Note: Descriptions are shown in the official language in which they were submitted.
-1-
A-17906/+/CGM 328
Melamine derivatives as stabilisers for chlorine-containing polymers
The present invention relates to compositions containing a) a chlorine-
containing polymer,
b) a melamine derivative and c) a metal salt, to the use of a mixture
comprising
components b) and c) for stabilising a chlorine-containing polymer against
thermal
degradation and to novel melamine derivatives.
It is known that chlorine-containing polymers have to be protected against the
damaging
effect of light and heat, in particular during the processing to give moulded
articles. A few
melamine derivatives and their use as stabilisers for chlorine-containing
polymers are
described, for example, in JP-A-Sho 56/43,342, US-A 3,084,135 and US-A
3,496,136.
The preparation of various melamine derivatives has already been described by
D.F.
Walker et al.; "J. Am. Pharm. Ass. 39, 393-396", 1951 by D.W. Kaiser et al.;
"J. Am.
Chem. Soc. 73, 2984-2986", 1963, by D.lr. O'Brien et al.; "J. Med. Chem. 6,
467-471",
1967 by Smolin et al.; "s-Triazines and Derivatives - The Chemistry of
Heterocyclic
Compounds, Chapter VI, pp. 309-388" and also in 1967 by A.B. Borkovec et al.;
"J. Med.
Chem. 10, 457-461" and in US-A 4,312,988. Melamine derivatives as odour-
binding
agents for polyvinyl chloride films are known from JP-A 79/6043 and JP-A
86/116,512.
The present invention relates to compositions containing
a) a chlorine-containing polymer,
b) O.U1 to 1% by weight, relative to the chlorine-containing polymer, of a
compound of the
formula I and/or its hydrochloride,
NHR
N i _N
(I)
H2N ~N NH2
in which R is C6-CZOalkyl, C3-C2oalkyl interrupted by 1 to S oxygen atoms, Ct-
C2oalkyl
~~~~~~~2
-2-
substituted by 1 to 5 OIi, C3-C2«alkenyl, C3-Cscycloalkyl, CI-Cnalkyl-
substituted
C3-C$cycloalkyl, C~-CI tphenylalkyl, C~-Cl tphenylalkyl which is substituted
on the
phenyl by 1 to 3 radicals, these radicals, independently of one another, being
hydroxyl,
chlorine, CI-Cnalkyl, methoxy or ethoxy, or R is furthermore a group of the
formula IIa or
IIb,
R1
-CH2-CH-CF12-X ,
I
OH R2
R3
(ITa) (IIb)
in which X is Ct-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio,
benzyloxy or
benzylthio, and Rt, R2 and R3, independently of one another, are hydrogen, C1-
CZOalkyl,
Ct-C2oalkyloxy, Cl-C2oalkylthio, C2-Cl2alkyloxycarbonyl, C2-Cl2alkanoyl,
phenyl,
phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and
c) 0.01 to 5% by weight, relative to the chlorine-containing polymer, of an
Me(II)
carboxylate and/or Me(II)-phenolate, in which Me(II) is Ba, Ca, Mg, Cd or Zn.
Component c) is preferably a mixture of Ba/Zn carboxylates if component b) is
phenyl-
melamine.
Examples of R as C6-C2oalkyl are hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl
or eicosyl.
R as C3-Gioalkyl which is interrupted by 1 to 5 oxygen atoms is preferably a
group of the
formula
CrH2r- Z ,
s
in which r is 2 or 3, s is 1, 2, 3, 4 or 5, and Z is, for example, methyl,
ethyl, propyl or
butyl.
4~'~t~~~
-3-
Examples of R as Ct-CZOalkyl which is substituted by 1 to 5 OH are
hydroxymethyl,
2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 4-hydroxybutyl, 5-
hydroxypentyl,
2-hydroxypentyl, 2,3,4,5,6-pentahydroxyhexyl, 8-hydroxyoctyl, 2-hydroxyoctyl,
2-hydroxynonyl, 2-hydroxydecyl or 2-hydroxyoctadecyl. Ci-Cghydroxyalkyl in
which the
hydroxyl group is in the terminal position or in the 2-position is preferred
as is
C~-CZOalkyl which is substituted by -OH in the 2-position. Ct-Cbalkyl which is
substituted
by -OH is particularly preferred.
Examples of R as C3-C2oalkenyl are allyl, 2-methallyl, 3-methylbut-2-enyl,
3-methylbut-3-enyl, hexenyl, decenyl, undecenyl, heptadecenyl or oleyl.
Preferred
meaning~~ are allyl, methallyl and oleyl.
Examples of R as C3-CBCycloalkyl which is unsubstituted or substituted by Ct-
C4alkyl are
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 4-
butylcyclohexyl,
cycloheptyl, cyclooctyl or cyclododecyl. CS-C~cycloalkyl, in particular
cyclohexyl, is
preferred.
R as C~-(a tphenylalkyl is, for example, benzyl or phenylethyl.
Example., of R as C~-Citphenylalkyl which is substituted by 1 to 3 radicals
according to
the definition are o-, m- or p-chlorobenzyl, 2,3-dichlorobenzyl, 2,4-
dichlorobenzyl,
2,5-dichlorobenzyl, 2,6-dichlorobenzyl, 3,4-dichlorobenzyl, 2,4,5-
trichlorobenzyl,
2,4,6-trichlorobenzyl, o-, m- or p-hydroxybenzyl, o-, m- or p-methylbenzyl,
2,3-dimethylbenzyl, 2,4-dimethylbenzyl, 2,5-dimethylbenzyl, 2,6-
dimethylbenzyl,
3,4-dimethylbenzyl, 3,5-dimethylbenzyl, 2-methyl-4-tart-butylbenzyl, 2-
ethylbenzyl,
2,6-diethylbenzyl, 2,6-diethyl-4-methylbenzyl, 2,6-diisopropylbenzyl, 4-tent-
butylbenzyl,
2-chloro-6-methylbenzyl, 3-chloro-2-methylbenzyl, 3-chloro-4-methylbenzyl,
4-chloro-2-methylbenzyl, 5-chloro-2-methylbenzyl, 2,6-dichloro-3-methylbenzyl,
2-hydroxy-4-methylbenzyl, 3-hydroxy-4-methylbenzyl, o-, m- or p-methoxybenzyl,
o-, m-
or p-ethoxybenzyl, 2,4-dimethoxybenzyl, 2,5-dimethoxybenzyl, 2,5-
diethoxybenzyl,
2-methoxy-5-methylbenzyl, 4-methoxy-2-methylbenzyl, 3-chloro-4-methoxybenzyl,
3-chloro-6-methoxybenzyl, 3-chloro-4,6-dimethoxybenzyl or
4-chloro-2,5-dimethoxybenzyl.
Examples of Rt, R2 and R3 as Ct-C2oalkyl are, in addition to the meanings
given above for
-4-
R = alkyl, methyl, ethyl, propyl, isopropyl, butyl, ten-butyl, pentyl, hexyl
and heptyl.
Examples of X, Rt, R2 and R3 as Ct-CZOalkyloxy are methoxy, ethoxy, butoxy,
pentyloxy,
hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, tridecyloxy,
hexadecyloxy or octadecyloxy. One of the preferred meanings for Rt, RZ and R3
is
Ct-C4alkyloxy, in particular methoxy and ethoxy.
Examples of X, Rt, RZ and R3 as Ct-C2oalkylthio are methylthio, ethylthio,
propylthio,
butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio,
dodecylthio,
tridecylthio, hexadecylthio or octadecylthio. C8-CtBalkylthio is preferred.
Examples of Rt, RZ and R3 as C2-Ct2alkyloxycarbonyl are methoxycarbonyl,
ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl,
hexyloxycarbonyl,
octyloxp:arbonyl and decyloxycarbonyl.
Examples of Rt, R2 and R3 as C2-Ct2alkanoyl are acetyl, propanoyl, butanoyl,
pentanoyl,
hexanoyl, heptanoyl, octanoyl or decanoyl.
Example: of group IIb are o-, m- or p-chlorophenyl, 2,3-dichlorophenyl,
2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-
trichlorophenyl,
2,4,6-trichlorophenyl, o-, m- or p-hydroxyphenyl, o-, m- or p-methylphenyl,
2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-
dimethylphenyl,
3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-4-ten-butylphenyl, 2-
ethylphenyl,
2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6-diethylphenyl,
3,5-diethylphenyl, 2,6-diethyl-4-methylphenyl, 2,6-diisopropylphenyl, 4-tent-
butylphenyl,
3,5-di-tett-butylphenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl,
3-chloro-4-methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl,
2,6-dichlaro-3-methylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-
ethoxyphenyl, o-, m-
or p-propoxyphenyl, o-, m- or p-butoxyphenyl, o-, m- or p-hexyloxyphenyl, o-,
m- or
p-octyloxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 2,5-
diethoxyphenyl,
2-methor:y-5-methylphenyl, 4-methoxy-2-methylphenyl, 3-ehloro-4-methoxyphenyl,
3-chloro-6-methoxyphenyl, 3-chloro-4,6-dimethoxyphenyl,
4-chloro-2,5-dimethoxyphenyl, o-, m- or p-methylthiophenyl, o-, m- or p-
ethylthiophenyl,
o-, m- or p-propylthiophenyl, o-, m- or p-butylthiophenyl, o-, m- or p-
pentylthiophenyl, o-,
m- or p-hexylthiophenyl, o-, m- or p-heptylthiaphenyl, o-, m- or p-
octylthiophenyl, o-, m-
or p-nonylthiophenyl, o-, m- or p-decylthiophenyl, o-, m- or p-phenylphenyl
and
-5-
2-hydroxy-4-methylphenyl, 3-hydroxy-4-rnethylphenyl and a group of the formula
ct-c4-alkyl
/ \ oft
C t-C4-alkyl
Preferred meanings for group IIb can be seen from Examples 1 to g given below.
In the group of the formula IIb, R1 and/or R2 are particularly prefererably
hydrogen.
Compositions which are of interest are those in which R is Cto-Ctg-alkyl, OH-
substituted
Cl-Cloallcyl, C3-Ctoalkenyl, CS-C~cycloalkyl, Ct-C4alkyl-substituted Cg-
C~cycloalkyl,
benzyl, benzyl which is substituted on the phenyl by 1 to 3 radicals, these
radicals,
independently of one another, being hydroxyl, chlorine, Ct-C4alkyl, methoxy or
ethoxy, or
R is furthermore a group of the formula lIa or IIb, in which X is Ct-
Ctoalkyloxy,
Cg-CtBalkylthio, phenyloxy, phenylthio, benzyloxy or benzylthio and Rt, R2 and
R3,
independently of one another, are hydrogen, Ct-Ctoalkyl, Ct-Ctoalkyloxy,
Cg-CtBalkylthio, C2-Ct2alkyloxycarbonyl, C2-C6alkanoyl, phenyloxy, phenylthio,
hydroxyl, mercapto or chlorine.
Compositions in which R is Cto-Ctgalkyl, OH-substituted Ct-C6alkyl, allyl,
cyclohexyl or
benzyl are also of interest.
R is preferably the group lIb.
Preference is also given to compositions in which R is a group of the formula
IIb and the
radicals Rt, R2 and R3, independently of one another, are hydrogen, Ct-
C4alkyl,
Ct-C4alkyloxy, Cg-Ct6alkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl, mercapto or
chlorine.
Particulw preference is given to compositians in which R is a group of the
formula IIb, RI
is hydrogen, R2 and Rg, independently of one another, are Cl-C4alkyl, Ci-
C4a(kyloxy,
Cg-Ctbalkylthio, C2-Ct2alkyloxycarbonyl, hydroxyl or chlorine and RZ is
additionally
hydrogen.
Compositions which are of particular interest are those in which R is a group
of the
formula IIb, Rt and R2 are hydrogen and R3 is CI-C4alkyl, Ct-C4alkyloxy,
Cg-Ctbalkylthio, C2-CF2alkyloxycarbonyl, hydroxyl or chlorine, in particular
CF-C4alkyloxy or hydroxyl.
According to a further preference, component b) can be present as
hydrochloride.
Componc;nt c) is preferably an Me(II) carboxylate, in which Me(II) is Ba, Ca,
Mg, Cd or
Zn. The c:arboxylates are preferably salts of carboxylic acids having 7 to 20
C atoms, for
example benzoates, alkanoates or alkenoates, preferably stearates, oleates,
laurates,
palmitates, hydroxystearates or 2-ethylhexanoates. Stearates, oleates or
p-tert-bmylbenzoates are particularly preferred.
Mixtures of Ba/Zn or CalLn carboxylates are also particularly preferred as
component c).
An Me(Il) phenolate as component c) is in particular a C~-CZp(o-, m- or p-
)alkylphenolate,
for example o-, m- or p-nonylphenolate.
According to a further preference, the compositions according to the invention
contain an
epoxy compound and/or a phosphite as additional component d).
The epoxy compound is preferably an epoxidised oil or an epoxidised fatty acid
ester, for
example epoxidised soya bean oil, epoxidised butyl oleate and epoxidised octyl
oleate.
The phosphites are preferably those of the formula
Al0 O O Al0 CH3
\ / \ \ t
A20-P, Al0-P P-OAZ, P-OCH2CH O, P-OCH2CHOCHCH2 ,
\ / / ~ i i
A30 O O A30 2 OAt CH3 CH3 n
in which A1, A2 and A3, independently of one another, are C4-Ctgalkyl, C6-
Ctgalkenyl,
CS-C~cycloalkyl, phenyl or phenyl which is substituted by one to three Ct-
Ct2alkyl
groups.
Examples are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl,
trioleyl, triphenyl,
tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite. Preference is given
to the aryl
_7_
dialkyl and the alkyl diaryl phosphates, for example phenyl didecyl,
(2,4-di-ten-butylphenyl) didodecyl, (2,6-di-tcrt-butylphenyl) didodecyl
phosphate and the
dialkyl and diaryl pentacrythritol diphosphitcs, for example distearyl
pentaerythritol
diphosphite. Preference is also given to the tetrapheny:l and tetraalkyl [1,2-
dipropylene
glycol] diphosphites and the poly[1,2-dipropylene glycol phenyl phosphates]
and the
poly[1,2-dipropylene glycol alkyl phosphates].
Particularly preferred organic phosphates are distearyl pentaerythritol
diphosphite,
tris(nonylphenyl)phosphite, phenyldidccylphosphite, tetraphenyl [1,2-
dipropylene glycol]
diphosphite and poly[1,2-dipropylene glycol phenyl phosphate].
The Me(II) carboxylates or phenolates are preferably used in amounts of 0.05
to 5% by
weight.
The phosphates are used, for example, in concentrations of 0.3 to 5,
preferably 0.5 to 1,
by weight, and the epoxy compounds, for example epoxidised soya bean oil,
advantageously in concentrations of 1 to 8, preferably 1 to 3, % by weight.
The compounds of the formula I are preferably incorporated in the chlorine-
containing
polymer in amounts of 0.05 to 1 or 0.01 to 0.9, in particular 0.1 to 0.7, % by
weight.
The % by weight given refers in each case to the material to be stabilised.
The chlorine-containing polymers are preferably vinyl chloride homopolymers or
copolymers. Examples of suitable comonomers for the copolymers are: vinyl
acetate,
vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene,
malefic acid,
acrylic acid, fumaric acid, itaconic acid. Further suitable chlorine-
containing polymers are
postchlorinated PVC and chlorinated polyolefins, furthermore graft polymers of
PVC with
EVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned
homo-
and copolymers, in particular vinyl chloride homopolymers, with other
thermoplastic
and/or elastomeric polymers, in particular with ABS, MBS, NBR, SAN, EVA.
Further preference is given to suspension and bulk polymers and to emulsion
polymers.
Polyvinyl chloride is particularly preferred as chlorine-containing polymer.
_g_
The invention further relates to the use of a stabiliser system containing
components b)
and c) for stabilising a chlorine-containing polymer against
thermodegradation.
Depending on the intended use of the polymers, further additives can be
incorporated
before or during the incorporation of the stabilisers, for example phenolic
antioxidants,
lubricants (preferably montan waxes or glycerol esters, fatty acid esters,
paraffins, amide
waxes, stear-ic acid, mono- and dihydroxystearic acid, higher fatty alcohols),
plasticisers,
fillers, carbon black, asbestos, kaolin, talc, glass fibres, modifiers,
(impact-resistant
additives), processing aids (for example polymethacrylic esters), fluorescent
whitening
agents, pigments, light stabilisers, ster-ically hindered amines, UV
absorbers, flame
retardant;> or antistatics.
Further possible additives are furthermore f3-aminocrotonates, for example the
compounds
described in DE-A 804,442, DE-A 807,207 and JP-A 75/17,454, pyrroles, for
example the
compounds mentioned in EP-A 22,087, aminouracils, for example the compounds
disclosed in EP-A 65,934, aminothiouracils, for example the compounds known
from
EP-A 41,479, polyols, for example the compounds described in DE-A 3,019,910,
f3-diketones, for example the compounds mentioned in DE-A 2,600,516,
hydrotalcites, in
particular the compounds described in DE-A 3,843,581, or also mixtures of f3-
diketones
and hydrotalcites, as described in EP-A 63,180, furthermore Mg/Al carbonates,
for
example the Mg/Al carbonates disclosed in JP-A-Sho 62/267,347 (=Chemical
Abstracts
108:168 635 h), and Alcamizers, for example 4 Mg0 A1203.C02.9 H20, 4 Mg0
Ai2O3.C02.6 H20, Zn0 3MgU A1203.C02.8-9 H20, Zn0 3 Mg0 A1203.C02.5-6 H20 and
Mg4A12(t~H)12(C03)t-Xn(C104)xmH20.
Possible additives are also chemical blowing agents for expanded rigid or
plasticised
polyvinyl chloride, for example NaHC03 and the blowing agents mentioned in
"Gachter,~iVliiller; Taschenbuch der Kunststoff-Additive (Handbook of plastic
additives),
Carl Hanser Verlag Munich-Vienna, 2nd edition, 1983" on page 651.
The stabiliser components are most favourably incorporated in the chlorine-
containing
polymer, as is usual, on mixed rolls, for example in a 2-roll mill at
temperatures between
150° and 200°C. In general, sufficient homogenisation can be
obtained within 5 to 1S
minutes. The components can be added individually or together as a premixture.
A liquid
premixture has proven to be advantageous, i.e, the homogenisation is carried
out in the
presence of inert solvents and/or plasticisers.
~~.~~~~'
-9-
The compositions according to the invention can be processed to give moulded
articles by
the moulding processes customary for this, for example by extrusion, injection-
moulding
or calandering. The use of plastisols is also possible.
The compositions according to the invention are preferably used for the
manufacture of
electro cables, hollow articles, for example pipes, and in particular sheets
in the
automobile industry. This use is also provided by the invention. A
particularly preferred
area of application is the manufacture of sheets for the interior of
automobiles, in
particulw for those as described in DE-A 3,227,107 and DE-A 3,401,482.
The compositions according to the invention are particularly advantageously
used for the
manufacture of deep-drawing sheets and flexible sheets based on PVC, in
particular for
the use in the automobile industry.
The compounds of the formula I can be prepared in analogy to known processes.
Preparation processes are described, for example, in the following
publications: D.F.
Walker et al.; J. Am. Pharm. Assoc. 39, 393 (1950), D.W. Kaiser et al.; J. Am.
Chem. Soc.
73, 2984 ( 1951 ), A.B. Borkovec et al.; J. Med. Chem. 10, 457 ( 1967). '
When R has one of the abovementioned meanings other than the group IIb, it is
advantageous to prepare the melamine derivatives by the following scheme:
Scheme ~~
Cl
i
N N base N N
+ RNH~ ---~ ~ + HC1
H2N Y NH2 H2N \N NH2
In general, water is a suitable reaction medium. In some cases, in particular
if R is a
long-chain allcyl radical, it is advantageous to add a solubiliser, for
example
dirnethyhicetamide. The base is, for example, alkali metal hydroxide,
preferably sodium
hydroxid.~.
The melamine obtained can be converted to the corresponding hydrochloride by
heating it
~~~ta~~
- 10-
with concentrated hydrochloric acid (slight excess). Inversely, it is possible
to obtain again
the melamine from the hydrochloride by treating with, for example, alkali
metal hydroxide
or alkali metal bicarbonate solution, which would constitute a further
purification step.
In some eases, it is also possible to prepare compounds of the formula I in
which R is a
group of the formula IIb by the above scheme A; however, in these cases, the
basicity of
the amine; must be higher.
Compounds of the formula I in which R is a group of the formula IIb are
preferably
prepared by Scheme B given below.
Scheme 13:
Cl NHR
N /~ N HCl N ~ N
+ RNH2 ----~ ~ HCl
H2N N NH2 H2N N NH2
In this case, too, water is a suitable reaction medium, it being possible, if
required, to add
again a solubiliser. The hydrochloride is advantageously converted into the
corresponding
melamine; derivative as described above.
In general, the compounds of the formula I and their hydrochlorides have a
defined
hydrated water content.
The starting materials are commercially available or can be prepared in
analogy to
processes known to one skilled in the art. The preparation of
diaminochlorotriazine is
described, for example, by J.T. Thurston et al. in "J. Am. Chem. Soc. 73, 2981
(1951)".
The compounds of the formula I can also be used against photolytic degradation
of
chlorine-containing polymers.
The invention also relates to the novel compounds of the formula Ia and
hydrochlorides
thereof,
-11-
NIiR
N i 'N
(la)
HZN \N NHZ
in which R is C~-Cttphenylalkyl which is substituted on the phenyl by 1 to 3
radicals, the
radicals, independently of one another, being hydroxyl, chlorine, Ct-C4alkyl,
methoxy or
ethoxy, or R is furthermore a group of the formula lIa, II-b-1, II-b-2 or II-b-
3,
Y1 . ~ Y4.
- CH2- CH- CH2-X ,
I
OH Y2 YS Y8
Y3 1'6 Y9
(IIa) (II-b-1) (II-b-2) (II-b-3)
in which X is Cl-C2oalkyloxy, Ct-C2oalkylthio, phenyloxy, phenylthio,
benzyloxy or
benzylthio, Yt, Y2 and Y3, independently of one another, are Ct-Czoalkylthio,
C2-Ct2allcyloxycarbonyl or mercapto, and Yt and Y2 are additionally hydrogen,
Y4 is
methoxy, ethoxy or hydroxyl, YS and Y6, independently of one another are Ct-
C2palkyl,
Ct-C2palkyloxy, Cl-CZpalkylthio, C2-Ct2alkyloxycarbonyl, C2-Ct2alkanoyl,
phenyl,
phenyloxy, phenylthio, hydroxyl, mercapto or chlorine, and YS is additionally
hydrogen,
Y~, Yg and Y9, independently of one another, are C2-C2ealkyl or C2-
Ct2alkyloxycarbonyl
and Yg is additionally hydrogen.
For the compounds of the formula Ia, the same preferences apply as for the
compounds of
the formula I, and the radicals Yt to Y9 correspond to the radicals Rt to R3.
The examples which follow illustrate the invention in more detail. Parts and
percentages
are by weight, unless stated otherwise.
Example 1: Preparation of N-(n-dodecyl)melamine (Com_pound 1-A-1).
A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 19.5 g (0.105 mol) of
n-dodecylamine and 4.0 g (0.1 mol) of sodium hydroxide in 200 ml of water is
refluxed
for 5 hours. The solid formed is filtered off with suction, washed until free
of chloride and
then treated with a mixture of methylene chloride/ether (1:1). The precipitate
is filtered off
and boiled in dimethylformamide. After filtration, the concentrated filtrate
is poured into
~, 5'~ F~ (''~ f
~~e~c.7~
-12-
water with stirring. The precipitate formed is dried to constant weight. The
yield is 65% of
theory. The product contains 0.1 mol of hydrated water per mole of melamine
and melts at
119°C.
Example 2: The compounds in Table 1 are prepared in analogy to the process
described in
Example 1.
Table l:
NHR
N i 'N
H2N~N- _NH2
Compound
No. R Melting Yield [% of theory]
point
1-A-2 -(CH2)3-OH160C 87
1-A-3 -(CH2)5-OH- -
1-A-4 -CH2-CH=CH2172C 57.2 (The product is present
in the form of
a hydrate (0.25 mol of
H20 per mol
of melamine).
66 (After recrystallisation
from acetic
acid. The product is present
in the
1-A-$ ~ 146
C
form of a hydrate (0.6
mol of F120
per mol of melamine).)
-A-6 CH2
i ~ i i
2J P~ ~ r9
- 13-
Example 3: Preyaration of N-benzylmelamine ~drochloride (Com-pound 1-A-7)
10.8 g (0.05 mol) of compound 1-A-6 are refluxed tol;ether with 6.84 g (0.06
mol) of 32%
hydrochloric acid for 1 hour with stirring. The clear solution is Gaoled to
0°C, and the
crystals formed are filtered off, washed and dried. The yield is 73.8% of
theory. The
product has a melting point of 275°C.
Example 3a: Preparation of N-f3-(2'-ethylhexyl)oxy-2-hydroxypropyllmelami_ne
Com ound 1A-8).
A mixture of 29.1 g (0.2 mol) of diaminochlorocriazine, 40.7 g (0.2 mol) of
3-(2'-ethylhexyl)oxy-2-hydroxypropylamine and 300 ml of water is refluxed. 0.2
mol of
NaOH in 80 ml of water are added dropwise over a period of 1 hour. The
reaction mixture
is then refluxed for 2 hours. 25 ml of concentrated hydrochloric acid are
added to the
resulting oil, giving a clear solution. Upon cooling, the hydrochloride of
N-[3-(2'-ethylhexyl)oxy-2-hydroxypropyl]melamine precipitates and is ehen
neutralised
with NaFIC03 at 40°C. The wax-like product obtained is washed until
free of chloride
with ice water and dried in vacuo. The yield is 86.6% of theory. The product
has a melting
point of 1.09 - 115°C.
Example 3b: Preparation of N-n-hexylmelamine (Compound 1-A-9).
The prep;~ration is carried out in analogy to Example 3a. The yield is 70.8%
of theory. The
product has a melting point of 116-119°C.
Example 4: Preparation of N-phenylmelamine (= Compound 2-A-1)
A mixture of 14.6 g (0.1 mol) of diaminochlorotriazine, 9.8 g (0.105 mol) of
aniline and
4.0 g (0.1 mol) of sodium hydroxide in 30 ml of water is refluxed for 2 hours
with the
addition of 200 ml of water. The cloudy solution is cooled, the precipitated
solid is filtered
off, washed until free of chloride and dried to constant weight. The product
obtained is
purified by dissolving it in glacial acetic acid and then treating it with
bicarbonate. The
yield is 62% of theory. The product has a melting point of 202°C.
Example 5: The compounds listed in Tables 2a to 2c are prepared in analogy to
the
process described in Example 4. The data given in Tables 2a to 2c refer to the
general
formula liven below.
ih!
- 14-
NHR
N i 'N . (HCI)n
H2N ~ N ~ NH2
Table 2a;
Comp. n R Melting point Yield [3'0
No. of theory]
2a-A-1 0 163'C 9g (The productis
present as
a
OCH3 hemihydrate.)
2a-A-2 0 184'C 96
OCH3
2a-A-3 0 ~ a OCH3 205'C 95
2a-A-4 0 ~ ~ 260'C 76 (After
re-
crystallisation
from
ethanol.)
OH
2a-A-5 1 271'C 36 (The product
is
present as
a
hydrate (1.3
mol
of H20 per
OH mol
of melamine).)
2a-A-6 0 ~ 288'C 39 (~~r re-
~
OH crystallisation
~ from methanol.)
-15-
Table 2b:
Comp. n R Melting point Yield [% of
No. theory]
2b-A-1 0 ~ ~ OCH3 215C 97
OCH3
Table 2c:
Comp. n R Melting Yield [% of theory]
No. point
CH3
70 (After recrystallisation
from ethanol/watcr.
2c-A-1 0 200C The product is
present
as a hemihydratc.)
OH
C1 '
58 (After recrystallisation
from ethanol/water.
2c-A-2 0 240C The productis
present
as a hydrate
(0.75 mol
of H20 per mol
of
OH melamine).)
Example 6: Preparation of N-phenylmelamine (Compound 1-B-1 (=2-A-1)).
A mixture of 19.7 g (0.135 mol) of diaminochlorotriazine, 15.5 g (0.140 mol)
of aniline,
1.3 ml of cone. hydrochloric acid (catalyst) is refluxed in 200 ml of water
for 1 hour with
stirring. The solution is filtered, and the filtrate is neutralised with cone.
sodium
bicarbonate solution (pH = 7.2). The precipitate formed is filtered off with
suction,
washed until free of chloride and dried to constant weight. The product
obtained has a
melting point of 206°C. The yield is 86.4% of theory.
Example 7: Preparation of N-phen~ elamine hemihydrochloride (Comp_ound 1-B-2).
A mixture of 36.4 g (0.25 mol) of diaminochlorotriazine, 24.4 g (0.26 mol) of
aniline and
7 ml of concentrated hydrochloric acid is refluxed in 500 ml of water for 1
hour. The
solution is filtered, and the filtrate is cooled. The colourless crystals
obtained are washed
and dried to constant weight. The yield is 68.3% of theory. The product has a
melting
point of 259°C and is present as a dehydrate.
~~~~~:~~~
- 16-
Example ~: The compounds in Table 3a to 3d are prepared in analogy to the
process
described in Example 6 or 7. The data given in Table 3a to 3d refer to the
general formula
given below.
IYHR
N N ~ (ilCl)n
H2N ~ N ~ NH2
-17-
Table 3a:
Comp. n K Melting yield [lo of tltcoryJ
No. point
~- 65 (The product
~ ~ is present in
3a-B-1 0 210C the form of a hydrate
(0.1 mol of H20
per mol of
CH3 mclatninc).)
/ ~
3a-B-2 0 220C 88.2 (The product
is present as
a hydrate (0.2 mol
of H20
CH3 per mol of melamine).)
3a-B-3 0 ~ ~ Chl 290C 83.8 (The product
is present as
3 a hydrate (0.15
mol of H20
per mol of melamine).)
/ \
3a-B-4 0 C4H9- 161C 43 (After rccrystallisation
from methanol.)
3a-B-5 0 ~ ~ 250C 76
C4H9_t
3a-B-6 0 ~ ~ 80C 81 (Addition of
dimcthyl-
acetamide. The product
is
S-C 16H33-n
present as a sesquihydrate.)
75 (In the reaction,
3a-B-7 0 320C the free
~ ~ acid is also formed,
(decomposition)which
can be separated
off by
customary methods.
The
COOCH3 product is present
as a
hydrate (U.2 mol
of H20
per mol of melamine).)
_z
Table 3a continued:
Comp. n k Melting Yield [% of theory]
No. point
5g (After recrystallisation
3a-B-80 / \ 165C from acetic acid.
The product
is pxescnt as a hydrate
COOC2IIS (0.2 mol of 1I20
per mol
of melamine).)
2g (Addition of dintethylacetamide.
3a-B-90 190C The product is present
as a
hydrate (0.1 mol
of 1-I20 per
COOC4H9-n of melamine).)
/
3a-B-100 \ COOC4H ~-n 280C
77
/ \
64 (Prepared by trans-
3a-B-110 152C
cstcrification of
3a-B-7 in
COOC8H17-i the presence of Ti(OC~4H9)4.)
*)
3a-B-120 / \ 65C 36.5 (Prepared by
trans-
esterification of
3a-B-8 in
the presence of Ti(OC4H~)4.
COOC8H17-' Purified by recrystallisation
from methylene chloride/
petroleum ether).
3a-B-130 ~ ~ 160C 43.8 (Addition of
dimethyl-
acetamide.)
COOC1pH21-n
73.1 (After recrystallisation
from
water in the presence
3a-B-141 ~ 294C of
activated carbon.
The
product is present
as a hydrate
OH (0.8 mol of H20 per
mol of
melamine).)
*) -C8H17-i- 2-ethylhexyl
-19-
Table 3a continued:
Comp. n R Melting Yicld [3'0 of theory]
No. point
9 (~op~od from the
89
3a-B-150 242C .
hydrochloride with
bicarbonate solution).
OH
73.8 (After recrystallisation
~ ~ from water in the
3a-B-161 OH 290C presence of activated
carbon. The product
is
present as a monohydrate.)
3a-B-170 278C 49.3 (Addition of
dimcthyl-
acetamide. The product
is present as a
hemi-
gH hydrate.)
89.8
3a-B-I80 203C
CI
85.0
3a-B-190 165C
C1
87.9
~
3a-B-200 Cl 23gC
~~C~~~~
-20-
Tabie 36:
Comp. n R Melting yield [~S'o of
No. point thcoryl
CFI3
36-B-1 0 ~ ~ 260C 78.2 (The product
is present as
_ a hydrate (1.2
mol of H2O
per mol of melamine).)
CH3
3b-B-2 0 / \ ~1C 76.8 (The product
is present as
a
hydrate (0.15 mol
of H20
per mol of melamine).)
CH3 CH3
3b-B-3 0 ~ ~ CH3 233C 87.0 (The product
is present as
a hydiate (0.15
mol of
CH H20 per mol of
3 melamine).)
gg,g (The product
/ \ is present as
a
3b-B-4 0 CH3 260C hydrate (0.1 mol
of H20 per
mol of melamine).)
CH3
CHg
~- 80 (The product
is present as
a
36-B-5 0 ~ ~ 277C hydrate (O.1S mol
of H20
per mol of melamine).)
CHg
CH3
gg,5 (fhe product
is present as
a
3b-B-6 0 ~ ~ ~O.C hydrate (0.1 mol
of H20
per mol of melamine).)
CHg
3b-B-7 1 ~ ~ OCH3 26S'C 61.5 (bet recrystallisation
from
water in the presence
of
activated carbon.
The
OCH~ product is present
as a
monohydrate.)
OCH3
76.0 (After recrystallisation
from
water in the presence
of
3b-B-8 1 256'C activated carbon.
The
product is present
as a
OCH hydrate (0.2 mol
of H20 per
mol melamine).)
-21 -
Table 3b continued:
Comp. n R Mciting Yield [~% of thcory~
No. point
OCH3 99.0 (Prepared
by treating
3b-B-9 0 ~ ~ Ig6C 3b-B-g with bicarbonate
solution.)
OCH3
OCH3 71.4 (After rccrystallisation
3b-B-10 1 ~ ~ 277C from water in
dte presence
of activated carbon.)
OCH3
OCH3 87.0 (Prepared
by treating
3b-B-11 0 103C 3b-B-10 with bicarbonate
/ \ solution. This
product is
present as a monohydrate.)
OCH3
79.5 (After recrystallisation
3b-B-12 1 OCH3 - from water in
the presence
of activated carbon.
The
OCH3 product is present
as a
hydrate (0.2 mol
of H20
per mol of melamine).)
99.4 (Prepared
~ ~ by treating
3b-B-13 0 OCH3 22SC 3b-B-12 with bicarbonate
solution. The
product is
OCH3 present as a hydrate
(0.2
mol of H20 per
mol of
melamine).)
COOCH3 50 ('I7te product
is present
as a hemihydrate.)
3b-B-14 0 ~ ~ 267C
COOCH3
COOC8H17-i 51 (Prepared by
Iransesterifi-
cation of 36-$-14
in the
3b-B-15 0 ~ ~ g9C presence of Ti(OC4H9)4.
Purification by
recrysLal-
lisation from
methylene
COOCgHI7-i chloride/ether.)
~j .T ra
J~ ~~
-22-
Table 3b continued
Comp. n R Melting Yield [Wo of theory)
No. point
85.0 (Addition
/ \ of dimcthyl-
3b-B-160 Cl 245'C acetamide.The
product
is present as
a hydrate
C1 (0.25 mol of H20
per
mol of melamine).)
Cl
3b-B-170 / \ 80.1 (Addition
234'C of dimcthyl-
aCCCamIdC).
Cl
C1
86.2 (Addition
~ \ of dimcthyl-
36-B-180 228C acetamide).
C1
3b-B-190 / \ 229'C 85.5 (Addition
of dimethyl-
acetamide).
C1 C1
81.3 (Addition
of dimethyl-
3b-B-200 ~ ~ CI 201'C acetamide).
C1
-23-
Table 3c:
Comp. n ~ Melting Yield [9'0 of theory]
No. point
3c-B-1 0 . ~ ~ O1~ 257C 61 (The product
is present as
a hydrate (0.7
mol of
H20 per mol of
melamine).)
CH3
/ \
3c-B-2 0 Crl3 255C ~ 80 (The Pr~uct
is present as
a hydrate (0.15
mol of H20
OH per mol of melamine).)
3c-B-3 0 ~ ~ CH3 232C 69.0 (The product
is present as
a hydrate (0.25
mol of
H20 per mol of
melamine).)
OH
3c-B-4 0 ~ ~ OCH3 240C ~' 70 (The product
is present as
a hydrate (0.25
mol of
OH
f120 per mol of
melamine).)
, \
3c-B-5 0 ~H3 262'C 75.2 (The product
is present as
a
hydrate (0.1 mol
of H20
CH per mol of melamine).)
3
CH3
3c-B-6 0 ~ ~ 268'C 89~ ~e Pr~uct is
present as a
hycfrate (0.15
mol of H20
OCH3
per mol of melamine).)
~~~~~~'~
-24-
Table 3d:
Comp. n R Melting Yield [!o of
No. point theory]
OCI-I3
230C (ACter84.3 (The product
purifi- is present
3d-B-1 0 OCH3 canon via as a hcmihydrate.
the hydro-
-~ chloride
210C.)
OCH3
77,4 (Prepared
by treating
OCH3 3d-B-1 with HCl.
Recrystallisation
from
3d-B-2 I ~ ~ 258C water in the
presence of
OCH3 activated carbon.
The
product is present
as a
OCH3 hydrate (0.75
mol of H20
per mol of melamine).)
C1
30.1 (Addition
of dimethyl-
3d-B-3 0 ~ ~ Cl 200C acetamide. Purifjcation
by rcprecipitation
using
dimethyl sulfoxidc/I-I20).
CI .
22.1 (Addition
of dimethyl-
3d-B-4 0 Cl 150C acetamide. Purification
by reprecipitation
using
dimethyl sulfoxide/H20).
Cl Cl
i
CI
91,7 (The productis
/ \ present
3d-B-5 0 OH > 300C as a hydrate
(0.4 mol of
H2U per mol of
Cl melamine).) I
I
Example 9: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17
parts of
dioctyl phthalate, 3 parts of epoxidised Soya bean oil, 0.33 part of zinc
oleate, 0.53 part of
barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44 part
of ~SHELL
SOL A (aromatic hydrocarbon mixture) and 0.2 part of the melamine derivative
listed in
Tables 4a to 4h is rolled on mixing rolls at 190°C for 5 minutes. Test
specimens of the
0.3 mm thick rolled sheet formed are subjected to thermal stress at
180°C in a test oven
-2S-
(~Mathi:; Thermotester). After the interval given, the: "yellowness index"
(YI) according
to ASTM D 1925 is determined on a test specimen. The results are listed in
Tables 4a
to 4h.
Table 4a:
Mclamina YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 9.2 17.6 16.8 15.7 13.8
Compow~d 4.1 5.1 5.2 5.3 6.3
2a-A-4
Compowid 2.0 8.1 7.7 7.8 8.3
3a-B-14
Table 4b:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 10.4 14.4 15.4 16.6 16.8
Compow~d 5.5 6.7 6.6 7.7 9.0
1-A-6
Table 4c:
Melamin~: YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 9.7 12.3 14.6 16.3 17.0
Compowtd 5.7 7.7 7.9 7.7 8.2
3a-B-18
Compowtd SS 6S 6.5 7.0 7.4
3a-B-19
Compowtd
3a-B-20 5.3 6.0 6.5 7.0 7.3
~~~~~Y~z
-2f>-
Table 4d:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 9.8 12.0 13.5 15.8 17.1
Compound 5.7 6.4 7.4 7.5 7.8
~
3a-B-1
Compound 5.4 6.5 6.7 7.0 7.3
3a-B-2
Compound
3a-B-3 5.3 7.0 7.5 7.4 7.6
Compound
3a-B-4 5.2 6.3 6.6 7.0 7.0
Compound
3a-B-5 5.6 7.3 7.3 7.6 8.3
Table 4e:
Melamine n
derivative after
exposure
time
in
minutes
0
5
10
IS
20
without 9.0 14.8 16.7 17.4 17.1
Compound 3,3 4.5 5.0 5.5 6.5
3b-B-1
Compound 3.2 4.8 4.7 5.1 5.6
3b-B-2
Compound
3b-B-3 2.9 4.4 5.0 5.2 5.8
Compound
3b-B-4 3.3 3.6 4.2 4.6 5.5
Compound
3b-B-5 2.7 3.5 3.7 4.7 4.9
-27-
Table 4f:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 8.4 13.8 15.0 16.3 16.5
Compound
3.0 4.4 4.6 4.9 5.9
1-A-5
Table 4g:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without
8.3 13.7 15.1 17.6 17.9
Compound
3.1 4.3 4.6 5.0 5.8
3a-B-8
Compound 3.p 5.1 6.0 6.1 6.3
3 a-B-10
Compotmd
4.3 5.2 5.7 6.6 7
7
3a-B-II .
Compound
3.8 5.6 6.2 6.7 8
2
3b-B-l.i .
Compotmd
4.3 5.7 5.9 7.1 7.6
3b-B-15
Table 4h:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 10,7 16.4 18.3 17.9 17.9
Compound 3.5 4.8 5.2 5.9 6.4
3b-B-2')
Compound 3.1 4.2 5.0 5.2 6.1
3b-B-6
~~~~~'~~
-28-
Example 10: A dry mixture comprising 100 parts of P'VC ( ~2 Solvic 2~4 GA), 3
parts of
epoxidised Soya bean oil, 0.35 part of calcium stearate, 0.15 part of zinc
stearate, 0.55 part
of diisodecylphenyl phosphite, and 0.3 part of the melamine derivative listed
in Tables Sa
to 5k is rolled on mixing rolls at 180°C for 5 minutes. Test specimens
of the 0.3 mm thick
rolled sheet formed are subjected to thermal stress at 180°C in a test
oven (~Mathis
Thermotester). After the interval given, the "yellowness index" (YI) according
to ASTM
D 1925 is determined on a test specimen. The results are listed in Tables 5a
to 5k.
Table Sa:
Yl
after
exposure
time
in
minutes
Melamine
derivative
0
5
10
IS
20
25
30
without 20.1
25.1
29.9
31.8
28.1
31.6
62.8
Compound
2a-A-3 2.6 4.7 4.0 6.9 10.5 18.7 35.7
Table Sb:
Melamine YI
derivative after
exposure
time
in
minutes
0
S
10
15
20
without 19.5 27.6 30.5 33.4 30.2
I
Compound 3.4 4.9 5.9 7.6 12.8
1-A-8
Table 5c:
Melamine YI
derivative after
exposure
time
in
minutes
I
0
S
10
15
20
without 22.4 37.4 38.5 36.9 41.2
Compound 2.7 7.1 10.3 14.7 24.5
3a-B-19
Compound 3.2 8.3 10.6 15.0 24.7
3a-B-20 ~
~~3~~'~2
-29-
Table Sd:
Melamine n
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 1G.9 36.6 36.4 34.9 53.3
Compotutd
36-B-5 2.5 10.4 12.8 16.6 26.6
Table Se:
Melamine n
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 17.5 36.2 36.8 345 33.3
Compound
3d-B-1 1.9 4.8 6.8 10.0 15.8
Table Sf:
Melamine n
derivative after
exposure
time
in
minutes
0
5
10
IS
20
without 18.0 38.3 38.5 34.7 37.0
Compottrtd
2c-A-1 3.6 6.1 8.8 13.3 18.2
Table SQ:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
IS
20
without 16.3 37.8 38.2 34.2 44.7
Compotutd
3a-B-12 2.8 7.0 9.4 14.0 23.7
-30-
Table Sh:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without . 17.5 36.3 37.4 57.2 79.0
Compotutd
2a-All 3.2 9.2 11.8 16.6 21.8
Compound
3 a-B-15 3.1 I 1.1 13.1 17.6 24.
I
Table Si:
Melamim: YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 15.7 36.2 37.3 49.3 74.0
Compotutd
3a-B-13 6.2 11.4 12.6 15.6 20.6
Table Si:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 17.0 38.4 37.5 33.8 44.5
Compound
36-B-11 .2.1 6.6 8.5 10.6 12.8
t I t
Table Sk:
Melamine YI
derivative after
exposure
time
in
minutes
0
5
10
15
20
without 15.0 32.1 37.7 36.9 31.8
Compotmd
3b-B-20 1.5 5.0 5.7 7.4 11.9
-31
Example 11: A dry mixture comprising 100 parts of S-PVC (~Vinnol H 70 DF), 17
parts
of dioctyl phthalate, 3 parts of epoxidised soya bean oil, 0.33 part of zinc
oleate, 0.53 part
of barium p-(t-butyl)benzoate, 0.7 part of diisodecylphenyl phosphite, 0.44
part of
butyldiglycol and 0.2 part of the melamine derivative listed in Table 6 is
rolled on mixing
rolls at 190°C for 5 minutes. Test specimens of the 0.3 mm thick rolled
sheet formed are
subjected to thermal stress at 180°C in a test oven (~Mathis
Thermotester). After the
interval given, the "yellowness index" (YI) according to ASTM D 1925 is
determined on a
test specimen. The results are listed in Table 6.
Table 6:
Melamine
derivativeYI
after
exposure
time
in
minutes
0
5
10
15
20
25
30
35
40
45
without 9.211.613.615.2 18.518.7 17.415.9 14.6 15.1
Compound
2a-A-3 2.83.0 3.2 3.7 3.8 4.3 5.2 5.1 5.5 7.7
