH3
H3C ~CH3
(80) N - C4Hs
H C CH N' 'N H C
3 3 ~ g CHg
H2C=HC-H2C-N N N ~ N N-CH -CH=CH
I I 2 2
HsC CHs Calls Calls H3C CH3
(f) oligomeric or polymeric compounds, whose structural repeating unit
contains a
2,2,6,6-tetraalkylpiperidine radical of formula III, preferably polyesters,
polyethers,
polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines,
poly(meth)acrylates, poly(meth)acrylamides and the copolymers thereof
containing such
radicals.
Typical examples of 2,2,6,6-polyalkylpiperidine light stabilisers of this
class are the
compounds of the following formulae, wherein m is a number from 2 to c. 200.
~~~~20~
-26-
CH3 CH3
O O
II 11
(g1) C-CH2-CH2 C-O-CH2-CH2-N O
CH3 ~CH3 m
82)
CH3 CH3 O O CH3 CH3 O O
II II
CH2 CH2- N O- C - (CH2)4 C - O N - CH2- CH2 O - C - (CH2)4 C
CH3 CH3 CH3 CH3 m
83)
CH3 C2Hs O O CH3 C2Hs O O
NH- (CH2)3- N NH- C ~ C - NH N - (CH2)3 NH- CI ~ C)
~~~CH3 ~ ~ CH3 ~ ~ m
CH3 C2Hs CH3 \C2Hs
CH3 CH3
NH-C-CH2 C-CH3
CH3 CH3
N ~ N N (CH2)s N
(84)
J
\N CH3 CH3 CH3 CH3 m
CH3 NH~CH3 CH3 NH~CH3
N CH2 CH(OH)-CH2
m
(85) CH3 CH3
CH3 NH CH3
21~~2~~~
-27-
CH3 CH3 CH3 CH3 i~ ~ aHs
(g6) O N-CH2 CH=CH-CH2-N~O-C- ~ C
J m
CH3 CH3 ~ CH3 CH3 C4H9
N
I N (CH2)s N
N,,N,N m
I CH3 1 'CH3 CH3 1 'CH3
(87) N_CaH ~ 'Y\s
CH3 H CH3 CH3 H CH3
CH3 1 .CH3
CH3 H CH3
CH3 CH3 CH3 CH3 O O
$$ O N-CH ~ ~ CH -N O-CI - CH -
( ) 2 2 ~ ( 2)4
m
CH3 CH3 ~ CH3 CH3
CH3 CH3
~2Hs O
C-C-C-O-CH2-CH2 N O~-
I m
C2Hs
CH3 CH3
CH3
90) -~- C - CH2--~-m
CH3 CH3
O=C
I \
O N-CH3
CH3 CH3
-28-
CH3
91) ~C-CH2~m
O=C H3C CH3
C6H~3-N N-CH3
H3C ~CH3
O
C~
N
N~N
92) ~ N ~ N (CH2)s N -m
H3C ~CH3 H3C 1 CH3
H3C N CH3 H3C N xCH3
H H
-~-- N -(CH2)s N - CH2-CH2-~-
m
93) H3C ~CH3 H3C ~CH3
H3C N ~'CCH3 H3C N J~CCH3
H H
O O
i1 II
--~ N -(CH2)6 N C - CH2 C -~
m
94) CH3 1 _CH3 CH3 1_CH3
CH3 H CH3 CH3 H CH3
R R
95) N -(CH2)2 N -(CH2)2 m
-29-
HsC CHs
N ~4H9
wherein R = ~ ~ N N - H or is a
N \ 'N
H3C CH3
CQH9 - N
H3C ~ CH3
H3C i CH3
H
R
branching of the chain _(CH2)2- N~ ; m' and m" are each an integer from
m
0 to 200, with the proviso that m' + m" = m.
Further illustrative examples of polymeric light stabilisers are reaction
products of
compounds of formula
CH3 CH3 CH2 -(CH~9
I I
O-C-CH2
HN~ I
?~ 'C-NH
CH3 CH3 I
O
with epichlorohydrin;
polyester of butane-1,2,3,4-tetracarboxylic acid with a bifunctional alcohol
of formula
HO\ C ~ 3 ~ -CH\ ~ 2 ; C i 3 OH
CH2 C--CH C CH-C-CH~
CH3 O-CH2 Ii2 O
whose carboxyl side chains deriving from the tetracarboxylic acid are
esterified with
2,2,6,6-tetramethyl-4-hydroxy-piperidine;
CH3
H2 ~C -CH2- CH
compounds of formula O - ~ O - ~ , wherein about one third of the
I
OCH3 OR m
21~~~0
-30-
H3C CHs
radicals R are -C2H5 and the others are , and m is a number from 2 to
N-H
H3C CH3
200; or
copolymers, whose structural repeating unit is composed of 2 units of
CH ' O ~ O
3 O-_y0 N
C = CH2 and 1 unit each of N and
C H CH3 CH3
13 27
CH3 NH CH3
(g) Compounds of formula IX
GCH2 CHs G1
G 1' N O (~)~
GCH2 ~CH3
wherein G, Gl and Gll are as defined under (a).
Preferred compounds are those of formula IX, wherein G is hydrogen or methyl,
and Gl1
is hydrogen or methyl.
Illustrative examples of such compounds are:
96) 2,2,6,6-tetramethyl-4-piperidone (triacetonamine)
97) 1,2,2,6,6-pentamethyl-4-piperidone
98) 2,2,6,6-tetramethyl-4-piperidon-1-oxyl
99) 2,3,6-trimethyl-2,6-diethyl-4-piperidone
(h) Compounds of formula X
2~.~~20
-31-
GCH2 CH3 O
G~i ~ G~a
GCH2 CH3
wherein n is 1 or 2, and G and G11 are as defined under (a), and G14 is as
defined under
(b), and Gi4 cannot have the meanings -CONH-Z and -CH.,-CH(OH)-CH2-O-D-O-.
Typical examples of such compounds are:
~CH3
CH3 \1 CH3 O
CH 2 N N - H
100) H = N N -CH2 ~~'~ (amine M)
O CH3 CH3
CH3
~CH3
CH3 \~~O
101) ''/~'~/ cH2 /~~-cH3
CH3 - N N -CH2
O CH3 CH3
CH3
CH3 \~~O
102) CHs - N N -CH2 ~ ~ .
CH3
The following amines are particularly preferred for use in the novel process:
Compounds of formula IV, wherein n is an integer from 1 to 4, G and Gl are
hydrogen,
and
G11 is hydrogen or C1-C1g-alkyl, and
G12, if n = 1, is a radical of formula -(C~H2~)-Si(Z')2Z", wherein j is an
integer from 2 to 5,
and Z' and Z" are each independently of the other C1-Caalkyl or C1-C4alkoxy,
and
G12, if n = 2, is a radical of an aliphatic dicarboxylic acid of 2 to 12
carbon atoms, which
radical may be substituted by -COOZ12, wherein Z12 is Cl-C2oalkyl,
G12, if n = 3, is a radical of an aromatic tricarboxylic acid of 9 to 15
carbon atoms,
G12, if n = 4, is a radical of an aliphatic tetracarboxylic acid of 8 to 12
carbon atoms;
2~.~~~Q~
-32-
particularly interesting amines of this class are those of formulae
CH3
CH3
CH3
i
HN O -(CH2)3- Si- OC2H5
(amine B),
CH3 OC2H5
CH3
CH CH3 CH3 CH
3 Q ~ 3
HN O - C -(CH2)$ C - O NH
(amine C),
CH3 ' CH3
CH3 CH3
CH CH3 CH3 CH
3 ~ ~ 3
CH3 - N O - C -(CH2)8- C - O N - CH3
(amine D),
CH3 'CH3
CH3 CH3
CHCH3 CH3
CH3
H H
CH3 - ~~~0 O N - CH3
CH3
CH O~ O~ CH3
3 CH3
CH CHz~H -CH -CHz (amlIle E),
CH 3 O ~ O ~ CH3
_ O O ~Ha
CH3 N H H N-CH3
CH3~"'~ CH
CH3 CH3 3
as well as esters of butane-1,2,3,4-tetracarboxylic acid containing 2 units
each of
1,2,2,6,6-pentamethyl-4-hydroxypiperidine and C13H2~-OH (amine F);
compounds of formula V, wherein n = 2, G and Gl are hydrogen,
Gl l is hydrogen or methyl, and
G13 is hydrogen or Cl-Cgalkyl, and
G14 is C2-Cgalkylene or 1-oxo-C2-Cgalkylene; a particularly interesting amine
of this class
21~62~~
-33-
CH3 CH3
CH
CH3 0 CH3
I ~i \
is the compound of formula HN N - C - C - NH NH
CH3 CH3 CH3
CH3 CH3
(amine G);
compounds of formula VIIC, wherein n = l, G, Gl and Gl~ are hydrogen,
Gll is hydrogen or methyl, and
Tl and T2, together with the linking nitrogen atom, form a CS-Cl4cycloalkane
ring; a
particularly interesting amine of this class is the compound of formula
CH CH3 O
NH
HN CH2~ (amine II);
CH3 O CH2)s
CH3 CH2
compounds of formula VIII, wherein n is 1 or 2,
G1g and G19 are a group of one of formula
CH3 CH3 G2 G' CH3 CH3
-E- CH N - G " ~ G"
or - E - (A~ N
CH3 CH3 CH3 CH3
G11 is hydrogen or methyl,
Gl and G2 are hydrogen or, taken together, are a substituent =O,
E is -O- or -NG13- , A is CZ-C6alkylene, and x is either 0 or l,
G13 is hydrogen, C1-Cl2alkyl or cyclohexyl,
G2°, if n = 1, has the meaning of Glg and, if n = 2, is a group -E-B-E-
, wherein B is
C2-Cgalkylene, or CZ-Cgalkylene which is interrupted by 1 or 2 groups -
N(G2i)_,
G21 is C1-Cl2alkyl, cyclohexyl, benzyl or C1-C4hydroxyalkyl, or a group of
formula
- ~14~~~~
-34-
GCH2 CH3 G
G~i N
GCH2 CH3
or G21 is a group of formula
HaC CHs
C4H9 N
G~~N N
N' / N
HsC CH ~3
C4H9 - N
H3C ~ CH3
H3C N CH3
G"
particularly interesting amines of this class are the compound (76)[ = amine
J] described
above and the compounds of formulae
CH3 CH3
CH3 CH3 O CH3 ~ ~~O
~1/N
HN~
~ 'N, CH3 ~N~CHZ
CH3 CH3 / H2 CH3 CH2
CHZ ~N ~ N
N' \ N N '_N
J~ J~ ~ ~d ~ J~
N N~ N N N N
CH ~ CH2 CHZ ~ CH CH2 . CH2 CH2 ~ CH2
O O N N O
~CH CH CH3 ~ CHa CH3 ~ CH3
CH3 NH -CH 3 3 ~N CH3 CH N CH3 CH3 N CH
CH3 3 CH3 CH3 3 CH CH
3 3
(amines K and L);
compounds of formula X, wherein n is 2, G11 is hydrogen or methyl, and G14 is
CrC i2~Ylene;
a particularly interesting amine of this class is the compound ( 100) [= amine
M] described
2~4~2~~
-35-
above, as well as
the oligomeric compounds having 2 to 10 structural repeating units obtainable
by reaction
CH3 CH3
24
(i) of G - N O - H ~ ""herein G24 is C2-Cshydroxyalkyl, with an aliphatic
CH3 CH3
C2-Cl2dicarboxylic acid or a suitable reactive derivative such as the diester,
the dichloride
or the anhydride;
(j) of a linear oligomeric polyester of a diol and butane-1,2,3,4-
tetracarboxylic acid with
2,2,6,6-tetramethyl-4-hydroxy-piperidine;
CH3 NH CH3 CH3 NH CH3 CI % CI
CH3 CH3 CH3 CH ~ . .
3
(k) of with ~ N , wherein A is
HN A NH T3iN~T
C2-C6alkylene, T3 is C1-Clgalkyl or cyclohexyl, T~ is hydrogen or C1-Clgalkyl,
or T3 and
T4, taken together, are C4-C6alkylene or C3-Csoxaalkylene;
CI
CH3 CH3 ~ CH3 CH3
HN N ~ N NH
(1) of H2N-A-NH-A-NH2 withCH3 ~ N ~ CH3 and
N N a \
CH3 ( ~ CH3
C4Hs C4Hs
Br-A-Br, wherein A is C2-C6alkylene;
CH3 CH3 CH i -(CH2)s
O-C-CH2
(m} of compounds of formula H ~C - NH ~'i~ epichlorohydrin;
CH3 CH3 II
O
O ~O
CH3 O~O N
(n) of ~ ~ C = CH2 with N and ,
C H CH3 CH3
13 27
CH3 NH CH3
as well as oligomeric compounds of formula
36
CH3
I
CH2 C -CH2- CH
(o) I I , wherein about one third of the radicals R are -C2H5 and
O=C O=C
I i
OCH3 OR m
HsC CHs
the others are , and m is a number from 2 to 10;
N-H
H3C CH3
particularly interesting oligomeric amines are those of formulae (m again is a
number
CH3
CH3 O O
.. ,.
from 2 to 10) H - O N -CH2-CH2- O - C CH2-CH2 C O - CH3 (CAS-No.
CH CH3 m
3
65447-77-0; amine N);
CH3 NH CH3 CH3 HN CH3 CH3 NH CH3 CH3 NH CH3
CH3 CH3CH3 CH3 CH3 CH3CH3 CH3
HN ~CHZ)s N 1 / ~ N ~CHZ)~ N H
N ' _N
iY I Ha f Ha
HN- j -CHI j -CH3
CH3 CH3 m
(CAS-No. 70624-18-9; amine P);
CH3 NH CH3 CH3 HN CH3 CH3 NH CH3 CH3 CH3
CH3 CH3CH3 CH3 CH3 CH3CH3 NH CH3
HN (CHZ)~- N / ~ N (CH2)~- N H
NYN
N
m
0
~~.4G2~~
-37-
CH3
I
H2- C -CH2- CH
(amine Q); I I (amine R), wherein about one third of the
O=C O=C
i i
OCH3 OR m
H3C CH3
radicals R are -C2H5 and the others are ; a linear polyester having 2 to
N-H
H3C CH3
structural repeating units of butane-1,2,3,4-tetracarboxylic acid and a diol
of formula
HO\ C ~ 3 ~ -CH\ ~ 2 \ C i 3 OH
CH2 C -CH C CH - C -CH2 , wherein the end groups and the side-chains
CH3 O-CHZ Fi2 O CH3
are formed by esterification of the free carboxyl groups with 2,2,6,6-
tetramethyl-
4-hydroxy-piperidine (amine S); a copolymer, whose structural repeating unit
is composed
CH3 O ~ O
of 2 units ~ ~ C = CH2 and 1 unit each of N and
C13H27
O ~O
N
(amine T); the reaction product of H2N-(CH2)2-NH-(CH2)2-NH2 with
CH3 1 'CH3
CH3 NH~CH3
CI
CH3 CH3 ~ CH3 CH3
HN N ~ N NH
CH3 N ~ N ~ N CH3 and Br-(CH2)2-Br (amine U); and the
_ v
CH3 ~ ~ CH3
Calls Calls
CH3 CH3 CH j -(CH2)s
O-C-CH2
reaction product of the compound of formula HN~C - NH
CH3 I\CH3 II
O
epichlorohydrine (amine W).
-38-
The oligomeric amines are often a mixture of compounds which differ from each
other
with respect to the length of their chains.
Of preeminent interest is the use of the amines A, B, C, D, E, F, G, H, J, K,
L, M, N, O, P,
Q, R, S, T, U, V and W specified above.
It is particularly preferred to add to the novel compositions those amines
whose molecular
weight or average molecular weight ~o is in the range from 300 to 10000, more
particularly from 1000 to 10000. To be highlighted in particular are in turn
those amines
whose molecular weight or average molecular weight ~n is in the range from
1500 to
10000, e.g. from 2000 to 7500.
The amines of higher molecular weight are, in particular, sterically hindered
amines.
To be highlighted in particular are those novel compositions comprising as
component (b)
two or more than two compounds of the type of the sterically hindered amines.
The indicated amines are known compounds; many of them are commercially
available.
The novel compositions preferably comprise phosphites or phosphonites
corresponding to
one of formulae ( 1 ) to (7)
/ORi /0R2
(1) R'1-Y'-P\ . (2) A X P\
OR3 OR3
n'
O O
(3) R'~ \P-O A~ (4) D~ ~P-O-
p CH O
q 3
O O
R'~ O P\ /P O R~> >
O O
-39-
Rn 4
P
O ~ ~ R,14 O n/ ~O
O
R'
(6) E, P Z, R~ls ~ (~) \P Q'
O
O ~ ' R z
X14
R~14
wherein the indices are integers, and
n'is2,3or4;pis 1 or2;qis2or3;ris4to l2;yis l,2or3;andzis 1 to6;
A', if n' = 2, is alkylene of 2 to 18 carbon atoms; alkylene of 2 to 12 carbon
atoms which is
interrupted by -S-, -O- or -NR'4-; a radical of one of formula
R,5 R,5
or B'
R,s R,s
or phenylene;
A', if n' = 3, is a radical of formula -Cl.H2r-n ;
A', if n' = 4, is the radical of formula C(CH~ ;
A", if n' = 2, has the meaning of A ;
B' is a radical of formula -CH2-; -CHR'4-; -CR'1R'4-; -S- or a direct bond; or
CS-C~cycloalkylidene; or cyclohexylidene which is substituted by 1 to 4 C1-
C4alkyl
radicals in position 3, 4 and/or 5;
D', if p = 1, is methyl and, if p = 2, is -CH20CH2-;
E', if y = 1, is alkyl of 1 to 18 carbon atoms, a radical of formula -OR'1 or
halogen;
E', if y = 2, is a radical of formula -.O-A"-O- ;
E', if y = 3, is a radical of formula R4C(CH20~ ;
Q' is the radical of an at least z-hydric alcohol or phenol, which radical is
bound through
the alcoholic or phenolic O-atoms) to the P-atom(s).;
-40-
R'1, R'2 and R'3 are each independently of one another alkyl of 1 to 30 carbon
atoms; alkyl
of 1 to 18 carbon atoms which is substituted by halogen, -COOR4', -CN or -
CONR4'R4 ;
alkyl of 2 to 18 carbon atoms which is interrupted by -S-, -O- or -NR'4- ;
phenyl-C1-C4alkyl; cycloalkyl of 5 to 12 carbon atoms; phenyl or naphthyl;
phenyl or
naphthyl which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy
radicals of a total
of 1 to 18 carbon atoms, or by phenyl-C1-C4alkyl; or a radical of formula
R~s
-{CHI m ~ ~ OH ~ wherein m is an integer from 3 to 6;
R~s
each R'4 is independently hydrogen; alkyl of 1 to 18 carbon atoms; cycloalkyl
of 5 to
12 Gabon atoms; or phenylalkyl of 1 to 4 carbon atoms in the alkyl moiety;
R'S and R'6 are each independently of the other hydrogen; alkyl of 1 to 8
carbon atoms or
cycloalkyl of 5 or 6 carbon atoms; R'~ and R's, if q = 2, are each
independently of the
other C1-C4alkyl or, taken together, are a 2,3-dehydropentamethylene radical;
and
R'~ and R'g, if q = 3, are methyl;
the substituents R'14 are each independently of one another hydrogen; alkyl of
1 to
9 carbon atoms or cyclohexyl;
the substituents R'15 are each independently of one another hydrogen or
methyl; and
R' 16 is hydrogen or Cl-C4alkyl and, if there is more than one radical R' 16,
said radicals
R' 16 are identical or different; '
X' and Y' are each a direct bond or -O-; and
Z' is a direct bond; -CH2-; -C(R'16)2- or -S- .
A particularly preferred process is that wherein the phosphite or phosphonite
is one of
formula ( 1 ), (2), (5) or (6), wherein
n' is 2, and y is 1 or 2 ;
A' is alkylene of 2 to 18 carbon atoms; p-phenylene or p-biphenylene;
E', if y = 1, is C1-Clgalkyl, -ORl or fluoro; and, if y = 2, is p-biphenylene;
R'1, R'2 and R'3 are each independently of one another alkyl of 1 to 18 carbon
atoms;
phenyl-C1-C4alkyl; cyclohexyl; phenyl; phenyl which is substituted by 1 to 3
alkyl
radicals containing a total of 1 to 18 carbon atoms;
the substituents R'14 are each independently of one another hydrogen or alkyl
of 1 to
9 carbon atoms;
~~~~~~e~9
-41 -
R'is is hydrogen or methyl;
X' is a direct bond;
Y' is -O-; and
Z' is a direct bond or -CH(R'16)-
A process meriting particular interest is a process for stabilising a
phosphite or
phosphonite of one of formula ( 1 ), (2), (5) or (6), wherein
n' is 2, and y is 1;
A' is p-biphenylene;
E' is C1-Clgalkoxy or fluoro;
R'1, R'2 and R'3 are each independently of one another alkyl of 1 to 18 carbon
atoms;
phenyl substituted by 2 or 3 alkyl radicals containing a total of 2 to 12
carbon atoms; the
substituents R'14 are each independently of one another methyl or tert-butyl;
R'is is hydrogen;
X' is a direct bond;
Y' is -O-; and
Z' is a direct bond, -CHZ- or -CH(CH3)-.
Phosphites are particularly preferred, especially those of formulae ( 1 ) and
(5).
The following compounds are exemplary of phosphites and phosphonites whose
stability
to hydrolysis can be particularly advantageously enhanced by the novel
process:
C'3
H2 CHC-CH
3
CH3 ~ CHI' _ CH3
CH3 ~ ~ /P-O ~ ~ C-CH3 (Ph-1);
CH3 C O CH3
CH3 'C~CH3 CH3
CH3 CH
3
-42-
CH
CH3 ~ ~ 3
CH3 _ C'CH3
i
CH3 - C ~ ~ O
CH CH3
p _ O / ~ C _ CH3 (Ph-2)~
CH3 - CH
CH3 - C / ~ ~ CH3 , C ' 3
CH CHs
CH3 C-CH3 3
CH3 ~ CH3
CH3 ~C CH3 CH~C~CH3
CH3 _ CH3 CH3 _ CH3
CH3 - C ~ ~ O O ~ / C - CH3
'3
CH3 / ~ / ~ ~ CH Ph-3
CH3 / ~ ~ CH3 ( )~
CH3 - C ~ O O ~ ~ C - CH3
CH3 ' C.CH3 . CH3 , - CH3
C
CH3 CH3 CH3 CH3
CH3 CH3
C.CH3
CH3 \ CH3 CH3
CH3 p-O ~ C-CH
CH3 - C ~ ~ O~ ~ ~ CH3 3 (Ph-4)~
CH3 C,CH3 CH3
CH3 CH
3
C(CH3)3 C(CH3)3
O O _
/ \ _
(CH3)3C ~ ~ O- p' p O ~ ~ C(CH3)3 (Ph S)
O ~O
_ ~146~~3
C(CH3)3 C(CH3)3
O O
CH3 ~ ~ O - p\ P - O CH3 (ph_6);
O O
C(CH3)3 C(CH3)s
CH3\ ,CH3
CH3 ~C .
CH3
1
O \ ~ C - CH3
CH3
CH30 - ~ CH - CH
3 CH3 (Ph-~);
O ~ ~ C-CH3
_ 1
CH3
CH3 . C
CH \CH3
3
CH3\ .CH3
n'CaHs CH3'C CH3
i
H5C2 ~ ~ O C - CH3
/ CHs
CH2 O - P CH2 (Ph-8);
CH3
C-CH
~ 3
CH3 CH3
CH ~CH3
3
CH3 CICH3
CH3 CH3
1
O \ ~ C - CH3
CH3
- P CH - CH3 (Ph-9);
CH3
C-CH
3
_ 1
CH3
CH3 . C
CH \ CH3
3
44
O O
HsW~s- O - P\ P -O - C~aHs~ (Ph-10).
O O
Said phosphites and phosphonites are known compounds; some of them are
commercially
available.
The invention also relates to a process for stabilising an organic phosphite
or phosphonite
or a mixture of organic phosphites or phosphonites against hydrolysis, which
comprises
adding as stabiliser (b) an organic amine and as stabiliser (c) an acid-
binding metal salt,
such that the stabilised phosphite or phosphonite comprises 0.01 to 50% by
weight of the
aminic component (b) and 0.01 to 25% by weight of the acid-binding metal salt
(c) (in
each case based on the total weight), as well as to the use of an organic
amine in
conjunction with an acid-binding metal salt as hydrolysis stabiliser for
organic phosphites
or phosphonites. Preferred amounts and single components for use in the novel
process are
as indicated above.
The invention also relates to an organic phosphite or phosphonite stabilised
against
hydrolysis obtainable by the above-described process.
It is preferred to use sterically hindered amines in combination with acid-
binding metal
salts, more particularly sterically hindered amines having a molecular weight,
or an
average molecular weight, in the range from 1500 to 10000 and, most
preferably, in
conjunction with hydrotalcites and/or zeolites, as stabilisers for organic
phosphites and/or
phosphonites against hydrolysis, particularly against hydrolysis during
storage in contact
with humid air. The use as hydrolysis stabilisers for organic phosphites is
particularly
preferred. To achieve the desired enhanced hydrolysis stability, any amount of
a sterically
hindered amine and acid-binding metal salt can be used, for example 0.01 to
200% by
weight, more particularly 0.1 to 100% by weight, preferably 0.01 to 50% by
weight and,
most preferably, 0.1 to 25% by weight, in each case based on the amount of
phosphite or
phosphonite. The amount of acid-binding metal salt is expediently at least
0.01% by
weight, based on the stabilised composition.
At the same time, the invention relates to a method of storing solid organic
phosphites or
phosphonites, which comprises adding to said phosphites or phosphonites 0.01
to 200% by
weight, typically 0.01 to 100% by weight, preferably 0.01 to 50% by weight
and, most
~~~s~o~
-45-
preferably, 0.1 to 25% by weight (based on phosphite or phosphonite) each of a
sterically
hindered amine and an acid-binding metal salt.
Some commercial organic phosphites or phosphonites are obtained as compound
mixtures
or in prestabilised form; an organic amine is often used as prestabiliser in a
concentration
of c. 1%. The stability to hydrolysis of such products can also be greatly
enhanced by the
novel process.
The novel compositions and the products obtained by the novel process may
advantageously be used as stabilisers for organic material, in particular
organic polymers,
typically synthetic polymers, against the harmful action of heat, oxygen
and/or light.
Illustrative examples of such polymers are disclosed, inter alia, in US-A-4
855 345, from
column 4, line 63, to column 7, line 54.
Amine and acid-binding metal salt (components b and c) can be added to the
phosphite or
phosphonite by customary mixing procedures or, for example, by milling them
together.
They are conveniently added to the solution or melt of the phosphite or
phosphonite prior
to the crystallisation thereof, e.g. to the solution resulting from the
synthesis. It is also
possible to add said components during the synthesis or to one of the educts.
In the novel process it is possible to use crude phosphite solutions or crude
phosphonite
solutions as obtained from the synthesis before crystallisation.
In a preferred embodiment, the amine and the acid-binding metal salt are
obtained in a
solution or a melt from which the phosphite or phosphonite is crystallised. In
this case the
amount of sterically hindered amine added to the solution or melt is usually
0.01 to 100%
by weight, preferably 0.01 to 50% by weight, more particularly 0.1 to 25% by
weight and,
most preferably, 0.5 to 20% by weight (in each case based on the phosphite or
phosphonite). The amount of acid-binding metal salt in the solution or melt is
expediently
0.05 to 25% by weight, based on the total weight of the solution or melt,
without taking
into account any solvent present, as indicated at the outset with respect to
the product. The
use of 0.05 to 25% by weight of acid-binding metal salt, based on the
phosphite or
phosphonite, is preferred.
The crystalline phosphite or phosphonite can then be obtained from the
solution or melt in
per se known manner, typically by cooling and/or concentration. It is possible
to
H
-46-
accelerate the crystallisation by addition of seed crystals. The solution can
conveniently be
concentrated by heating, by applying reduced pressure, by using entrainers
and/or by cold
trapping. If required, further customary working up processes can then follow,
such as
filtration, drying or milling.
The product of the novel process is a mixture comprising solid phosphite or
phosphonite,
acid-binding metal salt and amine. The product of the novel process preferably
contains
mixed crystals of amine and phosphite or phosphonite in admixture with
crystals of the
acid-binding metal salt. These mixed crystals preferably constitute at least
50% by weight,
more particularly at least 80% by weight, of the product.
A particularly preferred process for stabilising a crystalline organic
phosphite or
phosphonite against hydrolysis comprises adding a homogeneous melt, heated to
50-100°C, of phosphite or phosphonite, of a solvent or solvent mixture,
and of 0.1 to
100% by weight (based on phosphite or phosphonite) of an amine, in which melt
0.05 to
25% of acid-binding metal salt (based on phosphite or phosphonite) are
dispersed, to a
liquid crystallisation medium, the temperature of which during the addition is
kept at
10-70°C below the temperature of the melt.
The melt in this process is the liquid mixture comprising amine, solvent and
the phosphite
or phosphonite to be stabilised. The melt may contain a minor or larger amount
of solvent,
e.g. 20 or 500% by weight (based on phosphite or phosphonite), and accordingly
the melt
can have the character of a solution. It is important that the melt is
homogeneous, i.e. that
the indicated components are no longer crystalline and also that there is no
separation into
two or more than two liquid phases. The amine can be a single compound or a
mixture of
compounds.
The acid-binding metal salt is conveniently added to the mixture before or
during the
homogenisation in finely particulate form and dispersed in known manner,
typically by
stirring.
As solvent there may be used in principle all organic compounds or compound
mixtures
which are liquid in the temperature range from 10 to 60°C under normal
pressure and do
not cause solvolysis, and which are capable of dissolving a sufficient amount
of solid
phosphite or phosphonite above 50°C and, as appropriate, at up to
100°C, or which are
sufficiently miscible with the fused phosphite or phosphonite. The solubility
or miscibility
-47- ~~~ ~0~
is sufficient when, for example, the homogeneous liquid mixture is able to
contain up to
and including 15% by weight, more particularly up to and including 50% by
weight, of
phosphite or phosphonite. Suitable solvents are e.g. alcohols or hydrocarbons,
or mixtures
thereof.
The solvent used in the melt is preferably a compound or a mixture of two
compounds.
The main solvent is used in an amount of 20 to 500% by weight, based on
phosphite or
phosphonite, and the further solvent is used in amount of 0-50% by weight,
based on the
main solvent. The melt preferably contains as main solvent an alcohol or a
hydrocarbon in
an amount of 20 to 500% by weight, based on phosphite or phosphonite, and a
further
solvent in an amount of 0-50% by weight, more particularly of 0-20%, based on
the main
solvent.
It is also possible to use a mixture of alcohols or a mixture of hydrocarbons.
Suitable alcohols are, for example, lower alcohols such as Cl-Csalkanols, more
particularly C1-C3alkanols such as methanol, ethanol, propanol or isopropanol.
Isopropanol and methanol are particularly suitable.
Suitable hydrocarbons are typically C6-Cl3alkanes, cycloalkanes or alkylated
cycloalkanes
of 6 to 12 carbon atoms, benzene, or alkylated aromatic hydrocarbons of 6 to
10 carbon
atoms. Toluene, ligroin, petroleum ether and xylene are particularly suitable.
Toluene is
most preferred.
A hydrocarbon or a mixture of hydrocarbons is often used as further solvent if
the main
solvent is an alcohol or, if the main solvent is a hydrocarbon, an alcohol.
Suitable alcohols
and hydrocarbons are those indicated above.
The temperature of the melt is preferably in the range from 55 to 90°C,
more particularly
from 60 to 80°C.
In the preferred process the difference in temperature between the melt and
the
crystallisation medium is conveniently at least 20°C, typically from 30
to 70°C and,
preferably, from 40 to 60°C.
The crystallisation medium is preferably kept at a temperature which is at
least 10°C,
typically from 10 to 60°C, below the resulting liquidus temperature.
The temperature of
the crystallisation medium is preferably from 20 to 60°C below the
resulting liquidus
-48- ~~~f~~03
temperature.
The resulting liquidus temperature is the temperature at which a homogeneous
phase
formed from melt and crystallisation medium is in thermodynamic equilibrum
with
phosphite crystals or phosphonite crystals. Below this temperature,
crystallisation begins;
above this temperature, the mixture is a homogeneous melt. In practice, said
temperature
is conveniently determined by mixing experiments, typically using calorimetric
methods
(e.g. DSC) and/or optical methods.
As crystallisation medium it is expedient to use 80 to 800% by weight, more
particularly
100 to 500% by weight, of organic solvent, based on phosphite or phosphonite
in the melt.
Alcohols can conveniently be used as crystallisation medium, for example a C1-
Csalkanol
or a mixture of different C1-CSalkanoles. It is preferred to use C1-C3alkanols
as
crystallisation medium, e.g. methanol, ethanol, propanol or isopropanol.
It is expedient to add seed crystals to the crystallisation medium.
Accordingly, the
crystallisation medium preferably consists of a suspension of 2 to 20% by
weight of
crystalline phosphite or phosphonite, based on phosphite or phosphonite in the
melt.
Furthermore, it is advantageous if the crystallisation medium is saturated 50
to 100% with
the amine, 100% saturation corresponding to an amine concentration in which
dissolved
and solid amines may be obtained simultaneously.
The melt usually comprises 0.1 to SO% by weight of amine (component b), based
on
phosphite or phosphonite, preferably 0.2 to 25% by weight, more particularly
0.5 to 20%
and, most preferably 0.5 to 10% (based on phosphite or phosphonite in the
melt).
The acid-binding metal salt (component c) is usually added to the melt in an
amount of
0.05 to 20% by weight, more particularly of 0.05 to 15% by weight and, most
preferably,
of 0.1 to 10% by weight (based on phosphite or phosphonite in the melt).
The crystallisation medium is preferably stirred when adding the melt and
component (c)
dispersed therein. After the two mixtures have been combined, the further
working up can
be carried out in per se known manner, e.g. by cooling to 10-15°C and
by isolation of the
crystalline product.
The stabilised phosphite or phosphonite is usually obtained in powdered form,
wherein the
-49- ~~~~~0~
amine and the acid-binding metal salt are homogeneously dispersed. The powder
typically
comprises 0.01 to 20% by weight, more particularly 0.05 to 10% by weight and,
preferably, 0.1 to 5% by weight of amine (based on phosphate or phosphonite).
After
crystallisation, the metal salt dispersed in the melt is often present in
almost quantitative
amount in the product. If the melt is additionally filtered, which may be
expedient on
account of the apparatus employed, the content of acid-binding metal salt also
can be
reduced, often minimally.
The preferred process is particularly useful for stabilising the above-
mentioned phosphates
Ph-1, Ph-2, Ph-4, Ph-5, Ph-6, Ph-7 and Ph-8, and the phosphonite Ph-3.
The following Examples further illustrate the novel process. Unless otherwise
stated, all
parts and percentages are by weight, as likewise in the remainder of the
description and in
the claims. Percentages relating to phosphate or phosphonite will be taken to
mean
phosphate or phosphonite in the melt, unless otherwise stated.
Amines used in the Examples are:
amine A: triisopropanolamine;
amine C: bas{2,2,6,6-tetramethylpiperidin-4-yl)sebacate
CH CH3 O
NH
amine H: compound of formula HN cH
CH3 O ~CH2)9
CH3 CH2
R R
amine J: compound of formula R-NH-(CH2)g-N-(CH2)2-~-(CH2)g-NH-R
HaC CHs
N ~aHs
wherein R = ~ 1--- N N - CH3 ; CAS-No. 106990-43-6;
N Y N H3C CH3
C4H9 - N
H3C . ~ CH3
H3C N CH3
CH3
-50-
CH3
CH3 O O
;, ,.
amine N: oligomer of formula O N CH2-CH2 O - C CH2-CH2 C
wherein m is
CH3CH3 m
a number from 8 to 11; CAS-No. 65447-77-0;
amine P: oligomer of formula
CH3 NH CH3 CH3 HN CH3 CH3 CH3 3~
NH CH3 NH CH
CH3 CH3CH3 CH CH3 CH3CH3 CH
3
HN ~CHZ)~ N / ~ N ~CH2)~ N H
N ' 'N
'Y I Ha ( Ha
HN- j -CHI- i -CH3
CH3 CH3 m
wherein m is a number from 3 to 4 (CAS-No. 70624-18-9);
amine Q: oligomer of formula
CH3 NH CH3 CH3 HN CH3 CH3 NH CH3 CH3 CH3
CH3 CH3CH3 CH3 CH3 CH3CH3 NH CHa
HN ~CHZ)~- N / ~ N (CH2)~ N H
NYN
N
o m
(supplied by Cytec Inc., USA);
amine U: reaction product of H2N-(CH2)2-NH-(CH2)2-NH2 with
CI
CH3 CH3 ~ CH3 CH3
HN N \ N NH
CH3 N ~ N ~ N CH3 and Br-(CH2)2-Br (supplied
CH3 ~ ~ CH3
C4H9 C4H9
by: Sigma);
amine X: 2,2,6,6-tetramethylpiperidine;
amineY: 4-hydroxy-2,2,6,6-tetramethylpiperidine (HTMP);
amine Z: 1,3,5-trimethyl-2,4,6-triazine.
-51-
The zirconium carbonate (Zr carb.) used in some of the Examples as acid-
binding metal
salt is basic zirconium carbonate, supplied by Tilcom, Great Britain.
If not indicated in the Example or in the above list, the structural formulae
of the
phosphites, phosphonites and amines used in the Examples are listed in the
text above.
Example l: A mixture of 300 g of the phosphite Ph-1, 225 g of isopropanol,
2.25 g of
toluene, 6.0 g of the metal salt of formula IXc
Mg4.5~2(OH)13'CO3~3.S H2O, (IXc)
(stabiliser IXc; Kyowa Chem. Ind., Osaka, Japan) and 30 g of amine N is
heated, with
stirring, to 70-75°C. The resulting homogeneous melt containing
dispersed metal salt is
subjected to coarse filtration and then added over 1 hour, with stirring, to
450 g of
isopropanol, the temperature of which is kept at 20-30°C during this
addition. The mixture
is then cooled to 10-15°C and stirred for another 3 hours in this
temperature range. The
crystalline product is then isolated by filtration and dried at 60°C
under reduced pressure
(sample d}. The elemental analysis of the dried product gives a content of
9.0% of
amine N and 0.19% of metal salt (based on phosphite).
Three comparison samples are crystallised by the method described above, but
using in
one sample the amine (sample c}, in the second sample the metal salt (sample
b), and in
the third sample both additions are omitted (sample a).
Another sample (e) is crystallised by the above method, but further adding 6.0
g of amine
P to the melt. The elemental analysis of the dry product gives a content of 9%
of amine N,
0.5% of amine P and 0.19% of metal salt (based on phosphite).
Equal amounts of the product are then subjected to the following test for
stability to
hydrolysis:
The samples are stored at 50°C and 75% atmospheric humidity. The
content of phosphate
Ph-1 is determined at regular intervals by means of gas chromatography (begin
of storage
is set as 100 % Ph-1).
The results are shown in the following Table 1.
-52-
Tab. 1: Degradation of the phosphite Ph-1 during storage at 50°C and 75
% humidity
Sample Stabiliser Stab. in productDegradation
(%)
after
Oh
24h
41h
a none none 0 100 100
b 10% amine N 9.~ ~ amine N 0 13.635.9
c 2% IXc 1.7 % IXc 0 11.577.8
d 10% amine N +2% 9.0 % amine N 0 5.2 17.0
IXc
+ 0.19 % IXc
a 10% amine N +2% 9.0 % amine N 0 6.5 15.0
IXc
+ 2 % amine P + 0.19 % IXc
+ 0.5 % amine
P
The results in Table 1 show that the phosphite samples d and a of this
invention have
excellent stability to hydrolysis.
Example 2: Stabilised phosphite Ph-1 is prepared according to the method
described in
Example 1 and tested for stability to hydrolysis; the content of undegraded
phosphite is
determined by 31P-NMR after a storage time of 24 h, 48 h and 72 h. The
following Table 2
shows the amount and type of amine and metal salt used as well as the test
results.
Tab.2: Degradation of the phosphite Ph-1 during storage at 50°C and 75
% humidity;
amount based on phosphite
Phosphite
content
Metal salt -1 Amine of Ph-1 (%) after
of Ph
in product in product 24h 48h 72h
0 (unstabilised) 0 0 48.3 0 0
0 0 10% amine N 8% 79.4 21.2 0
0 0 10% amine P 1.4% 88.5 22.2 0
0 0 10% amine A 0.35% 60.4 15.6 0
0 0 10% piperazine0.35% 62.1 20.2 0
2% IXc 1.1% 0 0 85.7 20.3 0
~~~~~0~
-53-
10% IXc 1.3% 10% piperazine 0.02% 90.1 81.3 60.2
10% IXc 1.2% 10% amine X 0.03% 85.8 75.2 51
10% IXc 1.4% 10% amine Z 0.04% 87 78.1 52.4
10% IXc 1.6% 10% dibutylamine 0.01 % 90.2 81.5 60.5
10% IXc 1.4% 10% amine J 0.2% 100 95.8 80.4
10% IXc 1.5% 10% amine C 0.18% 94.5 89.8 72
10% IXc 1.3% 10% amine H 0.19% 98.4 92.1 75.9
10% IXc 1.2% 10 amine U 0.15% 96.3 90.8 74.1
10% IXc 1.4% 10 amine Q 0.21% 100 94.2 78.3
0.5% IXc 0.06% 0.5% piperazine 0.015% 85.3 74.1 50.9
0.5% IXc 0.07% 0.5% amine X 0.02% 79.7 68.9 45.2
0.5% IXc 0.08% 0.5% amine Z 0.01% 81.2 72.6 46.1
0.5% IXc 0.06% 0.5% dibutylamine 0.01% 84 75.9 54.2
0.5% IXc 0.07% 0.5% amine J 0.02% 98.4 90.8 75.2
0.5% IXc 0.07% 0.5% amine C 0.03% 90 84.2 66
0.5% IXc 0.08% 0.5% amine H 0.02% 93.3 87.4 71
0.5% IXc 0.09% 0.5% amine U 0.02% 91.5 85.7 69.1
0.5% IXc 0.06% 0.5% amine Q 0.02% 97.3 88.4 71.4
2% IXc 1.1% 10% amine N 8% 91.7 77.8 63.8
0.5% IXc 0.2% 0.5% amine N 0.3% 88.3 70.1 53.2
10% Zn0 1.4% 10% amine A 0.22% 85.4 73.2 48.5
10% Zn0 1.3% 10% amine N 8.3% 89.8 75 59.4
10% Zn0 1.5% 10% amine P 0.24% 98.6 90.4 72.2
0.5% Zn0 0.06% 0.5% amine A 0.05% 80.1 61.8 35.4
0.5% Zn0 0.08% 0.5% amine N 0.21% 84.6 66.4 49.9
0.5% Zn0 0.07% 0.5% amine P 0.04% 95.8 86.3 69.1
10% Ca0 1.3% 10% piperazine 0.03% 85 75.4 53.2
10% Ca0 1.4% 10% amine P 0.27% 97.2 89.8 71.4
10% Ca0 1.2% 10% amine J 0.26% 95.4 86.9 68.1
10% Ca0 1.2% 10% amine U 0.27% 91.8 82.4 61.9
0.5% Ca0 0.1% 0.5% piperazine 0.02% 78 68.8 42
0.5% Ca0 0.08% 0.5% amine P 0.03% 90.6 83.4 65.9
0.5% Ca0 0.07% 0.5% amine J 0.02% 87.9 79.1 60
0.5% Ca0 0.09% 0.5% amine U 0.03% 84.1 75.9 53
i4~z~~
-54-
Tab.2: Continuation
Phosphite
content
Metal salt 'Amine of Ph-1 (%)
of Ph-1 after
in product in product24h 48h 72h
10% Mg0 1.3% 10% amine J 0.25% 94.8 88.1 70
10% Mg0 1.2% 10% amine C 0.23% 88:2 79.2 60.2
0.5% Mg0 0.08% 0.5% amine J 0.02% 86.8 78 58
10% CaC03 1.3% 10% amine P 0.25% 90.8 83 50.4
10% CaC03 1.4% 10% amine H 0.26% 89.4 81.1 43.7
0.5% CaC030.08% 0.5% amine P 0.02% 85.4 78.4 42.9
10% Ca(OH)21.6% 10% amine Q 0.27% 90.4 82.6 48.7
2% Zr carb.1.2% 10% amine N 6.3% 85.6 66 43.8
0.5% Zr 0.15% 0.5% amine N 0.23% 80.4 57.3 32.5
carb.
2% Al(OH)31.1% 10% amine N 6.3% 76.3 50.6 42.3
0.5% Al(OH)30.2% 0.5% amine N 0.25% 73.2 41.8 25.6
Example 3: Stabilised phosphite Ph-2 is prepared according to the method
described in
Example 1. Stability to hydrolysis is determined by storing at 70°C and
75% atmospheric
humidity, and the content of undegraded phosphite is tested by 31P-NMR after a
storage
time of 24 h, 48 h and 72 h. The following Table 3 shows the amount and type
of the
amine and metal salt used as well as the test results.
Tab.3: Degradation of the phosphite Ph-2 during storage at 70°C and 75
% humidity;
amount based on phosphite
Phosphite
content
Metal salt Amine of Ph-1 (%) after
of Ph-1
in product in product24h 48h 72h
0 (unstabilised) 0 0 95.4 60.3 0
0 0 10% amine J 1.6% 97.1 86 21.4
0 0 10% amine N 8.7% 97.2 85.3 20.6
0 0 10% amine A 1.55 80.2 25.4 0
10% IXc 3.8% 0 0 90.2 40.9 0
~1~~~Q~
-55-
10% IXc 3.6% 10% amine J 1.5% 100 96 74.1
% IXc 3.7% 10% amine N 8.7% 100 95.3 70.2
10 % IXc 3.6% 10% amine A 0.9% 100 80.6 45.3
0.5 % IXc 0.26% 0.5% amine 0.03% 100 89.4 50.9
J
0.5 % IXc 0.27% 0.5% amine 0.3% 100 88.8 48.7
N
0.5 % IXc 0.25% 0.5% amine 0.07% 100 70.8 30.3
A
10% Zr carb.3.5% 10% amine J 1.4% 100 89.4 55.7
10% Zr carb.3.4% 10% amine N 9% 100 88.8 53
10% Zr carb.3.6% 10% amine A 1.2% 100 73.2 38.6
0.5% Zr carbØ23% 0.5% amine 0.03% 100 82.1 47.9
J
0.5% Zr carbØ24% 0.5% amine 0.3% 100 81.6 45
N
0.5% Zr carbØ25% 0.5% amine 0.06% 100 61.9 29.7
A
10% Ca0 2.9% 10% amine J 1.2% 100 93.3 62.8
10% Ca0 3.1% 10% amine N 8.6% 100 92.4 61.2
10% Ca0 3.3% 10% amine A 1.1% 100 86.6 41.4
0.5% Ca0 0.24% 0.5% amine 0.04% 100 85.4 48.4
J
0.5% Ca0 0.25% 0.5% amine 0.35% 100 83.9 47.1
N
0.5% Ca0 0.25% 0.5% amine 0.06% 100 70.8 30
A
Example 4: Stabilised phosphonite Ph-3 is prepared according to the method
described iri
Example 1. Stability to hydrolysis is tested by storing at 50°C and 75%
of atmospheric
humidity, and the content of undegraded phosphonite is tested by 31P-NMR after
a storage
time of 24 h and 48 h. The following Table 4 shows the amount and type of the
amine and
metal salt used as well as the test results.
Tab.4: Degradation of the phosphonite Ph-3 during storage at 50°C and
75 % humidity;
amount based on phosphonite
Phosphonite content
Metal salt of Ph-3 Amine of Ph-3 (%} after
in product in product24h 48h
0 (unstabilised) 0 0 45 20.3
0 0 10% amine J 6.0% 60.8 40.7
0 0 10% amine N 10% 64.9 46.3
0 0 10% amine A 6.1% 55.4 32.6
~~~~2~~
-56-
10% IXc 7.9% 0 0 61.2 44.7
10% IXc 7.4% 10% amine J 5.8% 84.6 72.1
% IXc 7.5% 10% amine N 10% 90.5 78.4
10 % IXc 7.3% 10% amine A 6.0% 72.3 52.4
0.5 % IXc 0.4% 0.5% amine 0.4% 76.6 64.6
J
0.5 % IXc 0.4% 0.5% amine 0.5% 82.3 69.1
N
10% Zr carb.7.5% 10% amine J 5.7% 79.4 67.5
10% Zr carb.7.5% 10% amine N 10% 84.9 67.5
0.5% Zr carbØ35% 0.5% amine 0.4% 71.3 60
J
0.5% Zr carbØ35% 0.5% amine 0.5% 77.4 64.7
N
10% Ca0 7.6% 10% amine J 5.8% 79.8 67
10% Ca0 7.5% 10% amine N 10% 85.4 74.1
0.5% Ca0 0.3% 0.5% amine 0.4% 71.6 61.2
J
0.5% Ca0 0.3% 0.5% amine 0.5% 78 65
N
The test results show a markedly enhanced stability of the phosphites and
phosphonites
stabilised according to this invention in comparison with the unstabilised
product and with
products stabilised only by addition of amine or metal salts.
