Note: Descriptions are shown in the official language in which they were submitted.
_ , _ ;~c~s:~sss
A-18442/A/CGM 378
Stabilised chlorine-containing polymers
The invention relates to stabilised chlorine-containing polymer compositions
which
contain a sterically hindered amine in combination with other stabilisers.
It is known that sterically hindered amines, for example derivatives of
2,2,6,6-tetramethylpiperidine, are excellent stabilisers for polymers against
damage by
short-wave light. However, addition of sterically hindered amines of this type
to polyvinyl
chloride or other chlorine-containing polymers frequently results in
discoloration during
processing or on use. Only addition of costabilisers allows this discoloration
to be
prevented or reduced.
Thus, JP-A-82/168 933 describes films made from plasticised polyvinyl chloride
which
are protected against light by means of a sterically hindered amine and a UV
absorber and
contain, as costabilisers, zinc stearate, barium stearate and epoxidised soya
oil.
JP-A-86/163 965 describes the stabilisation of PVC by means of a sterically
hindered
amine, a calcium/zinc stabiliser and epoxidised Soya oil.
EP-A-237 485 recommends a combination of sterically hindered amines and
organotin
stabilisers for stabilising rigid PVC, with further possible additives being
titanium dioxide
and calcium stearate. EP-A-421 933 proposes a combination of sterically
hindered amines
and zinc compounds and a hydrotalcite for stabilising chlorine-containing
polymers,
where further possible additives are 1,3-diketones and calcium compounds.
EP-A-432 096 proposes a combination of sterically hindered amines and zinc
compounds
and a blowing agent or foaming agent, it also being possible to use calcium
compounds
and 1,3-diketones.
It has now been found that stabiliser combinations of this type give very
satisfactory
results, even without organotin stabilisers and without hydrotalcite and
without blowing
agents or foaming agents, if they contain a zinc compound, a calcium,
magnesium or
barium compound and a 1,3-dicarbonyl compound.
2 - ~C~~.~'.J~J
The invention therefore relates to a stabilised chlorine-containing polymer
composition
comprising
a) at least one chlorine-containing polymer,
b) at least one sterically hindered amine,
c) at least one organic or inorganic zinc compound,
d) at least one organic or inorganic calcium, magnesium and/or barium
compound, and
e) at least one 1,3-dicarbonyl compound,
but no organotin compounds, no hydrotalcite compounds and no blowing agents or
foaming agents.
The chlorine-containing polymer may be, for example, a polymer or copolymer of
vinyl
chloride or of vinylidene chloride or a post-chlorinated polymer or copolymer
of vinyl
chloride or of vinylidene chloride, a chlorinated polyolefin, for example a
chlorinated
polyethylene, a chlorinated polymer or copolymer of styrene or of butadiene or
a
chlorinated rubber or a rubber hydrochloride, or a mixture of a chlorine-
containing
polymer of this type and another chlorine-containing or chlorine-free polymer.
The
chlorine-containing polymer is preferably a polyvinyl chloride or a copolymer
containing
at least 80 % of vinyl chloride or a mixture (polyblend) of a homopolymer or
copolymer
of this type with another chlorine-containing or chlorine-free polymer. The
chlorine-containing polymer may be an emulsion, suspension or bulk polymer.
The sterically hindered amine is preferably a polyalkylpiperidine derivative
and preferably
contains at least one group of the formula I
RCH2 CH3 R
-N
RCH2 ~CH3
in which R is hydrogen or methyl, and is in particular a derivative of
2,2,6,6-tetramethylpiperidine of the formula I in which R is hydrogen. These
compounds
are preferably substituted in the 4-position of the piperidine ring by one or
two polar
groups or by one spiro ring system. These compounds may be low-molecular-
weight or
oligomeric or polymeric compaunds.
~CI~ vSDJ
-3-
The following classes of polyalkylpiperidines are particularly important:
a) Compounds of the formula II
RCH2 CH3 R
Rtt N O Rt2
II
RCH2 CH3
n
in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or
methyl, Rt l is
hydrogen, oxyl, hydroxyl, Ct-Ct2alkyl, C3-Cgalkenyl, C3-Cgalkynyl, C~-
Ct2aralkyl,
Ct-Ct8alkoxy, CS-CBCycloalkoxy, C~-Cgphenylalkoxy, Ct-Cgalkanoyl, C3-
Csalkenoyl,
Ct-Cl8alkanoyloxy, benzyloxy, glycidyl or a -CH2CH(OH)-Z group in which Z is
hydrogen, methyl or phenyl, Rtt preferably being H, Ct-C4alkyl, allyl, benzyl,
acetyl or
acryloyl, and Rt2, if n is 1, is hydrogen, Ct-Ctgalkyl, which may be
interrupted by one or
more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an
aliphatic,
cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic
acid or
phosphorus-containing acid, or a monovalent silyl radical, preferably a
radical of an
aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic
carboxylic acid
having 7 to 15 carbon atoms, of an a,(i-unsaturated carboxylic acid having 3
to 5 carbon
atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms; if n is
2, Rt2 is
Ct-Ct2alkylene, C4-Ct2alkenylene, xylylene, a divalent radical of an
aliphatic,
cycloaliphatic, araliphatic or aromatic dicarboxyli~ acid, dicarbamic acid or
phosphorus-containing acid, or a divalent silyl radical, preferably a radical
of an aliphatic
dicarboxylic acid having 2 to 36 carbon atoms, of a cycloaliphatic or aromatic
dicarboxylic acid having 8 to 14 carbon atoms or of an aliphatic,
cycloaliphatic or
aromatic dicarbamic acid having 8 to 14 carbon atoms; if n is 3, Rt2 is a
trivalent radical
of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic
tricarbamic
acid or of a phosphorus-containing acid, or a trivalent silyl radical; and if
n is 4, R12 is a
tetravalent radical of an aliphatic, cycloaliphatic or aromatic
tetracarboxylic acid.
Any Ct-Ct2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-
butyl, sec-butyl,
~~IUvi~~a~
-4-
tort-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-
dodecyl.
Ct-Ctxalkyl Rtt or Rt~ is, for example, one of the abovementioned groups or,
for example,
n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
C3-CBalkenyl Rt t may be, for example, 1-propenyl, allyl, methallyl, 2-
butenyl, 2-pentenyl,
2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
C3-CBalkynyl Rt t is preferably propargyl.
C~-Ct2aralkyl Rt t is, in particular, phenethyl or especially benzyl.
Ct-CBalkanoyl Rt t is, for example, formyl, propionyl, butyryl or octanoyl,
preferably
acetyl, and C3-Csalkenoyl Rt t is, in particular, acryloyl.
A monovalent carboxylic acid radical Rt2 is, for example, an acetic acid,
caproic acid,
stearic acid, acrylic acid, methacrylic acid, benzoic acid or
(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid radical.
A divalent dicarboxylic acid radical Rt2 is, for example, a malonic acid,
succinic acid,
glutaric acid, adipic acid, suberic 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
radical.
A trivalent tricarboxylic acid radical Rtz is, for example, a trimellitic
acid, citric acid or
nitrilotriacetic acid radical.
A tetravalent tetracarboxylic acid radical Rt2 is, for example, the
tetravalent radical of
butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
A divalent dicarbamic acid radical Rt2 is, for example, a
hexamethylenedicarbamic acid
or 2,4-toluylenedicarbamie acid radical.
Preference is given to compounds of the formula II in which R is hydrogen, Rtt
is
hydrogen or methyl, n is 2 and Rt2 is the diacyl radical of a dicarboxylic
acid having 4 to
~C~..'~'.:~JE~J
_5_
22 carbon atoms.
The following are examples of polyalkylpiperidine compounds of this class:
I ) 4-hydroxy-2,2,6,6-tetramethylpiperidine
2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
3) I-benzyl-4-hydroxy-2,2,6,6-tetramethylpipeiidine
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-pentamethylpiperidin-4-yl ~i-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate
9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)maleate
10) di(2,2,6,6-tetramethylpiperidin-4-yl)succinate
I1) di(2,2,6,6-tetramethylpiperidin-4-yl)glutarate
12) di(2,2,6,6-tetramethylpiperidin-4-yi)adipate
13) di(2,2,6,6-tetramethylpiperidin-4-yl)sebacate
14) di(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate
15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)sebacate
16) di(1-a:lyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate
17) 1-hydroxy-4-(3-cyanoethyloxy-2,2,6,6-tetramethylpiperidine
18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate
20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate
22) di(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate
23) di(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl(3,5-di-ten-butyl-4-
hydroxybenzyl)
malonate
24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
25) di(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
26) hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)
27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
28) tetra(2,2,6,6-tetramethylpiperidin-4-yl) butanetetracarboxylate
29) tetra(I,2,2,6,6-pentamethylpiperidin-4-yl) butanetetracarboxylate
30) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate
- 6 - 2~~ 3J~J
32) phenyl bis-(1,2,6,6-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) I-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
b) Compounds of the formula III,
RCH2 CH3 R
R13
Rlt N N R14
III
RCH2 CH3
n
in which n is the number 1 or 2, R and R11 are as defined under a), R13 is
hydrogen,
Cl-Cl2alkyl, C2-Cshydroxyalkyl, CS-C~cycloalkyl, C~-C8aralkyl, C2-Clgalkanoyl,
C3-Csalkenoyl, benzoyl or a group of the formula
RCH2 CH3 R
Ril N
RCH2 \CH3
and, if n is l, R14 is hydrogen, Cl-Clgalkyl, C3-Csalkenyl, CS-C~cycloalkyl,
Cl-C4alkyl
which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group,
glycidyl, a
group of the formula -CHZ-CH(OH)-Z or of the formula -CONH-Z in which Z is
hydrogen, methyl or phenyl; if n is 2, R14 is Gz-Cl2alkylene, C6-Cl2arrlene,
xylylene, a
-CH2-CH(OH)-CH2 group or a -CHZ-CH(OH)-CH2-O-D-O- group in which D is
C2-Clpalkylene, C6-Clsarylene or C6-Clzcycloallylene, or, with the proviso
that R13 is not
alkanoyl, alkenoyl or benzoyl, R14 is alternatively a divalent radical of an
aliphatic,
cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or may
alternatively be the
-CO- group, or, if n is I, R13 and R14 together may be the divalent radical of
an aliphatic,
cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
~
C; ~~ t-' r
I4i~.~....1J~J
.Any C~-C~~alkyl or C~-C~~alkyl substituents are as defined above under a).
Any CS-C~cycloalkyl substituents are, in particular, eyclohexyl.
C~-CBaralkyl Rt3 is, in particular, phenylethyl or especially benzyl.
C2-Cshydroxyalkyl Rt3 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
C2-CtBalkanoyl Rt3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl,
hexadecanoyl or octadecanoyl, but preferably acetyl, and Cg-Csalkenoyl Rt3 is,
in
particular, acryloyl.
C2-Cgalkenyl Rt4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-
hexenyl or
2-octenyl.
Ct-C4alkyl Rt4 which is substituted by a hydroxyl, cyano, alkoxycarbonyl or
carbamide
group may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl,
methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or
2-(dimethylaminocarbonyl)ethyi.
Any C2-Ct2alkylene substituents are, for example, ethylene, propylene,
2,2,-dimethylpropylene, tetramethylene, hexamethylene, octamethylene,
decamethylene or
dodecamethylene.
Any C6-Ctsarylene substituents are, for example, o-, m- or p-phenylene, 1,4-
naphthylene
or 4,4'-diphenylene.
C6-Ct2cycloalkylene D is, in particular, cyclohexylene.
Preference is given to compounds of the formula III in which n is 1 or 2, R is
hydrogen,
Rtt is hydrogen or methyl, Rt3 is hydrogen, Ct-Ct2alkyl or a group of the
formula
~C~~~J~J
_g_
Rcn, ctt; R
Rtt N
RCH2 \CH3
and, if n is 1, Rt4 is hydrogen or Ct-Ct2alkyl and, if n is 2, Rt4 is C2-
CBalkylene.
The following are examples of polyalkylpiperidine compounds of this class:
37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yi)hexamethylenel,6-diamine
38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenel,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)-succinamide
45) di(2,2,6,6-tetramethylpiperidin-4-yl)
N-(2,2,6,6-tetramethylpiperidin-4-yl)-(3-aminodipropionate
46) The compound of the formula
CH3 CH3
C4H9
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
2~'5~5~5
_g_
47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine
48) 4-(3-methyl-4-hydroxy-5-ten-butylbenzamido)-2,2,6,6-tetramethylpiperidine
49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine
c) Compounds of the formula IV
RCH2 CH3 R
O
Rtt - N R15
IV
0
RcH2 cH3
n
in which n is the number 1 or 2, R and Rt t are as defined under a), and, if n
is 1, Rts is
C2-C8alkylene, C2-Cghydroxyalkylene or C4-C22acyloxyalkylene, and, if n is 2,
Rts is the
(-Cl-i2)ZC(CH2-)2 i;TOUp.
C2-Csalkylene or C2-Cghydroxyalkylene Rt5 is, for example, ethylene, 1-
methylethylene,
propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
C4-C22acyloxyalkylene Rts is, for example, 2-ethyl-2-acetoxymethylpropylene.
The following are examples of polyalkylpiperidine compounds of this class:
50) 9-aza-8,8,1U,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
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-pentamethyll,5-
dioxaspiro[5.5]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,I0,10tetramethyl-1,5-
dioxaspiro[5.5]undecane
55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(I',3'-dioxane)-
5'-spiro-5"-(1 ",3"-dioxane)-~2"-spiro-4"'-
(2"',2"',6"',6"'tetramethylpiperidine).
d) Compounds of the formulae VA, VB and VC
- l~ - 2~~::5s~
R16
RCH2 CH3~R
I
N-C=O
R'~ - N ( VA
~C-N R 1~
Ii
RCH2 CH3 O
n
RCH2 CH3 R Tt
O-C-T2
R N
\N-C=O VB
I
RCH2 CH3 H
RCH2 CH3~R T1
O-C-T2
RyN ~ VC
~C -N R 1~
RCH2 CH3 O
n
in which n is the number 1 or 2, R and Rtt are as defined under a), R16 is
hydrogen,
Ct-Cl2alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl, and, if n is l, R1~
is hydrogen,
C1-Cl2alkyl, C3-Csalkenyl, C~-Cgaralkyl, Cs-C~cycloalkyl, C2-C4hydroxyalkyl,
C2-C6alkoxyalkyl, C6-Cloaryl, glycidyl or a group of the formula -(CH2)P COO-Q
or of
the formula -(CH2)P O-CO-Q in which p is 1 or 2 and Q is Ct-C4alkyl or phenyl,
and, if n
is 2, Rl~ is C2-Ct2alkylene, C4-Cl2alkenylene, C6-Cl2arylene, a
-CH2-CH(OH)-CH2-O-D-O-CHI,-CH(OH)-CHZ- group in which D is C2-Ctoalkylene,
C6-Clsarylene or C6-Cl2cycloalkylene, or Rl~ is a
-CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- group in which Z' is hydrogen, C~-Clgalkyl,
allyl, benzyl, C2-Cl2alkanoyl or benzoyl, Tl and T2, independently of one
another, are
hydrogen, Cl-Cl8alkyl or unsubstituted or halogen- or Ct-C4alkyl-substituted
C6-Cloaryl
or C~-Cyaralkyl, or Tl and T2, together with the carbon atom connecting them,
form a
Cs-Ct2cycloalkane ring.
Any Cl-Cl2alkyl substituents are, for example, 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.
2(~5~5f~5
-I1-
Any Ct-CtHalkyl substituents may be, for example, the abovementioned groups
or, for
example, n-tr-idecyl, n-tctradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl,
ethoxymethyl,
propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl,
tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
C3-Csalkenyl R~~ is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-
pentenyl.
C?-C9aralkyl R~~, Tl and T2 are, in particular, phenethyl or especially
benzyl. If Tt and T2,
together with the carbon atom, form a cycloalkane ring, this may be, for
example, a
cyclopentane, cyclohexane, cyclooctane or cyclododeeane ring.
C2-C4hydroxyalkyl R~~ is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-
hydroxybutyl
or 4-hydroxybutyl.
C6-Ctparyl Rl~, Tt and T2 are, in particular, phenyl, a- or ~i-naphthyl,
unsubstituted or
substituted by halogen or Ct-C4alkyl.
C2-Ct2alkylene Rl' is, for example, ethylene, propylene, 2,2-
dimethylpropylene,
tetramethylene, hexamethylene, octamethylene, decamethylene or
dodecamethylene.
C4-Ct2alkenylene R~~ is, in particular, 2-butenylene, 2-pentenylene or 3-
hexenylene.
C6-CtZarylene R17 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or
4,4'-diphenylene.
C2-Ct2alkanoyl Z' is, for example, propionyl, butyryl, octanoyl or dodecanoyl,
but
preferably acetyl.
C2-Ctoalkylene, C6-Ctsarylene or C6-Ct2cycloalkylene D is as defined under b).
Preferred compounds of class d) are the compounds of the formula VA in which n
is 1, R
is hydrogen, Rtt is hydrogen or methyl, Rt6 is hydrogen or Ct-Ct2alkyl, and
R~~ is
Ct-Ct2alkyl.
- 12 _ i4:C~~.~1J~J
The following are examples of polyalkylpiperidine compounds from class d):
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-oxospiro[4.5]decane
62) 2,2-dibutyl-7>7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane
64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4,5]decane
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 formulae below:
2C'~~S~o
M
x
U
U ~ U
J
M
x ~M
z U=o x ~ v
U .i.
z U=O
U-z V x
z U U -_ z
O
M ~ O
N U U
N
x
U
O_
x Z U
x
U
U-z
N
U O N
x
U
I N
x x
x U x n
O ~ U x
U
v o x
N
II I U j ~~-z
U z ~Z U=o ~ ~ z
U=O
x O U=O
z UFO
M M
U ~ U U x r,
U U
U U z en x ~ U
x x x ~ M
U U U U x x
z
U I U U
M
x
U
0o O~
~~,~'. iJ~
- 14-
e) Compounds of the formula VI,
R18
N N VI
~ ~ R20
R19/ \N
n
in which n is the number 1 or 2, and Rlg is a group of the formula
R CHg CH2R
- E - (A x ~N - Rll
CH3 ~CH2R
in which R and Rl1 are as defined under a), E is -O- or -NR21-, A is C2-
C6alkylene or
-(CH2)3-O-, and x is the number 0 or 1, Rl9 is identical to Rlg or one of the
groups
-NR21R22, -ORS, -NHCH20R~ or -N(CH2OR23)2, R2~, if n is 1, is identical to Rl8
or R19
and, if n is 2, is an -E-B-E- group in which B is C2-C6alkylene which may be
interrupted
by -N(R21)-, R21 is C1-Cl2alkyl, cyclohexyl, benzyl, Cl-C4hydroxyalkyl or a
group of the
formula
R CH3 CH2R
~N-Ril
CH3 ~CH2R
R22 is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl, and R23 is
hydrogen,
C1-Cl2alkyl or phenyl, or R21 and R22 together are C4-Csalkylene or C4-
Csoxaalkylene,
for example
~C~~~J~J
-15-
-CH2CHy~ -CH2CH2 \
o , or a group of the formula /N _ R1 t
- co.~cH~~ - CH2CH2J
or R2t and R~ are alternatively each a group of the fornlula
N\
~NH-A-
_ 'N
CH3 CH ~T'%3
C4H9 - N
CH3 CH3
CH3 N CH3
H
Any C1-Ct2alkyl substituents are, for example, 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.
Any Cl-C4hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-
hydroxypropyl,
3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
C2-C6alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene,
tetramethylene or hexamethylene.
If R2t and R22 together are C4-Csalkylene or C4-CSOxaalkylene, this is, for
example,
tetramethylene, pentamethylene or 3-oxapentamethylene.
Preference is given to compounds of the formula VI in which n is 4, Rt8 and
Rt9 are a
CHg CH3
R21
N \N-Rtl
CH~CHg
CH3 CH3
C4H9
HN N
N
~C~~:5f~5
- 16-
~~roup in which Rtt is hydrogen or methyl and R2t is hydrogen or Ct-C6alkyl,
and R2~ is a
tetravalent radical of an aliphatic tetramine.
The following are examples of polyalkylpiperidine compounds from class e):
CH3
H3C N CH3
H3C ' CH3
7l)) N - C4H9
N' \ N
(CH CH ) N- _N_ 'N(CH CH )
3 22 2 32
N(C4H9)2
CH3 CH3 CH3 CH3
N N
71 ) C2H5 - N N ~ ~ N ~N - C2H5
C2H5 N C2FI5
CH3 CH3 CH3 ~CH3
R H3C CH3
N~N -NH-CH CH CH -O N-CH
72) ~ ~ where R = 2 2. 2 3
R \N R H3C CH3
2(~~~Sf~~
-m-
M ,y.M
x ~ U
U
x x
U U
a
M
v z x v v
~z v
z~~ ~ z z x
- /z
M
M x
x U
V
M M
x x
o. v U
x
v z ~ z U
x z zx
U
M ~ N
x x
M U x U
M M
U Z V ~ U U
x z -( z
\ M U (V M x
U U x Vcv ~ - V U
U x
! U
N z z z zx
x
U ~~ ,
N
x
U-z z U M x
x U
U
z
M M
x x
! U U
N
/ z
z ~~ z z x
U -z
U
Ov ~~~ M
M M M
v-z v
U U
x z x U U
U x V
U
x U
M
- 1$ - 2C'~~,~'.J~J
R K
75) R-NH- (Cli1)3N- (CH2)2-N- (CH2)3~NH-R
where R =
CH3 CH3
N ~~H9
~N ~NH
N ' 'N
~/ CH3 CH3
CaH9 N
CH3 ' .CH3
CH3 N CH3
H
R R
7 C~ R - NH- (CH2)3 N - (CH2)2- N - (CH2y3 NH- R
where R =
CH3 CH3
N t4H9
N ,N - CH3
N ' 'N
CH3 CH3
C4H9 N
CH3 I .CH3
CH3 CH CH3
3
- ~9 - 2t~~~S~S
CFi3 R R CH3
i i I
~~ R - N (CH.'S N - (CH's-N - (CH2)3 N R
where R =
CH3 CH3
N ~4H9
~N ~N-CH3
N ~ ~ ~N
CH3 CH3
C4H9 - N
CH3 I.CH3
CH3 I CH3
CH3
CHg
CgHI~ N
CH3
N N
N~NH(CH2y3
CBHI~- N
CHg I'CH3
CH3 N CH3
H
~~~u v~~a.~
_ 7~ _
CH2CH20H
CH3 N CH3
CH3 ~ ~CHg
79) N - C4H9
CH3 CH3 N ~;V CH3 CH3
HO-CH CH -N N~N~N N-CH CH -OH
2 2 I 1 2 2
C4H9 C4H9
CH3 CH3 CH3 CHg
CH2-CH=CH2
HgC N CH3
H3C ~ _CH3
g0) N - C4H9
CH3
H3C CH3 N~N CH
/ 'N' \ 3
H2C= HC-H2C- N N N N - CH2-CH= CH2
I 1
C4H9 C4H9
H3C CH3 CH3 CHg
f) Oligomeric or polymeric compounds whose recurnng structural unit contains a
polyalkylpiperid~ne radical of the formula (I), in particular polyesters,
polyethers, ,
polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines,
poly(meth)acrylates, poly(meth)acrylamides, and copolymers thereof which
contain these
radicals. Of these, the polyesters and polyaminotriazines are preferred.
Examples of 2,2,6,6-polyalkylpiperidine light stabilisers from this class are
compounds of
the formulae below, in which rn is a number from 2 to about 200.
iW',r'.;~J~J
-21 -
R1)
CH3 CH3
O O
II II
~C-CH2-CH2-C-O-CH2-CH2-N O
m
CH3 CH3
82)
CH3 CH3 O O CH3 CHg O O
II II II II
(~ v
-j-CH2-CH2-N O-C- (CH2)4-C-O N-CH2-CH2-O-C- (CH2)4-C
~m
CH3 CH3 CHg CHg
83)
CH3 C2H5 O O CH3 C2H5 O O
NH- (CH2~-N NH-- ~~ ~ ~~ -NH N-. (CH2y~_NH- ~~
m
CH3 ~ ~ CH3
CH3 \C2H5 CH3 ~CoHc
84)
H3 I H3
NH- ~ - CH2- ~ - CH3
N% \NCH3 CH3
N (CHZ)6 N
-N m
CH3 CH3 CHg CH3
CH3 ~ H CH3 CH3 H CH3
_ 7'? _ ~~1~~i5~.~
85)
N CH2- CH(OH~- CH2
~m
CH3 I 'CH3
CH3 H CH3
86)
CHg CH3 CH3 CH3 O C H
~O N-CH2-CH=CH-CH2-N O-C-C C
L m
CH3 CH3 CH3 CH3 C4H9
87)
N
N - (CH2)6 N
N ' 'N
CH3 CH3 CH3 , _CH3
N /y\H
CH3 H CH3 CH3 H CH3
88)
CH3 CH3 CH3 CH3 O O
O N-CHZ ~ ~ CH2-N O-C- (CH2)4-C
CH3 CH3 CH3 CH3
m
~~WjS~J
-23-
gc))
O C2H~ O CH3 CHg
II I ~
C -C C-O CH2-CH2-N O-f-
m
C2H5 CH3 CH3
90)
CH3
C - CH2-f-
~m
O=C CH3 CH3
O N CH3
CH3 CH3
91)
CH3
~C-CH2
L ~m
O=C CH3 CHI
C6H~3 -N N CH3
CH3 CH3
~C'~ ::5~~
-24-
92)
93)
0
N
N i 'N N- (CH2)6 N
N ~ H3 CH3 CH3 CH3
CH3 N _CH3 CH3 N- 'CH3
H H
N (CH2)6 N CH2~ CH2
~m
CH3 / IC' f'CH3 CH3 CH3
CH3 7 N//''~~CH3 CH3 N CH3
H H
94)
0 0
II II
N (CH2)6 N C CH2 C
CH3 CH3 CH3 \?~~CH3 m
CH3 N CH3 CHg N CH3
H H
Of these classes, a), d), e) and fj are particularly preferred, in particular
the compounds 10,
13, 14, 23, 24, 28, 29, 63> 65, 75, 77, 81, 84 and 92.
These sterically hindered amines are known compounds and many are commercially
available. It is also possible to use two different sterically hindered
amines, for example
one of low molecular weight and one of higher molecular weight, as described
in
US-A-4 692 486.
The zinc compound used as component c) may be an organozinc compound, for
example
the zinc salt of a carboxylic acid, sulfonic acid, phosphonic acid or
phosphinic acid, or the
zinc salt of a phenol or a zinc chelate, for example the enolate of a 1,3-
diketo compound.
2C~~:~5~~
Component c) may alternatively be an inorganic zinc compound, for example an
oxide,
hydroxide, carbonate, phosphate, phosphite, sulfate, chloride, fluoride or
hypophosphite.
c) is preferably the zinc salt of a Ct-C~carboxylic acid, of a C6-Ctgphenol or
of a
CS-C22-1,3-diketone. The carboxylic acid may be a saturated or unsaturated
aliphatic or
cycloaliphatic carboxylic acid or an aromatic or aromatic-aliphatic carboxylic
acid.
Examples are formic acid, acetic acid, propionic acid, butyric acid, caproic
acid,
2-ethylhexanoic acid, caprylic acid, lauric acid, myristic acid, enanthic
acid, neodecanoic
acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid,
oleic acid, behenic
acid, montanic acid, benzoic acid, chlorobenzoic acid, p-ten-butylbenzoic
acid,
p-dodecylbenzoic acid, salicylic acid, 3,4-di-tert-butyl-4-hydroxybenzoic
acid, toluic acid,
dimethylbenzoic acid, thioglycolic acid, lactic acid, abietic acid, ~3-
mercaptopropionic
acid, (3-dodecylmercaptopropionic acid, phenylacetic acid and monoesters and
monoamides of dicarboxylic acids. Zinc salts of long-chain a-aminocarboxylic
acids and
of a-acylaminocarboxylic acids are also suitable for this purpose.
Examples of C6-CtBphenols are phenol, cresol, xylenol, 4-ten-butylphenol, 4-
nonylphenol,
4-dodecylphenol, 4-chlorophenol and 2-hydroxybiphenyl.
Examples of CS-C22-1,3-diketones are acetylacetone, butanoylacetone,
stearoylacetone,
lauroylacetone, benzeylacetone, dibenzoylmethane, lauroylbenzoylmethane,
stearoylbenzoylmethane and bis(4-methylbenzoyl)methane.
c) is preferably the zinc salt of an aliphatic C~-C2ocarboxylic acid. It is
also possible to use
mixtures of zinc compounds, for example zinc salts of technical grade
carboxylic acid
mixtures or technical grade alkylphenol mixtures. Particular preference is
given to zinc
stearate, zinc laurate, zinc 2-ethylhexanoate and zinc oleate.
The calcium, magnesium or barium compound used as component d) may be an
organic
compound, for example the calcium, magnesium or barium salt of a carboxylic
acid,
sulfonic acid, phosphonic acid, phosphinic acid, phenol or enol. Component d)
may
alternatively be an inorganic compound, for example an oxide, hydroxide,
carbonate,
phosphate, phosphite or hypophosphite of calcium, magnesium or barium.
d) is preferably the calcium, magnesium or barium salt of a Ct-CZZCarboxylic
acid or of a
~C~~::J~J
_ 26 _
C~-C;sphenol, in particular the salt of an aliphatic C~-C~pcarboxylic acid.
Examples of
such carboxylic acids and phenols are as described for the zinc salts. The
stearates,
laurates and oleates of calcium, magnesium and barium are particularly
suitable.
1,3-Dicarbonyl compounds which can be used as component e) are linear or
cyclic
dicarbonyl compounds. Preference is given to dicarbonyl compounds of the
formula VII
0 0
II II
Rt-C-CHR2-C R3 VII
in which R1 is Ct-C22alkyl, CS-Ctohydroxyalkyl, C2-Ctgalkenyl, phenyl, phenyl
which is
substituted by OH, Ct-C4alkyl, Ct-C4alkoxy or halogen, C~-Ctpphenylalkyl,
CS-Ct2cycloalkyl, CS-Ct2cycloalkyl which is substituted by Ct-C4alkyl, or an -
RS-S-R6 or
-RS-O-R6 group, R2 is hydrogen, Ct-CBalkyl, C2-Ct2alkenyl, phenyl, C~-
Ct2alkylphenyl,
C~-Ctpphenylalkyl or a -CO-R4 group, R3 is as defined for Rt or is Ct-
CiBalkoxy, R4 is
Ct-C4alkyl or phenyl, RS is C1-Ctpalkylene, and R6 is Ct-Cl2alkyl, phenyl,
C~-CtBalkylphenyl or C~-Ctophenylalkyl.
These include the hydroxyl-containing diketones of EP-A-346 279 and the oxa-
and
thiadiketones of EP-A-307 358.
Alkyl Rt and R3 may be, in particular, Ct-CtBalkyl, for example methyl, ethyl,
n-propyl,
isopropyl, n-butyl, ten-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or
octadecyl.
Hydroxyalkyl R1 and R3 are, in particular, -(CHz)n OH groups in which n is 5,
6 or 7.
Alkenyl Rl and R3 may be, for example, vinyl, allyl, methallyl, 1-butenyl, 1-
hexenyl or
oleyl, preferably allyl.
OH-, alkyl-, alkoxy- or halogen-substituted phenyl Rt and R3 may be, for
example, tolyl,
xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl,
chlorophenyl or
dichlorophenyl.
Phenylalkyl Rt and R3 are, in particular, benzyl.
Cycloalkyl or alkylcycloalkyl RZ and R3 are, in particular, cyclohexyl or
iG~''..~'.3J~J
mcthylcyclohexyl.
Alkyl RZ may be, in particular, Ct-C4alkyl.
C2-Ct2alkenyl R2 may be, in particular, allyl. Alkylphenyl R2 may be, in
particular, tolyl.
Phenylalkyl R2 may be, in particular, benzyl. R2 is preferably hydrogen.
Alkoxy R3 may be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy,
dodecyIoxy, tridecyloxy, tetradecyloxy or octadecyloxy.
Ct-Ctoalkylene RS is, in particular, CZ-C4alkylene.
Alkyl R6 is, in particular, C4-Ct2alkyl, for example, butyl, hexyl, octyl,
decyl or dodecyl.
Alkylphenyl R6 is, in particular, tolyl. Phenylalkyl R6 is, in particular,
benzyl.
Examples of 1,3-dicarbonyl compounds of the formula VII are acetylacetone,
butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone,
lauroylacetone,
7-tert-nonylthioheptane-2,4-dione, benzoylacetone, dibenzoylmethane,
Iauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane,
5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis(4-
methylbenzoyl)methane,
benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)methane,
4-methoxybenzoylbenzoylmethane, bis(4-methoxybenzoyl)methane,
1-benzoyl-i-acetylnonane, benzoylacetylphenylmethane,
stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane,
benzoylformylmethane, benzoylphenylacetylmethane, bis(cyclohexanoyl)methane,
di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl and octadecyl
acetoacetate,
ethyl, butyl, 2-ethylhexyl, dodecyl and octadecyl benzoylacetate and ethyl,
propyl, butyl,
hexyl and octyl stearoylacetate.
Component e) is preferably a compound of the formula VII in which R1 is Ct-
Ctgalkyl,
phenyl, phenyl which is substituted by OH, methyl or methoxy, C7-
Ctophenylalkyl or
cyclohexyl, R2 is hydrogen, and R3 is as defined for R1.
The compositions according to the invention preferably comprise 100 parts by
weight of
componem (a), from 0.01 to 2 parts by weight of component (b), from 0.01 to 3
parts by
weight of component (c), from 0.01 to 3 parts by weight of component (d) and
from 0.05
2C'~~SL~~
-28-
to ? parts by weight of component (e), in particular 100 parts by weight of
component (a),
from 0.1 to 1 part by weight of component (b), from 0.1 to 2 parts by weight
of component
(c), from 0.1 to 2 parts by weight of component (d) and from 0.: to 1 part by
weight of
component (e).
In addition, the composition may contain further additives which are known and
conventional for processing and stabilising chlorine-containing polymers, for
example
plasticisers, phosphates, lead compounds, cadmium compounds, metal-free PVC
stabilisers, impact modifiers, heat resistance improvers, epoxide compounds,
antioxidants,
UV absorbers, light stabilisers, pigments, dyes, fillers, lubricants and
flameproofmg
agents.
Examples of plasticisers are the esters of phthalic acid, adipic acid, azelaic
acid, sebacic
acid and trimellitic acid, polyesters made from aliphatic diols and
dicarboxylic acids,
phosphoric acid esters, chloroparaffins and epoxidised fatty acid esters.
Further examples
are given in "Taschenbuch der Kunststoff-Additive" [Pocketbook of Plastics
Additives],
R. Gachter, H. Miiller, Hanser-Verlag 1983, pages 280-307. The plasticisers
may be used
in an amount of from 15 to 100 parts by weight, based on 100 parts by weight
of the
chlorine-containing polymer.
Organic phosphates are known costabilisers for chlorine-containing polymers
stabilised by
means of metal carboxylates, in particular in combination with stabilisers
based on zinc,
barium, magnesium or cadmium. Examples of phosphates of this type are trioctyl
phosphate, tridecyl phosphate, tridodecyl phosphate, decyl Biphenyl phosphate,
triphenyl
phosphate, phenyl didecyl phosphate, tris(nonylphenyl) phosphate, trilauryl
phosphate,
trioctadecyl phosphate, distearyl pentaerythritol diphosphite, 2,4-di-ten-
butylphenyl
di(dodecyl) phosphate, tris(2,4-di-tert-butylphenyl) phosphate, diisodecyl
pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
tristearyl sorbitol
triphosphite and 3,9-bas(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-
diphosphaspiro[5.5]undecane.
Compounds of lead and cadmium have a similar action to the calcium, magnesium
and
barium compounds, but are ecologically suspect. Examples of these are the
metal salts of
fatty acids, for example stearates, palmitates and oleates, and inorganic
salts, for example
basic sulfates and phosphates.
~
~ ,rr~r~~~-
~.( .....J uJ
_~y_
Examples of metal-free stabilisers for chlorine-containing polymers are
aliphatic polyols,
such as pentaerythritol, dipentaerythritol, trimethylolpropane, tris(2-
hydroxyethyl)
isocyanurate, sorbitol, mannitol and furan; aminocrotonic acid esters;
mercaptobenzoic
acid esters; dehydracetic acid; 2,4-dihydroxybenzophenone; enol carbonates, as
described
in EP-A-224 438; aromatic amides, as described in EP-A-122 228 and 174 412;
and
nitrogen-containing heterocyclic compounds, as described in EP-A-2007, 22 087,
22 749,
41 479, 65 934, 260 226 and 354 179, DE-A-3 048 659 and 3 124 853, GB-A-2 170
203
and US-A-4 908 398.
Examples of impact modifiers are polyacrylates, ethylene-vinyl acetate
copolymers and
chlorinated polyethylene, and examples of heat resistance improvers are
poly(meth)acrylates, acrylate-maleimide copolymers and acrylonitrile-
methylstyrene
copolymers.
Epoxide compounds are also known stabilisers for chlorine-containing polymers.
If they
have a suitable structure, they may simultaneously function as plasticisers.
Examples of
epoxide stabilisers are epoxidised polybutadiene, epoxidised Soya oil,
epoxidised linseed
oil, epoxidised fish oil, epoxidised tallow, methylbutyl and 2-ethylhexyl
epoxystearate,
tris(epoxypropyl) isocyanurate, epoxidised castor oil, epoxidised sunflower
oil,
3-(2-phenoxy)-1,2-epoxypropane, bisphenol A polyglycidyl ether,
vinylcyclohexene
diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl-3,4-epoxy-
cyclohexane carboxylate.
Examples of antioxidants are:
1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol,
2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol,
2,6-diactadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-dinonyl-4-rnethylphenol.
2. Alkylated hydro uinones, for example 2,6-di-tert-butyl-4-methoxyphenol,
2,5-di-tert-butylhydroquinone, 2,5-di-ten-amylhydroquinone and
2,6-diphenyl-4-octadecyloxyphenol.
3. Hydrox 1~ ated diphenyl thioethers, for example
~:C~5~5~5
2,2'-thiobis(6-ten-butyl-4-mcthylphenol), 2,2'-thiobis(4-octylphencl),
4,4'-thiobi::(6-tert-butyl-3-methylphenol) and 4,4'-thiobis(6-ten-butyl-2-
methylphenol).
4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tent-butyl-4-
methylphenol),
2,2'-methylenebis(6-ten-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(«-methylcyclohexyl)phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-
butylphenol),
2,2'-ethylidenebis(4,6-di-ten-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(«-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(«,«-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-ten-butylphenol),
4,4'-methylenebis(6-ten-butyl-2-methylphenol),
I ,1-bis(5-ten-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
I,l-bis(5-ten-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene
glycol bis[3,3-bis(3'-tent-butyl-4'-hydroxyphenyl) butyrate],
bis(3-ten-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene and
bis[2-(3'-tent-butyl-2'-hydroxy-5'-metltylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
5. Benzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris(4-tent-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
dioctadecyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, the calcium salt of monoethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate, and
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
6. Acylaminophenois, for example 4-hydroxylauranilide, 4-hydroxystearanilide,
2,4-bis(octylmercapta)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine and
octyl
~~'W~~r r
...:J~J
_3I_
N-(3,S-di-tert-butyl-4-hydroxyphenyl)carbamate.
7. Esters of 3-(3,S-di-ten-bull-4-hydroxyphenyl)propionic acid with monohydric
or
polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol,
neopentyl
glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol,
tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
8. Esters of Q-(S-tert-but~ydroxy-3-meth~phenyl)propionic acid with monohydric
or
polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol,
neopentyl
glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol,
tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
9. Esters of (3-(3,5-dicyclohexyl-4-hydroxyphen~propionic acid with monohydric
or
polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol,
neopentyl
glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol,
pentaerythritol,
tris(hydroxyethyl) isocyanurate and N,N'-bis(hydroxyethyl)oxalamide.
10. Amides o~3-(3,S-di-tert-but~ydroxyphenyl)propionic acid, for example
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and
N,N'-bis(3,S-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
Examples of UV absorbers and light stabilisers are:
1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-ten-
butyl,
5'-tent-butyl, 5'-(1,1,3,3-tetramethylbutyl), 5-chloa°o-3'>5'-di-tert-
butyl,
5-chloro-3'-ten-butyl-S'-methyl, 3'-sec-butyl-5'-tent-butyl, 4'-octoxy, 3',5'-
di-ten-amyl
and 3',5'-bis(a,a-dimethylbenzyl) derivatives.
2. 2-HydroxybenzoQhenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy,
4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and
2'-hydroxy-4,4'-dimethoxy derivatives.
3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-
butylphenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-ten-butylphenyl
~C'~~5~fi i
-32-
3,5-di-ten-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-ten-butyl-4-
hydroxybenzoate.
4-Acr-ylates, for example ethyl and isooctyl a-cyano-(3,[3-diphenylacrylate,
methyl
a-carbomethoxycinamate, methyl and butyl a-cyano-(3-methyl-p-methoxycinamate,
methyl a-carbomethoxy-p-methoxycinnamate and
N-((3-carbomethoxy-~3-cyanovinyl)-2-methylindoline.
5. Nickel compounds, for example nickel complexes of
2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 and 1:2
complexes, if
desired with additional ligands, such as n-butylamine, triethanolamine or
N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of
monoalkyl
4-hydroxy-3,5-di-ten-butylbenzylphosphonates, such as of the methyl or ethyl
esters,
nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecyl
ketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, if desired with
additional
ligands.
6. Oxalic acid diamide.s, for example, 4,4'-dioctyloxyoxanilide,
2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-
butyloxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide,
2-ethoxy-5-tent-butyl-2'-ethyloxanilide and the mixture thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and mixtures of o- and p-
methoxy- and of o-
and p-ethoxy-disubstituted oxanilides.
The pigments used may be inorganic, organic or metallic. Examples of fillers
are chalk,
carbon black, graphite, talc, kaolin or silicate minerals. However, the
compositions
according to the invention do not contain any hydrotalcite compounds.
Lubricants are, in particular, fatty acids and the salts, esters and amides
thereof, fatty
alcohols, paraffins and polyethylene waxes. Flameproofing agents are, in
particular,
antimony oxide, aromatic bromine compounds and phosphoric acid esters.
A review on the use of impact modifiers, colorants, fillers, lubricants and
flameproofing
agents in chlorine-containing polymers, in particular in PVC, is given in
"Taschenbuch der
Kunststoff Additive" [Pocketbook of Plastics Additives], R. Gachter, H.
Miiller,
Hanser-Verlag, 1983.
I~iC~.~n~S~J
3_
The compositions according to the invention can be prepared in a conventional
manner. In
general, the stabiliser system is incorporated into the polymer, for which
purpose a range
of known equipment, for example calenders, mixers, kneaders and the like,
exists.
The compositions stabilised in accordance with the present invention can be
shaped in a
conventional manner. Examples of such processes are calendering, extrusion,
injection
moulding, sintering and spinning, furthermore extrusion blowing or processing
by the
plastisol process.
The compositions according to the invention are particularly suitable in the
form of rigid
formulations for hollow articles (bottles), packaging films (thermoformed
films), blown
films, crash-pad films (automobiles), tubes, heavy profiles (window frames),
projection
screen profiles, building profiles, sidings, fittings, office films and
equipment casings
(computers and domestic appliances).
Other compositions in the form of soft formulations are suitable for wire
sheathing, cable
insulation, decorative films, roof sheeting, agricultural sheeting, tubes,
seal profiles, office
films and sheeting for air halls.
Examples of the use of the compositions according to the invention as
plastisols are
artificial leather, flooring, textile coatings, curtains, coil coatings and
underseal for motor
vehicles.
Examples of sintered PVC applications of the compositions according to the
invention are
slush, slush mould and coil coatings.
The examples below illustrate the invention in greater detail. All parts and
percentages
relate to the weight, unless stated otherwise.
The hindered amines and 1,3-diketones below are used in the examples:
H- I 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-
tetramethylspiro[4,5]decane-2,4-dione
'c:~.~'~:3J~J
-34-
CH3 CH3
H-~ H O N - CH2CH20COCH2CH2C OCH3
CH3 CHg n
Mn _ 2000
H-3 di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
NH-CgHt~-tert
N- 'N
H-4 ( ~ N (CH2)6 N
H3C 1'CH3 H3C 1'CH3 n
H3C N CH3 H3C N CH3
H H
Mn _ 2500
H-S di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate
HzC rH.,
14H9
H-S O CH2- C -(- CH3)2
(CH~j3C
D-1 Dibenzoylmethane
D-2 Benzoylstearoylmethane
Example 1: A semi-rigid PVC composition is prepared in accordance with the
following
recipe:
2(~~~SSS
-35_
100 p;uts by weight of suspension PVC having a K-value
of 70 (Vinnol~ H 70 DF),
17 parts by weight of dioctylphthalate,
3 parts by weight of epoxidised Soya oil (Reoplast~ 39),
1 part by weight of didecyl phenyl phosphite,
0.5 part by weight of zinc oleate,
0.8 part by weight of barium p-tent-butylbenzoate,
0.6 part by weight of butyl glycol and
0.3 part by weight of sterically hindered amine.
One part of the samples is additionally mixed with 0.3 part of a diketone. The
constituents
are homogenised for 5 minutes at 180°C on mixing rolls, forming a 0.3
mm thick film.
Samples are cut from the film and warmed to 180°C in a test oven
(Mathis Thermotester~
LTF-ST). The discoloration which occurs is measured in accordance with ASTM D
1925-70 as the yellowness index (YI). The higher this index, the greater the
discoloration.
Table 1 shows the results.
°
l ur: /' f ' f-'
~.C ~.:.i~J
_ 36 _
Table 1
I-lindered Diketone*) Yellowness
index
after
amine*)
0 6 12 1824 30 36 42 min
0.3 H-1 - 141519 2325 21 21 24
0.3H-1 0.3D-1 8 9 9 9 9 11 13 15
0.3 H-2 - 111317 1820 18 18 20
0.3 H-2 0.3 D-1 7 8 8 9 9 10 15 17
0.3 H-3 - 9 1216 1821 17 17 18
0.3 H-3 0.3 D-1 8 9 10 1110 1 12 9
U
0.3 H-4 - 141722 2430 35 37 42
0.3 H-4 0.3 D-1 121314 1514 17 18 20
0.3 H-5 - 9 1115 2117 I9 20 23
0.3 H-5 0. 3 D-1 8 9 10 1010 11 13 14
0.3 H-6 - 9 1316 2123 26 21 20
0.3 H-6 U.3 D-1 8 9 9 ~>'20 91 11 I 1
*) Parts per 100 parts of PVC
It can be seen that the samples containing the diketone (D-1) remain paler
over the entire
measured time than the samples without diketone.
Example 2: A rigid PVG formulation is mixed from the following components:
2C'~~5~~
_37_
100 parts by weight of suspension PVC having a K-value
of 60 (Corvic~ S 60/104),
3 parts by weight of epoxidised Soya oil (Reoplast~ 39),
1.2 parts by weight of zinc stearate and
0.6 pan by weight of calcium stearate
The amounts of hindered amine and diketone indicated in Table 2 are added. The
constituents are mixed for 5 minutes at 190°C on mixing rolls to give a
0.3 mm thick film.
The samples cut from the films are heated at 180°C as in Example 1, and
the yellowness
index is measured at intervals of 5 minutes.
Table 2
Hindered Diketone*) Yellowness index after
amine*)
10 15 20 25 30 35 40 min
0.3 H-4 I - 149 56 63 64 66 68 69 69
0.3 H-4 I 0.1 D-2 I 11 13 16 22 33 48 55 58
0.3 H-4 I 0.3 D-2 I 10 12 15 17 20 29 44 50
*) Parts per 100 parts of PVC
The paling effect of the diketone, which is particularly pronounced in the
first 25 minutes,
can also be seen here.
Example 3: Samples of a rigid PVC formulation are prepared as described in
Example 2
from the following components:
l0U parts by weight of a suspension PVC having a K-value
of 67 (Vestolit~ P 1982 K),
~~'W i~~
6 parts by w~i~~ht of chalk (OmyaC~ 95 T),
4 parts by weight of titanium dioxide (Kronos~ CL 220),
1 part by weight of P1ZMA-based processing assistant
(Irgamod~ F 138),
0.5 part by weight of didecyl phenyl phosphite
0.8 pan by weight of zinc stearate,
1.1 part by weight of barium laurate and
0.1 part by weight of bisphenol A
The amounts of hindered amine and 1,3-diketone indicated in Table 3 are added.
Table 3
shows the values for the yellowness index on heating at 190°C.
Table 3
Hindered Diketone*) Yellowness index after
amine*)
10 I S 20 25 30 35 40 min
0.3 H-4 , - ~ 23 25 37 40 43 44 46 55
0.3 H-4 I 0.1 D-2 I 18 20 24 26 29 33 36 41
0.3 H-4 ~ 0.3 D-2 ~ 11 13 14 17 19 23 29 37
*) Parts per 100 parts of PVC
Example 4: Samples of a semi-rigid PVC composition are prepared as described
in
Example 2 from the following components:
100 parts by weight of a suspension PVC having a K-value
of 71 (Corvic~ S 71/102),
20 parts by weight of dioctyl phthalate,
0.64 part by weight of didecyl phenyl phosphite
0.52 part by weight of zinc oleate,
0.59 part by weight of barium tert-butylbenzoate,
0.07 part by weight of 2,6-di(tert-butyl)-p-kresol and
.~r,-r r
,:..3JE3._)
_3y_
0.1( part by wei~~ht of an arotr~atic solvent mixture
(ShcllsolCO A).
The amounts of hindered amine and 1,3-diketone indicated in Table 4 are added.
Table 4
shows the yellowness index of the samples on heating at 190°C.
Table 4
Hindered Diketone*) Yellowness index after
amine*)
10 IS 20 25 30 35 40 min
0.3 H-4 - ~ 8 14 18 23 26 30 39 59
0.3 H-4 ~ 0.1 D-2 ~ 5 5 7 9 12 17 25 43
0.3 H-4 I 0.3 D-2 I 4 5 5 6 7 10 13 22
*) Parts per 100 parts of PVC
The considerable paling action of the diketone over the entire test period can
be seen here.
Example 5: Samples of the following semi-rigid composition are prepared as
described in
Example 2:
100 parts by weight of a suspension PVC hav_ng a K-value
of 71 (Corvic~ S 71/102),
20 parts by weight of dioctyl phthalate,
0.6 part by weight of didecyl phenyl phosphite,
0.57 part by weight of zinc oleate,
0.27 part by weight of calcium p-tent-butylbenzoate, and
0.52 part by weight of an aromatic solvent mixture
(Shellsol0 A).
The amounts of hindered amine and 1,3-diketone indicated in Table 5 are added.
Table 5
shows the yellowness index of the samples on heating at 190°C.
2C'~~5~~
-40-
Table 5
Hindered Diketone*) Yellowness index after
amine*)
S 10 15 20 25 30 min
0.3 H-4 ~ - ~ 6 7 9 13 17 23
0.3 H-4 I 0.1 D-2 I 4 5 6 8 12 19
0.3 H-4 ~ 0.3 D-2 ~ 4 4 5 7 9 17
*) Parts per 100 parts of PVC
A considerable positive effect of the diketone over the entire test period can
be seen here.
