Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~3:L !~3 3
- 1- '
A-17863/+/CGM 365
Stabilized, chlorine-containing composition
The invention relates to stabilized, foarnable, chlorine-containing polymer compositions
and to the foams obtainable therefrom.
It is known that chlorine-containing polymers tend to discolour even at moderatetemperatures and therefore can only be processed as thermoplastics with addition of -
stabilizers. While basic additives, such as organic amines, generally increase the
discoloration, specific sterically hindered amines have recently been disclosed which can
act both as light screens and as therrnal stabilizers, as described, for example, in JP-~
82/168 933 and JP-A 86/163 965.
In the production of foams from chlorine-containing polymers, the risk of discoloration is
particularly high due to the high foaming temperatures and due to the basic foaming
agents or catalysts (kickers) which are frequently present. It has surprisingly been found
that sterically hindered amines of this type can also be used for the production of foams ` ~`
from chlorine-containing polymers if, in addition, certain thermostabilizers or
costabilizers are additionally employed. In the foam, the hindered amines act not only as a
light screen, but also as n so-called long-term thermal stabilizer.
This is aellieved nccording to the invention using compositions containing
n) nt lenst one chlorine-contnining polymer,
b) nt least one blowing agent or foaming agent,
c) at least one sterically hindered amine, and
d) at least one zinc, calcium/zinc and/or barium/zinc compound.
The compositions according to the invention may contain, for example, as the
chlorine-containing polymer:
polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure,
such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl
acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with
acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated
' ~ ' ,' ' `:
' :- :
.. ~ . ... - . ..
.. . . .
:-
2~31l~$
- 2 -
dicarboxylic acids or anhydrides thereof, such as copolymers of vinyl chloride with
diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and
copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with
unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl
ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene
chloride and copolymers thereof with vinyl chloride and other polymerizable compounds;
polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl
acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid;
polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers;
chlorinated polymers of ethylene; polymers and post-chlorinated polymers of
chlorobutadiene and copolymers thereof with vinyl chloride, rubber hydrochloride and
chlorinated rubber hydrochloride; and mixtures of said polymers with one another or with
other polymerizable compounds.
This also includes graft polymers of PVC with EVA, ABS and MBS. Preferred substrates
are also mixtures of the abovementioned homopolymers and copolymers, in particular
vinyl chloride homopolymers, with other thermoplastic and/or elastomeric polymers, in
particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA,
EPDM, polylactones and nitrile rubber.
particul,lrly preferred chlorine-containing polymer is polyvinyl chloride, in particular as
a suspension polymer, emulsion polymer or bulk polymer.
Vario~ls processes which are known per se are suitable for producing foam articles or
expnncled articles from the composition according to the invention.
ï'he compositions can be expanded by means of finely divided gases, it being possible to
use various types of gases. For example permanent gases, usually nitrogen, can be
incorporated into PVC melts at a pressure of about 200 bar. For expansion, the mouldings
cooled in a press mould under pressure are, for example, heated in the open in a two-step
process. For example, soft foams are also produced from corresponding plastisols, ie.
mixtures of polymers and plasticizers, with addition of surface-active foaming agents and
compressed air or CO2 as blowing gas or foaming agent, for example by continuousextrusion.
Other processes use physical blowing agents, such as readily evaporating hydrocarbons,
2a311 ~
- 3 -
eg. pentane to heptane, or chlorinated hydrocarbons, such as methyl chloride, methylene
chloride, trichloroethylene or chlorofluoroalkanes. For example, the physical blowing
agents are dissolved in the raw materials or precursors or added under pressure during
processing. The formation of closed pores can be promoted by crosslinking.
Also known per se are chemical blowing agents. These are substances which decompose
at elevated temperatures to form inert gases. These are inorganic blowing agents, such as
NaHCO3, or organic blowing agents, eg. azo compounds, N-nitroso compolmds and
sulfonyl hydrazides, for example having initiation temperatures of between 90 and 275C,
from 100 to 300 ml of nitrogen being eliminated per gram.
Examples of such blowing agents are azodicarbonamide; modified azodicarbonamide;4,4'-oxybis(benzenesulfohydrazide), diphenyl sulfone 3,3'-disulfohydrazide, diphenylene - ` -
oxide 4,4'-disulfohydrazide; trihydrazinotriazine; p-tolylenesulfonyl semicarbazide;
5-phenyltetrazole and isatoic anhydride. A particularly preferred blowing agent is
azodicarbonamide, for example having an initiation temperature of 200-235C or areduced initiation temperature of 155-200C. In order to reduce the initiation temperature,
so-called kickers, eg. Zn stabilizers present in the polymer mixture, can be used. The
kicker can also be used in the form of zinc oxide/stearic acid. Other kickers which can be
used are alkali metal compounds, for example sodium compounds or potassium
compounds, such as alkali metal bicarbonates, preferably Na~ICO3, or alkali metal
compounds from the series comprising the aliphntic, saturated Cl-C22carboxylates,
aliphatic, olefinic C2-C22carboxylates, aliphatic C2-C22carboxylates which are substituted
by at least one O~l group, cyclic and bicyclic carboxylates having S-22 carbon atoms,
~romntic C6-C22carboxylatc9, aromatic C6-C22carboxylates which are substituted by at
least one O~l group, Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl
Cl-CI6alkylcarboxylates, C6-CI8phenolates, dehydroacetic acid and derivatives thereof,
mercaptides based on mercaptocarboxylates, and glycinates.
The alkali metal compounds from the series comprising the carboxylates are preferably
salts of carboxylic acids having from 7 to 20 carbon atoms, for exarnple benzoates,
alkenoates or alkanoates, preferably stearates, oleates, laurates, palmitates,
hydroxystearates or 2-ethylhexanoates. Particular preference is given to stearates, oleates
and p-tert-butylbenzoates. The potassium compounds are particularly preferred here, and
potassium 2-ethylhexanoate is very particularly preferred.
,
-.
2~3~ ~3~
The compositions may also contain nucleating agents and pore regulators which are
known per se. Examples of nucleating agents and pore regulators added to the foam
mixtures are small amounts of finely divided solids or C02-eliminating mixtures of
NaHCO3 and solid organic acids.
The compositions of the present invention may be blowing agent-containing PVC
moulding compositions which are ready for processing, for example for extrusion of
structural foarned pipes and profiles or for therrnoplastic foam casting. Or they may be
plastisols for conversion into foamed soft PVC articles.
Foamed articles can also be obtained from the compositions of the present invention by
the high-pressure processes which are known per se for the production of hard and soft
PVC foarns.
The compositions according to the invention can be used to produce PVC foams, for
example soft PVC foams, by the low-pressure process, which is known per se. In addition,
the compositions according to the invention can be employed, for example, in thepressureless process, which is known per se.
The said processes are described, for example, in Hansjurgen Saechtling,
Kunststoff-rraschenbuch [Pocketbook of Plastics], 22nd Edition, Carl Hanser Verlag,
Munich. :
Component tc) in the composition according to the invention can be any cyclic ornoncyclie sterically hindered amine. te) is preferably a compound which contains at least
one ~roup of the formula III
RCH2 CH3 R
-N~ (III)
RCH2 CH3
in which R is hydrogen or methyl. R is preferably hydrogen. These are derivatives of
polyalkylpiperidines, in particular of 2,2,6,6-tetramethylpiperidine. These
polyalkylpiperidines preferably carry one or two polar substituents or a polar spiro ring
.~ ~
~3~3~
system in the 4-position.
The following classes of polyalkylpiperidines are of particular importance.
a) Compounds of the formula IV
~ .,
RCH2~R
Rl,-N~O---R12 (IV),
RCH2 CH3 n
in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, Rl1 is
hydrogen, oxyl, hydroxyl, Cl-Cl2alkyl, C3-C8alkenyl, C3-C8aL~cynyl, C7-CI2aralkyl,
Cl-Cl8alkoxy, C5-C8cycloalkoxy, C7-CgphenylaL1coxy, Cl-C8aL~anoyl, C3-CsaLtcenoyl,
C1-Cl8alkanoyloxy, benzyloxy, glycidyl or a -CH2CH(OH)-Z group, in which 7. is
hydrogen, methyl or phenyl, Rll preferably being H, C1-C4alkyl, allyl, benzyl, acetyl or
acryloyl, and Rl2, if n is 1, being hydrogen, Cl-Cl8alkyl which is uninterrupted or
intermpted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent
rndicnl of nn aliphatic, cycloaliphatic, arnliphatic, unsaturated or aromatic carboxylic acid,
cnrbamic slcid or pllosphorlls-containing acid or a monovalent silyl radical, preferably a
rndicnl of nn nliphsltic carboxylic acid having from 2 to 18 carbon atoms, of a
cyclonliphntic carboxylic ncid having from 7 to 15 carbon atoms, of an a,~-unsaturated
cnrboxylic ncid hnving from 3 to 5 carbon atoms or of an aromatic carboxylic acid having
from 7 to 15 carbon ntoms, Rl2 being, if n is 2, Cl-CI2alkylene, C4-C12alkenylene,
xylylene, n divalent rndicnl of an aliphatic, cycloaliphatic, araliphatic or aromatic
dicnrboxylic acid, dicarbamic acid or phosphorus-containing acid, or a divalent silyl
rndical, prefernbly a radical of an aliphntic dicarboxylic acid having from 2 to 36 carbon
atoms, of n cycloaliphatic or aromatic dicarboxylic acid having from 8 to 14 carbon atoms
or of an aliphatic, cycloaliyhatic or aromatic dicarbamic acid having from 8 to 14 carbon
atoms, Rl2 being, if n is 3, a trivalent radical of aliphatic, cycloaliphatic or aromatic
tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a
trivalent silyl radical, and Rl2 being, if n is 4, a tetravalent radical of an aliphatic,
cycloaliphatic or aromatic tetracarboxylic acid~
.
'
:, .
: ' . . ' . -
î $ ~ q ~
If any substituents a~e Cl-Cl2alkyl, they 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.
Cl-CI8ALl~yl Rll or Rl2 may be, for example, the abovementioned groups and
additionally, ~or example, n-tridecyl, n-tetradecyl, n-hexadeeyl or n-octadecyl.
C3-C8ALIcenyl Rll may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl,
2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.
C3-C8Alkynyl Rll is preferably propargyl.
C7-CI2Aralkyl Rll is in particular phenethyl and especially benzyl.
Cl-C8Alkanoyl Rll is, for example, formyl, propionyl, butyryl or octanyl, bu~ preferably
aeetyl and C3-Csalkenoyl Rl1 is in particular aeryloyl.
A monovalent earboxylie aeid radieal Rl2 is, for example, an aeetie aeid, eaproic aeid,
stearie aeid, aerylie aeid, methaerylic aeid, benzoie acid or
p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic aeid radieal.
A divnlent diearboxylie aeid radieal Rl2 is, for example, a malonie aeid, sueeinie aeid,
~lutarie aeid, adipie aeid, suberie aei(l, sebaeie acid, maleie aeid, itaconie acid, phthalie
neid, dibutylmalonie aeid, dibenzylmalonie acid,
butyl(3,5-di-tert-butyl-4~hydroxybenzyl)malonie aeid or bieyeloheptenediearboxylic acid
radieal.
A trivalent triearboxylie aeid Rl2 is, for example, a trimellitie aeid, eitrie aeid or
nitrilotriaeetie acid radieal.
A tetravalent tetraearboxylie aeid radical Rl2 is, for example, the tetravalent radical of
butane- 1 ,2,3,4-tetraearboxylie aeid or of pyromellitie aeid.
A divalent diearbamie aeid radieal Rl2 is, for example, a hexamethylenediearbamie aeid
or 2,4-tolylenediearbamie aeid radieal.
: ' , ' ~ . ~ '' ' " - '
. . .
2~3~3~ :
- 7 -
':
Preference is given tO compounds of the formula IV in which R is hydrogen, Rll is
hydrogen or methyl, n is 2, and Rl2 is the diacyl radical of an aliphatic dicarboxylic acid
having from 4 to 12 carbon atoms.
The following Gompounds are examples of polyalkylpiperidine compounds of this class:
1) 4-hydroxy-2,2,6,6-tetramethylpiperidine
2) 1-allyl-4-hydroxy-2,2,6,6-tetrarnethylpiperidine
3) 1-benzyl-4-hydroxy-2,2,6,6-tetrarnethylpiperidine
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-pentarnethylpiperidine
8) 1 ,2,2,6,6-pentamethylpiperidin-4-yl ,B- (3 ,5-di-tert-butyl-4-hydroxyphenyl)propionat
9) di(l-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleinate
10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate
I l) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate
12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate
13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate
14) di(l,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
15) di(l,2,3,6-tetrnmethyl-2,6-diethyl-piperidill-4-yl) sebacate
16) di(1-allyl-2,2,6,6-tctramethylpiperidin-4-yl) phthalate
17) 1-hydroxy-4-,~-cyanoethyloxy-2,2,6,6-tetramethylpiperidine
18) 1-acetyl-2,2,6,6-tetrnmethylpiperidin-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(l,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate
23) di( 1 ,2,2,6,6-pentamethylpiperidin-4-yl)
butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate
24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
25) di(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
26) hexan-l ',6'-bis-(4-carbarnoyloxy- 1 -n-butyl-2,2,6,6-tetramethylpiperidine)27) toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
28) dimethylbis~2,2,6,6-tetramethylpiperidin-4-oxy)silane
29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane
.
2 ~ 3 ~
30) ~is(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
31) tris(1-propyl-2,2,6,6-te~ramethylpiperidin-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 the formula (V) ~ .
RCH2~R
R, 1 - N~>--N ~ ~ R14 (V)
RCH2 CH3 n
in which n is the number 1 or 2, R and Rll are as defined under a), Rl3 is hydrogen,
Cl-CI2alkyl, C2-Cshydroxyalkyl, Cs-C7cycloalkyl C7-C8aralkyl, C2-CI8alkanoyl,
C3-Csalkenoyl, benzoyl or a group of the forrnula
RCH2~R
R~l-N~}
RCH2 CH3
and Rl4, if n is 1, is hydrogen, Cl-CI8alkyl, C3-C8alkenyl, Cs-C7eycloalkyl, Cl-C4alkyl
whieh is substituted by a hydroxyl, eyano, alkoxyearbonyl or earbamide group, glycidyl, a
group of the formula -CH~-CH(OH)-Z or of the formula -CONH-Z in which Z is
hydrogen, methyl or phenyl; if n is 2, Rl4 is C2-CI2alkylene, C6-C12arylene, xylylene, a
-CH2-CH(OH)-CH2- group or a -CH2-CH(OH)-CH2-O-D-O- group, in which D is
C2-CI0alkylene, C6-CIsarylene, C6-CI2cycloalkylene or, as long as Rl3 is not alkanoyl,
alkenoyl or benzoyl, Rl4 may alternatively be a divalent radieal of an aliphatie,
cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternadvely the -CO-
group, or Rl3 and Rl4 together, if n is 1, may be the divalent radical of a aliphatie,
eyeloaliphatie or aromatie 1,2- or 1,3-dicarboxylie acid.
.
-~ -
2 ~ 3 ~
g
Any Cl-CI2 or Cl-Cl8alkyl substituents are as defined under a).
Any Cs-C~cycloaL~syl substituents are, in particular, cyclohexyl.
.
C7-C8AraL~yl Rl3 is, in particular, phenylethyl or especially benzyl. C2-CsHydroxyalkyl
Rl3 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
C2-CI8Alkanoyl Rl3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl,
hexadecanoyl or octadecanoyl, but preferably acetyl and C3-CsaL~cenoyl Rl3 is, in
particular, acryloyl.
C2-C8Alkenyl Rl4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or
2-octenyl.
Hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted Cl-C4aLtcyl Rl4 may be, for
example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethy],
2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
~ny C2-CI2alkylene substituents are, for example, ethylene, propylene,
2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or
dodccnmethylene.
Any C6-CIsnrylene subslitucnts are, for example, o-, m- or p-phenylene, 1,4-naphthylene
or 4,4'-diphenylene.
C6-CI2Cyclonlkylene D is, in particular, cyclohexylene.
Preferred compounds of the formula V are those in which n is 1 or 2, R is hydrogen, Rll is
hydrogen or methyl, Rl3 is hydrogen, Cl-CI2alkyl or a group of the formula
RCH2~R
R, 1 - N~
RCH2 CH3
-
. ` ` . . ` . . .
2a3~ ~3~
- 10-
and Rl4 is, in the case where n = 1, hydrogen or Cl^Cl2aLI~yl, and, in the case where n = 2,
is C2-C8alkylene.
The following are examples of polyaL~cylpiperidine compounds of this class:
37) N,N'-bis(2,2,6,6-tehamethylpiperidin-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-hydroxypropylen-1,3-
diamine
43) N,N'-bi~(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine
44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-succindiamide
45) di(2,2,6,6-tetramcthylpiperidin-4-yl)
N-(2,2,6,6~Tetramcthylpiperidin-4-yl)-~-aminodipropionate
46) The compound of the formula
-
' ' ?
- ~
2~3~'~3~
CH3 CH3
CH3 - N~ N--CH2- CH(OH~ CH2-O
CH3 011,
CH3--C--CH3
CH3~
CH3 ~ N ~ N--CH2- CH(OH)- CH2- 0
\~ C4Hg
CH /\CH
47) 4-(bis-2-hydroxyethyl-amino)-1,2,2,6,6-pentamethylpiperidine
48) 4-(3-Methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpipendine
49) 4-methacrylamido- 1 ,2,2,6,6-pentnmethylpiperidine
c) Compounds of the formula (VI)
RCH2~R
R11 ~ N~< ~ R15 (VI)
RCH2 CH3 n
in which n is the number 1 or 2, R and Rl 1 are as defined under a), and Rls, if n is 1, is
C2-C8alkylene or -hydroxyalkylene or C4-C22acyloxyalkylene, and, if n is 2, is the
(-CH2)2C(CH2-)2 group.
C2-C8Alkylene or -hydroxyalkylene Rls is, for example, ethylene, 1-methylethylene,
propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylprowlene.
C4-C22Acyloxyalkylene Rls is, for example, 2-ethyl-2-acetoxymethylpropylene.
.~ - .
,
2~3~3~
- 12-
The following are examples of polyalkylpiperidine compounds of this class:
50) 9-aza-8,8,10,10-tetramethyl-l,S-dioxaspiro[5.5]undecane
Sl) 9-aza-8,8,10,10-tetramethyl-3-ethyl-l,S-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-pentarnethyl-1,5-dioxaspiro[S.S]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro-[S.S]undecane
SS) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-S'-spiro-
S"-(1 ",3"-dioxane)-2"-spiro -4"'-(2"',2"',6"',6"'-tetramethylpiperidine).
d) Compounds of the formulae VIIA, VIIB and VIIC
\~/ I ~ ' .
/~N--C _ O (VII~)
~/ C--N _ R~7
RCH~ CH3 n
RCH2 CH3 R Tl
R~ -N)~o_ I -T2 (VIIB)
~ ~ ~ C--N=O
RCH2 CH3 H '
¦--FI N~ (VIIC)
C--N----R17
RCH2 CH3 0 _ n
2~3~3~
- 13-
in which n is the number 1 or 2, R and Rll are as defined under a), Rl6 is hydrogen,
Cl-Cl2alkyl, allyl, benzyl, glycidyl or C2-C6aL~oxyalkyl, and R17, if n is 1, is hydrogen,
Cl-Cl2alkyl, C3-Csalkenyl~ C7-C9aralkyl, Cs-C7cycloalkyl, C2-C4hydroxyalkyl,
C2-C6alkoxyalkyl, C6-C1Oaryl, glycidyl or a groap 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 Cl-C4alkyl or phenyl, and, if n
is 2~ Rl7 is C2-Cl2alkylene, C4-C12alkenylene, C6-Cl2arylene, a
-CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2- group in which D is C2-ClOalkylene,
C6-Clsarylene, C6-Cl2cycloalkylene, or a -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2-
group in which Z' is hydrogen, Cl-Cl8alkyl, allyl, benzyl, C~-C12aL~anoyl or benzoyl, T
and T2, independently of one another, are hydrogen, C1-Cl8aLkyl or C6-ClOaryl orC7-Cgaralkyl, each of which is unsubstituted or substituted by halogen or C1-C4aLkyl, or
Tl and T2, together with the carbon atom connecting them, form a Cs-C12cycloaLkane ring.
Any Cl-Cl2alkyl 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-Cl8alkyl substituents may be, for example, the abovementioned groups and in
addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl,propoxymethyl, tert-butoxyrnethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl,
tert-butoxyethyl, isopropoxycthyl or propoxypropyl.
C3-C5Alkcnyl Rl7 is, for cxarnple, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C7-CgAralkyl R17, T1 and T2 are, in particular, phenethyl or especially benzyl. If T1 and
T2, to~ether with the carbon ntom, forrn a cycloalkyl ring, it may, for example, be a
cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
C2-C4Hydroxyalkyl Rl7 is, for example, 2-hydroxyethyl, 2-hydroxypropyl,
2-hydroxybutyl or 4-hydroxybutyl.
C6-C1OAryl R17, T1 and T2 are, in particular, phenyl, a- or ~-naphthyl, which are
unsubstituted or substituted by halogen or C1-C4alkyl.
~ .
'
. . ' ~ ,
.
. .
,~3~3i~
- 14 -
C2-CI2Alkylene Rl7 is, for example, ethylene, propylene, 2,2-dimethylpropylene,
tetramethylene, hexamethylene, octa nethylene, decamethylene or dodecamethylene.
C4-CI2Alkenylene Rl7 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.
C6-Cl2Arylene R17 is, for example, o-, m- or p-phenylene, 1,4-naph.~hylene or
4,4'-diphenylene.
C2-Cl2AL~canoyl Z' is, for example, propionyl, butyryl1 octanoyl or dodecanoyl, but
preferably acetyl.
C2-CIOAlkylene, C6-CIsarylene or C6-CI2cycloalkylene D is as defined under b). ~ -
The following are examples of polyalkylpiperidine compounds of this class:
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-glyciclyl-1,3,8-t~iaxn-7,7,8,9,9-pentamethylspiro[4~5]decane-2,4-dione
60) 1,3,7,7,8,9,9-heptnmethyl-1,3,8-trillznspiro[4.5]decane-2,4-dione
61) 2 iso-propyl-7,7,9,9 tetrnmethyl-1-oxn-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[S.1.1 1.2]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 following formulae:
- . .
- ~
. .
,
.
.
.
~3~
- 1s-
CH3 CH3 CH3 CH3
)~\ HN-C=O O=C-NH ~--Y
66) CH3 - N X I I ~( N--CH3
CH3k~ C-N--CHzCH(OH)CH2-lOCH2-CH(OH)CH2]2 N ~C
CH3 CH3 CH3 CH3
)~ HN--C=O O=C--NH ~Y
67) CH3--N X ~ N--CH3
CH3k~ C--N--(CH2)6~ N - C \~
CH3 CH3 CH3 CH3
Y--~ HN--C=O O=C--NH ~--Y
C~ I kC~ ~ CH2~ o~3 0110
H3C~ CH2)l,
69) UN
>~ C--N--CH2CH2COOC12H2s
H3C CH3
c) Compounds of the ~ormula VIII
[R~ R~o (Vlll),
in which n is the number 1 or 2 and Rl8 is a group of the for nula
~'
.. . : ~. . :, . . : . :
2 ~ 3 ~
R~CH2R
-E-(A)~N - Rl,
CH3 CH2R
in which R and R,l are as de~lned under a), E is -O- or -NRll-, A is C2-C6alkylene or
-(CH2)3-O-, x is the number O or 1, Rlg is identical with Rl8 or is one of the groups : :
-NR21R22, -OR23, -NHCH20R23 or -N(CH20R23)2, R20, if n is 1, is identical with Rl8 or
Rlg and, if n i~ 2, is an -E-B-E- group in which B is C2-C6aLkylene which is uninterrupted
or is intenupted by -N(R2,)-, Rll is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl
or is a group of the forrnula
R~CH2R
~N-Rtl,
CH3 CH2R
R22 is Cl-CI2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl, and R23 is hydrogen,
Cl-Cl2alkyl or phenyl, or R21 and R22 together are C4-C5alkylenè or -oxaalkylene, for
-CH2CH2~ -CH2CH2
exnmple / or n group of the formula N--R,l or alternatively R21 and Ræ
-CH2CH2 -CH2CH2
arc cnch a group of the formula
CH3\/CH3
HN/~ HN--A--
k ~
CH3 CH3 C4Hg--N
CH3 ~<CH3
CH3 H CH3
,~ . ` ` ' , ,:
.` . : . ` `-, . :
`
2~ l3~
Any Cl-Cl2alkyl 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-C6AL'cylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene,
tetramethylene or hexarnethylene.
If R2l and R22 ~ogether are C4-Csalkylene or -oxaaL1cylene, this is, for example,
tetramethylene, pentamethylene or 3-oxapentamethylene.
The following are examples of polyalkylpiperidine compounds of this class:
ICH3
H3CyN yCH3
H3C I~J CH3
N--C4Ho
NJ~N
(CH3CH2)2N ~ N N(CH2CH3)2
CH3~ Ho)2
71) C2H~--N )'--Nl ~ ,~LN ( N--C2H5
k C2~,5 C2Hs 7~
CHa CH3 CHa CH3
72) N~N whereR= NH-c~2cl~2c~2-o~;_CH
'~'. '~ "' ~' '''- ' ' ' ` .
2 ~ 3 ~
- 18-
,~CH3
CH2 CH2~NH
NH
CH3~ ~ CH3CH3~CH3
HN ,~CH2-CH2-NH 1~ J NH-CH2-CH?.--~ NH
CH3 CH3 CH3 CH3
74)
CH3 CH3 CH3 CH3
HN~ NHCHzC~CH2CH~NH --
CH3 h CH3 ~N~N~ N,C4Hg ~
CH3~N~CH3 l l CH3l ~CH3
H J~ ~-- CH3~N CH3
CH3 ~ CH3 CH3 ~ <CH3 H
CH3 N CH3 CHa N CH3
H H
7~i) R N~I-(C~12)3-N-(CI-12~2-N-(CH2)3-NH.R
CH3 CH3
_~N~
N~N
C4Hg--N CH3 CH3
CH3~<CH3
CH3 NH CH3
R R
76) R-NH-(cH2)3-l~-(cH2)2-~-(cH2)3-NH R
,~ ' `' ~' ' ' '
.
, . , ' . ~, ~'~ ,' `
, .
2~3~1~3~
- 19 -
CH3 CH3
C4HD~y
N ~ N - CH3
N ~ N ~
where R = C4H9 - N CH3 CH3
CH3 ~ CH3
CH3 N CH3
CH3
CIH3 IR R ~H3
77) R-N-(cH2)3-N-(cH2)2-~-(cH2)3-~-R
CH3 CH3
N ~ N - CH3
N ~ N ~
where R = C4HD - N CH3 CH3
CH3~<CH3
CH3 N CH3
CH3
C ~ CH3
C8H17--N ~ NH
78) N N CH3 CH3
C~H~7 - N N NH(CH2)3
CH3 ~ CH3
CH3 N CH3
.
- ` ' ~ ''`: .
.
:
` ~3~3l3
- 20 -
CH2CH;~OH
H3C N CH3
H3C>~<CH3
N C4H3 .
79)CH3~;1 ~1 /~<
HO-CH2CH2--N ~ N N N ~ N--CH2CH2-OH
k-- C4H9C4Hs 7~ ~ .
CH3 CH3 CH3 CH3
CH2-CH=C~2
H3C~N~",,CH3
H3C1 T~CH3
\I~ :,
N--C4Hs
80)H3C~ NJ~N C~CH3
H2C~HC-H2C--N )--NlNlN_~\N--CH2-CH.CH2
~ C4H8 C4H9 7~ `
H3C CH3 CHa CH3 :.
Preference is given to f) oligomers or polymeric compounds whose recurring structural
unit contnins a 2,2,6,6-tetraalkylpiperidine radical of the formula III, in particular
polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas,
polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof
which contain such radicals.
The following are examples of 2,2,6,6-polyalkylpiperidine light screens of this class,
where m is a number from 2 to about 200.
H3C CH3
O O ~
81 ) -E C--CH2-CH2 - C--O-CH2-CH2 - Nj~ }m
H3C CH3
.~:
,, . -
. - , . . . .
- 2~ '13~
- 21 -
CH3>~ 0 ~CH3 0 0
82) ~CH2-CH2--Nk~O'C--(CH2)4--C-O~N-CH2-CH2-O--C- (CH2)4--C~
CH3 CH3 CH3 CH3
83) tNH(cH~ NH-c~o-N~cH~)~NH-o~3--C~
CH3
84) the particularly preferred compound of the forrnula
Cl H3 Cl H3
NH--C--CH2--C--CH3
J~ CH3 CH3
f~ JLN (CH2)~ ]m
CH~>~ J<CH3 CH3>~ CH3
CH3 N CH ~ CH3 N CH3
H H
[ N - cH2-cH(oH) c~l2~i~
85) CH3~CH3
H
~CH3 CH3~ o C4Hs 1l
86) ~0~7~N--CH2-CH=CH CH2-Nk~o-C-C--C~m
CH3 CH3 CH3 CH3 C4H9
~3~
22 -
N ~I N (CH2)6 N - - ]m~
~ CH3~<CH3 CH3~CH3
87) -C4HE, CH3 N CH3 CH3 N CH3
C~13~ CH3
CH3H CH3
88) E~ CWz~C~o-C-(CHz)~-~
Ct C2Hs o H3C~;
89) ~ C - C----C ~CH2-CH2 - N. ~-- ~i~t
C2Hs H3CCH3
ICH3
90) t C--CH2~
~CH3 ~.
O~<N-CH3
CH3 CH3
C~113
91 ) [ C--CH2~
~CH3
CsHt3--N ~N CH3
CH3 CH3
: . ' ~ '
- -
2 ~ 3 ~
- 23 -
'?
92) ~N~N tCH2)6 N }m
CH3 >~J)<CH3 CH3 '>~CH3
C~3 N CH3 CH3 N CH3
93) [ - N _ (CH2)6----N--CH2-CH2--3jj;~
CH3 >~)<CH3 CH3 >~<CH3
CH3 N CH3 CH3 N CH3
94) [ ~ - N _ (CH2)6--N--CH2--C ~;;~
CH3~)<CH3 CH3~)<cH3
CH3 N CH3 CH3 N CH3
g) Compounds of the forrmlla IX
RCH2~ R
Rl 1 N ~= O (Ix)
~r
RCH2 CH3
in which R and R11 are as defined under a).
Preferred compounds of the formula IX are those in which R is hydrogen or methyl, and
R11 is hydrogen or methyl.
Examples of such compounds are:
95) 2,2,6,6-tetramethyl-4-piperidone (aminotriacetone)
. : ,
- .
'
: .
- :.
3 ~
- 24 -
96) 1 ,2,2,6,6-pentamethyl-4-piperidone
97) 2,2,6,6-tetramethyl-~-piperidone 1-oxide
98) 2,3,6-trimethyl-2,6-diethyl-4-piperidone.
Expedient compositions are those as described above which contain, as d), at least one
organic zinc compound andlor at least one inorganic zinc compound from the series
comprising the carbonates, chlorides, sulfates, oxides, hydroxides, basic oxides and mixed
oxides.
Examples of organic zinc compounds are those from the series comprising the aliphatic,
saturated Cl-C22carboxylates, aliphatic, olefinic C2-C22carboxylates, aliphatic
C2-C22carboxylates which are substituted by at least one OH group, cyclic and bicyclic
carboxylates having 5-22 carbon atoms, aromatic C6-C22carboxylates, aromatic
C6-C22carboxylates which are substituted by at least one OH group,
Cl-Cl6alkyl-substituted phenylcarboxylates, phenyl-CI-Cl6alkylcarboxylates,
C6-CI8phenolates, Cs-C26chelates of 1,3-diketones or p-ketocarboxylates, dehydroacetic
ncid and derivatives thereof~ mercaptides based on mercaptocarboxylates, and glycinates.
Preference is given to polymer compositions containing, as d), an organic zinc compound,
the zinc compollnd being a salt of carboxylic acid having from 7 to 20 carbon atoms or a
C7-C20alkylphcnolate.
The zinc compounds from the series comprising the carboxylates are preferably salts of
carboxylic acids having from 7 to 20 carbon atoms, for example benzoates, alkenoates or
alkanoates, preferably stearates, oleates, laurates, palmitates, hydroxystearates or
2-ethylhexanoates. Particular preference is given to stearates, oleates and
p-tert-butylbenzoates.
A Zn phenolate component d) is, in particular, a C7 C20alkylphenola~e, for example
nonylphenolate.
Compounds which may be mentioned by name as examples are zinc salts of monobasiccarboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, caproic
acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid,
'' ' ': ' .' ' :
. . . ~ .
,. . -: . : . ~ :
. . - . ~ . . -
3 ~
capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmilic acid,
isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic
acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid,
3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic
acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid,
acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid, elaidic acid,
sorbic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid and
octylmercaptopropionic acid; monoesters and monoamides of dibasic carboxylic acids,
such as oxalic acid, malonic acid, succinic acid, glutamic acid, adipic acid, pimelic acid,
suberic acids azelaic acid, sebacic acid, phthalic acid, isophthalic acid,~terephthalic acid,
hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid,
citraconic acid, mesaconic acid, haconic acid, aconitic acid and thiodipropionic acid; and
diesters or triesters of tribasic or tetrabasic carboxylic acids, such as hemimellitic acid,
trimellitic acid, mellophanic acid, pyromellitic acid and mellitic acid.
Examples of chelates of 1,3-diketones and p-ketocarboxylates are compounds of the
formula
Zn~R ~-CR R ~ R )2
in whicll R, R', R" and R"' are alkyl having from 1 to 18 carbon atoms, alkenyl having
from 2 to 18 carbon atoms, cycloalkyl having from 5 to 12 ring carbon atoms, mono- to
tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 carbon atoms, alkyl having from
I to 18 c~rbon atoms which is substitllted by cycloalkyl having from 5 to 12 ring carbon
atoms, phenyl-CI-C18alkyl, Cl-CI8alkylphenyl, phenyl, alkoxyalkyl or alkylenedioxyalkyl
or -phenyl~
Examples of R, R', R" and R"' are methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl,
sec-butyl, tert-butyl, 1-pentyl, 3-pentyl, 1-hexyl, 1-heptyl, 3-heptyl, l-octyl,2,4,4-trimethylphenyl, tert-octyl, nonyl, decyl, tridecyl, pentadecyl, heptadec-8-en-1-yl,
n-octadecyl, allyl, methallyl, 2-hexenyl, 1-methylcyclopentyl, cyclohexyl,
cyclohexylpropyl, phenyl, m-tolyl, p-ethylphenyl, tert-butylphenyl, benzyl, phenylpropyl
and nonylbenzyl.
Alkoxyalkyl may be ethoxymethyl, n-butoxymethyl, 2-methoxyethyl, 2-methoxyphenyl or
2~ 3~
- 26 -
4-n-octoxyphenylbenzyl Alkylenedioxyalkyl or -phenyl may be, for example,
3-(ethylenedioxypropyl) or 3,4-methylenedioxyphenyl~.
Analogously, for example, all 1,3-diketones mentioned below which are not covered by
the above list may also be employed in their zinc chelate form as the organic zinc
compound.
The polymer compositions may contain, as component d), inorganic Ca/Zn and/or Ba/~Zn
compounds from the series comprising carbonates, chlorides, sulfates, oxides, hydroxides,
basic oxides and mixed oxides. Preference is given to calcium/zinc compounds.
In addition, organic Ca/Zn or BatZn compounds may be used as component d), for
example those from the series comprising the aliphatic Cl-C22carboxylates, olefinic
C2-C22carboxylates, aliphatic C2-C22carboxylates which are substituted by at least one OH
group, cyclic and bicyclic carboxylates having 5-22 carbon atoms, aromatic
C6-C22carboxylates, aromatic C6-C22carboxylates which are substituted by at least one
OH group, Cl-CI6alkyl-substituted phenylcarboxylates, phenyl-CI-C16aLtcylcarboxylates,
C6-CI8phenolates, Cs-C26chelates of 1,3-diketones or ~-ketocarboxylates, dehydroacetic
acid and derivatives thereof, mercaptides based on mercaptocarboxylates, glycinates,
phosphates, phosphites, phosphonites, phosphonates, partial esters of phosphonates,
sulfonates and sulfinates. -
Componellt d) in the composition according to the invention is particularly preferably a
~n, Ca/Zn or Ba/Zn cnrboxylnte. The cnrboxylates are preferably salts of carboxylic acids
hnvillg frorn 7 to 20 cnrbon atoms, eg. benzoatcs, alkanoates or alkenoates, preferably
stenrates, olcates, lnurates, palmitates, hydroxystearates or 2-ethylhexanoates. Pal~icular
prefcrence is given to octanoates, stearates, caprylates, oleates and p-tert-butylbenzoates.
~ixtures of Ba/Zn or Ga/Zn carboxylates are particularly preferred as component d), the
C.llZn carboxylates being very particularly preferred.
Zinc octanoate or zinc caprylate is likewise particularly preferred as component d).
A Ca/Zn or Ba/Zn phenolate component d) is, in particular, a C7-C20alkylphenola~e, for
example nonyl phenolate.
, . ,
. -
, . . ~ .
:. ' . . ,
.
3 ~
The present compositions may also contain further stabilizers or stabilizer mixtures whichimprove the processing or service properties of such compositions and the articles
produced therefrom.
Stabilizers of this type include Mg, Al, Mg/Al and Mg/Zn compounds, the individual
compounds mentioned for inorganic and organic zinc compounds being suitable. In each
of these, the zinc may be replaced by Mg, Al, Mg/A1 or Mg/Zn.
Further stabilizers which may be used in sorne cases are compounds which are known per
se, such as 1,3-diketones.
The 1,3-diketones may have the general formula II
Ra-e-CHRb ~ RC ~ :
where Rn iS alkyl having from 1 to 22 carbon atoms, Cs-Cl0alkoxyalkyl, alkenyl having
from 2 to 22 carbon atoms, phenyl, phenyl which is substituted by from 1 to 3 groups from
the series comprising -OH, Cl-C4alkyl, Cl-C4alkoxy or halogen, or is phenyl-CI-C4alkyl,
a group of the formula f ~. cycloalkyl having from S to 12 ring carbon atoms,
CH2- 0
or mono- to tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms;
Rc is alkyl having from 1 to 22 carbon atoms, Cs-CI0hydroxyalkyl, alkenyl having from 2
~o 22 carbon atoms, phenyl, phenyl which is substituted by from 1 to 3 groups from the
series comprising -O~l, Cl-C4alkyl, Cl-C4alkoxy or halogen, or is phenyl-CI-C4alkyl, a
grollp of the formula 1 ~, cycloalkyl having from 5 to 12 ring carbon atoms,
CH2- 0
or mono- to tri-CI-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms,
and Rb is -H, alkyl having from 1 to 18 carbon atoms, alkenyl having from 2 to 12 carbon
atoms, phenyl, Cl-C4alkyl-substituted phenyl, phenyl-CI-C4alkyl, or a group of the
formula
p~d
.
.,., , : . , -., . :
- 28 -
where Rd is -CH3, -C2Hs or phenyl, or in which Ra and Rb together are a tetramethylene
radical or a tetramethylene radical which is fused to a benzo radical, or Ra and Rc together
are a trimethylene radical or a mono- to tri-CI-C4alkyl-substituted trimethylene radical, or
Ra and Rc together are a ~rirnethylene radical, and form a compound of the formula Ila
[ 3~x (lla),
where Rb is as defined above, and X is alkylene having from 1 to 4 carbon atoms.
Cl-C22Alkyl Ra and Rc may be, for example, methyl, ethyl, propyl, n-butyl, tert-butyl, ~ -
pentyl, hexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, octadecyl or eicosyl,
and Cl-Cl8alkyl Rb may be, for example, as defined above with the exception of eicosyl.
~ .
Examples of Cs-Cl0hydroxylalkyl R~ and Rc are S-hydroxypentyl, 6-hydroxyethyl and
7-hydroxyheptyl.
Examples of C2-C22alkenyl Rn and Rc are vinyl, propenyl, allyl, butenyl, methallyl,
hexenyl, decenyl nnd heptndccenyl. Corresponding examples of C2-CI2alkenyl Rb can be
tnken annlo~ously from the nbovc list.
Phcnyl grollps, which are preferllbly substituted from one to three groups from the series
comprising -OH, Cl-C4nlkyl, Cl-C4alkoxy or halogen, as mentioned for Rn and RC, may be
4-hydroxypllenyl- or 4-hydroxy-3,5-di-CI-C4alkylphenyl where Cl-C4alkyl is, for
example, methyl or t-butyl, or methylphenyl, dimethylphenyl, ethylphenyl, n-butylphenyl,
tert-butylphenyl, methyl-tert-butylphenyl, di-tert-butylphenyl, methoxy, ethoxyphenyl or
monochlorophenyl.
Cl-C4Alkyl-substituted phenyl Rb is, for example, methylphenyl, ethylphenyl or
tert-butylphenyl.
Phenyl-CI-C4alkyl Ra, Rb and Rc is, for example, benzyl or methylbenzyl.
' ' -
3 ~
- 29 -
Ra and Rc may also be cycloalkyl having from S to 12 ring carbon atoms or mono- to
tri-C1-C4alkyl-substituted cycloalkyl having from 5 to 12 ring carbon atoms. Examples of
these are cyclopentyl, cyclohep~yl, cyclobutyl, cyclononyl, cyclododecyl, etc., and
methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl and tert-butylcyclohe~yl.
Examples of 1,3-diketones are: dehydroacetic acid, dehydropropionylacetic acid,
dehydrobenzoylacetic acid, cyclohexane-1,3-dione, dilttedone,
2,2'-methylenebiscyclohexane-1,3-dione, 2-benzylcyclohexane-1,3-dione, acetyltetralone,
palrnitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone,2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione,
benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane,
bis(2-hydroxybenzoyl)methane, benzoylacetone, t~ibenzoylmethane,
diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane,
lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane, ;
bis(4-methoxybenzoyl)methane, bis(4-chlorobenzoyl)methane,
bis(3,4-methylenedioxybenzoyl)methane, benzoylacetyloctylmethane,
benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane,
bis(4-t-butylbenzoyl)methane, butanoylacetone, heptanoylacetone, distearoylmethane,
acetylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylformylmethane,
bellzoylphenylacetylntethnne, bis(cyclohexanoyl)methane and dipivaloylmethane.
I ,3-Diketo compounds which can be used as costabilizers are also those described in
DE-B 2 600 516 and EP-A 35 268, for example those of the forrnula given in the patent
clnim of DE-B 2 600 516. Other 1,3-diketo compounds are benzoylstearoylmethane,
nlkyl(f;~r cxnmple ethyl) 2-benzoylacetoacetate and triacylmethanes.
Other 1,3-diketo compoun~s which cnn be used have the formula lIb
Rl -~-cH2 ~-R2 (IIb),
in which Rl is Cl-CI0atkyl, Cs-CI0hydroxyalkyl, phenyl, hydroxyphenyl,
C7-CI0phenylalkyl or C7-CI0phenylalkyl which is substituted on the phenyl ring by an OH
group, and R2 is C~;-CIOhydroxyalkyl, hydroxyphenyl or C7-CIOphenylalkyl which is
substituted on the phenyl ring by an OH group, with the proviso that R2 is not
hydroxyphenyl if Rl is phenyl or hydroxyphenyl.
,
-
. . . .
2 ~ 3 ~
- 30-
C1-CloAlkyl R1 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl,
n-pentyl, n-hexyl, n-heptyl, n-octyl or n-decyl. C1-C4Alkyl, in particular methyl or
tert-butyl, is preferred.
Examples of Cs-ClOalkoxyalkyl R1 and R2 are 5-hydroxypenytyl,
1,1-dimethyl-3-hydroxypropyl, 6-hydroxyhexyl, 8-hydroxyoctyl and 10-hydroxydecyl.
S-Hydroxypentyl, 6-hydroxyhexyl and 7-hydroxyheptyl are preferred. The hydroxyaLIcyl
group is preferably not in the -position. R2 is, in particular, a group of the forrnula
-(CH2)n-OH in which n is an integer from 5 to 7. 5-Hydroxypentyl R2 is of particular
interest. ~ ~ -
If R1 and R2 are hydroxyphenyl, the OH group may be in the ortho-, me~a- or
para-position. o-Hydroxyphenyl is preferred.
Examples of C7-ClOphenylalkyl Rl are benzyl and 2-phenylethyl.
R1 and R2 as C7-Cl0phenylalkyl which is substituted on the phenyl ring by an OH group
are, for example, (2-hydroxyphenyl)methyl, (3-hydroxyphenyl)methyl,
t4-hYdroxyphenyl)methyl~ 2-(2-hydroxyphenyl)ethyl and 2-(4-hydroxyphenyl)ethyl.
Within this group of stabilizcrs, preferred compounds are those of the above forrnula IIb in
which R1 is Cl-Cl0alkyl, Cs-CI0hydroxyalkyl, phenyl, hydroxyphenyl, C7-C10phenylalkyl
or C7-C10phenylalkyl which is substitllted on the phenyl ring by an OH group, and R2 is
Cs-ClOhydroxyalkyl, hydroxyphcnyl or C7-ClOphenylalkyl which is substituted on the
phcnyl ring by an OH group, with the proviso that R2 is not hydroxyphenyl if Rl is phenyl
or hydroxyphenyl.
P~urticularly preferred compounds of the above forrnula IIb are those in which Rl is
Cl-CIOalkyl, Cs-CI0hydroxyalkyl or phenyl, and R2 is C5-C10hydroxyalkyl or
hydroxyphenyl, and very particularly preferred compounds of the forrnula IIb are those in
which Rl is C1-C4alkyl or phenyl, and R2 is Cs-C10hydroxyalkyl or hydroxyphenyl,furtherrnore those in which R2 is a -(CH2)n-OH group where n is an integer from S to 7.
Further examples of particularly preferred compounds of the above formula IIb are those
in which R1 is rnethyl, butyl or phenyl, and R2 is ~-hydroxypentyl, 6-hydroxyhexyl,
,
` . ,
- . .
2~3;~3~
- 31 -
7-hydroxyheptyl or ortho-hydroxyphenyl.
Preferred compounds of the formula IIb which should be mentioned by name are
stearoylbenzoylmethane, dibenzoylmethane, l-phenyl-8-hydroxyoctane-1,3-dione,
1-t-butyl-8-hydroxyoctane-1,3-dione, 1-methyl-8-hydroxyoctane-1,3-dione and
1-(o-hydroxyphenyl)butane-1,3-dione.
Other suitable compounds have the formula IIc
R4
R~ H'&-R2-S-R3 (IIc)
in which R1' and R3', independently of one another, are Cl-C12alkyl, phenyl, mono- to
tri-CI-Cl2alkyl-substituted phenyl, C7-CI0phenylalkyl or mono- to
tri-Cl-CI2aLlcyl-substituted C7-CI0phenylalkyl, and Rl' is additionally -R2'-S-R3', R2' is
Cl-CIOalkylene, and R4' is hydrogen, C2-CsaL~coxycarbonyl or C2-CsaL~canoyl. Further ~ ;
details on these compounds, and examples and preferences are given in EP 307 358.
Expedient compositions are those as described above which contain, based on 100 parts by
weight of thc composition,
from 0.0001 to 8 parts by weight of blowing agent or foaming ngent,
from 0.01 to 3.0 pnrts by wcight of sterically hindered amines, and
from 0.01 to 8 parts by wcight of a zinc, Ca/Zn or Ba/Zn compound.
Prcfcrred rangcs for the amaunt of blowing agent or foaming agent are from 0.01 to S
parts by weight, particularly preferably from 0.1 to 3 parts by weight, very particularly
preferably from 0.1 to 2 parts by weight, in each case based on 100 parts by weight of the
composition.
Preferred ranges for the amaunt of sterically hindered amines in the composition are from
0.05 to 1.0 parts by weight, based on 100 parts by weight of the composition. An arnount
of from 0.1 to 0.5 part by wcight is particularly preferred.
Preferred ranges for the amount of the zinc, Ca/Zn or Ba/Zn compound in the composition
are from 0.05 to 3 parts by weight, particularly preferably from 0.1 to l.S parts by weight,
.
.
. ~ ,. ~ : . . .
.. . . . ~ ~. -
. ~ ' . ..
2~33 ~
- 32 -
in particular from 0.5 to 1.0 part by weight, in each case based on 100 parts by weight of
the composition.
Preferred ranges for the amount of so-called kickers in the composition are from 0.01 to 5
parts by weight, particularly preferably from 0.05 to 3 parts by weight, based on 100 parts
by weight of the composition.
If the composition also contains a 1,3-&etone, it preferably does so in an amount of from
0.05 to 5 parts by weight, in particular from 0.1 to 1 part by weight based on 100 parts by
weight of the composition.
The chlorine-containing polymer may contain a plasticizer.
Suitable plasticizers may come, for example, from the following groups:
A) Phthalates (phthalic acid esters) Examples of plasticizers of this type are dimethyl,
diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, diisoortyl, diisononyl, diisodecyl,
diisotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethyl glycol, dibutyl glycol,
benzylbutyl and diphenyl phthalate, and mixtures of phthalates such as C7-Cg- and
C9-Cllalkyl phthnlates comprising prcdominantly linear alcohols, C6-C1O-n-alkyl
phthalates and C8-C1O-n-alkyl phthalates. Of these, preference is given to dibutyl, dihexyl,
di-2-ethylhexyl, di-n-octyl, diisooctyl, diisononyl, diisodecyl, diisotridecyl and benzyl
butyl phthalate, and said mixtures of alkyl phthalates. Particular preference is given to
di-2-cthylhcxyl phtllalate (I)OP).
U) Estcrs of aliphatic dicarboxylic acids, in pMticular esters of adipic, azelaic and sebacic
acid.
Examples of plasticizers of this type are di-2-ethylhexyl adipate, diisooctyl adipate
(mixture), diisononyl adipate (mixtllre), diisodecyl adipate (mixture), benzyl butyl adipate,
benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and diisodecyl
sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and diisooctyl adipate.
C) Trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyl trimellitate
(mixture), triisotridecyl trimellitate, triisooctyl trimellitate (mixture) and tri-C6-C8alkyl,
tri-C6-ClOalkyl, tri-C7-Cgalkyl and tri-Cg-Cllalkyl trimellitates. The last-mentioned
trimellitates are produced by esterifying trimellitic acid with the corresponding alkanol
- '
2 ~ 3 ~L ~ 3 ~
- 33 -
mixtures. Preferred trimellitates are tri-2-ethylhexyl trimellitate and said trimellitates from
alkanol mixtures.
D) Pol~mer plasticizers
A definition of these plasticizers and examples thereof are given in "Plastics Additives
Handbook", editors H. Gachter and H. Muller, Hanser Publishers, 1985, page 284, chapter
5.7.10, and in "PVC Technology", editor W.V. Titow, 4th Ed., Elsevier Publ., 1984, pages
165-170. The most common starting materials for the preparation of polyester plasticizers
are: dicarboxylic acids, such as adipic, phthalic azelaic and sebacic acid; diols, such as
1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and
diethylene glycol; monocarboxylic acids, such as acetic, caproic, caprylic, lauric, myristic,
palmitic, stearic, pelargonic and benzoic acids; monofunctional alcohols, such as
isooctanol, 2-ethylhexanol, isodecanol and C7-CgaL~canol and Cg-C1laLtcanol mixtures.
Pa~ticularly advantageous polyester plasticizers are those made from said dicarboxylic
acids and monofunctional alcohols.
E) Phosphoric acid esters
A definition of these esters is given in the abovementioned "Plastics Additives Handbook"
on page 271, chapter 5.7.2. Examples of such phosphoric acid esters are tributylphosphate, tri-2-ethylbutyl phosphate, ~i-2-ethylhexyl phosphate, trichloroethylphospllate, 2-ethylhexyldiphenyl phosphate, cresyldiphenyl phosphate, triphenyl
phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to
tri-2-ethylhexyl phosphnte.
F) Chlorinatcd hydroc,lrbons (paraffins)
G) Hydrocnrbons
H) Monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate
and alkylsulfonic acid esters.
I) Glycol esters, for example diglycol benzoates.
Definitions and examples of group F) to I) plasticizers are given in the following
handbooks:
~, . . . .
~: .
. . :
:'
. ~": . ,
~:~
~03~ ~3~
- 34 -
"Plastics Additives H~mdbook", editors H. Gachter and H. Muller, Hanser Publishers,
1985, page 284, chapter 5.7.11 (group F)) and chapter 5.7.13 (group G)).
"PVC Technology", editor W.V. Titow, 4th Ed., Elsevier Publishers, 1984, pages 171-173,
chapter 6.10.2 (group P)), page 174, chapter 6.10.5 (group G)), page 173, chapter 6.10.3
(group H)) and pages 173-174, chapter 6.10.4 (group I)).
Particularly preferred plasticizers are those from groups A) to E), in particular A) to C), in
particular those emphasized as being preferred in these groups. Di-2-ethylhexyl phthalate
(DOP) is particularly favourable.
The plasticizers may be used in an amount of, for example, from 15 to 100 parts by
weight, expediently from 15 to 70 parts by weight, in particular from 20 to 50 parts by
weight, based on 100 parts by weight of the chlorine-containing polymer.
The compositions according to the invention may also conta;n further stabilizers which are
customary for chlorine-containing thermoplastics, for example organic phosphites. Such
phosphites may be present, for example, in an amount of from 0.01 to 3 parts by weight, in
particular from 0.01 to 1.5 parts by weight, preferably from 0.1 to 0.6 part by weight.
Exnmples of phosphites of this type are, for example, those of the forrnulae
Rl Q~ / ~ \
R2"~7P nnd R~ O-P~ _)CO~P_OR2"
in WiliCh Rl", R2" and R3" nre idcntical or different and are C6-C18alkyl and
C6-Cl8alkcnyl, substituted or unsubstituted phenyl or Cs-C7cycloalkyl.
C6-Cl8Alkyl Rl", R2" and R3" are, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl,
tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having from 8 to 18
carbon atoms.
Substituted phenyl Rl", R2" and R3" are, for example, tolyl, ethylphenyl, xylyl, cumyl,
cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl,p-n-octylphenyl, p-n-nonylphenyl or p-n-dodecylphenyl.
.
2~3~3~
- 35 -
Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl,
trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite, particularly
preferably ar,vldialkyl and alkyldiaryl phosphites7 for example phenyldidecyl,
(2,4-di-tert-butylphenyl)didodecyl and (~,6-di-tert-butylphenyl)didodecyl phosphites and
dialkyl- and diarylpentae.~thritol diphosphites, such as distearylpentaerythritol
diphosphite.
Prefcrred organic phosphites are distearylpentaerythritol diphosphite, trisnonylphenyl
phosphite and phenyldidecyl phosphite.
The compositions according to the invention may furthermore contain further known
costabilizers. Examples of costabili7ers of this type which may be mentioned areaminocrotonic acid esters, 2,4-dihydroxybenzophenone,
2,4-dihydroxy-4'-tert-butylbenzophenone and pyrrole deAvatives. The amounts of such
costabilizers may be, for example, 0.01 to 1.5 parts by weight, preferably from 0.1 to 1
part by weight, based on the composition.
Suitable aminocrotonic acid esters are, in particular, those with monohydric, straight-chain
C8-C20, in particular Cl2-Cl8alcohols andlor with 1,3- or 1,4-butanediol and/or
1,2-dipropylene glycol and/or thiodiethylene glycol.
P;urticularly suitable pyrrolc costnbilizers are those described in EP-A 22 087 and GB-A
2,078,761. ~n exnmple which may be mentioned is
2-mcthyl-3-cyclohexyloxycnrbonyl-4-phenyl- lH-pyrrole.
'I'hc compositions according to the invention may furthermore contain further optional
constitucnts, eg. organic antimony compounds, such as antimony
tris[isooctylthioglycolate] .
Other stabilizers which can be used in the compositions according to the invention are
polyols. The amounts to be used are, for example, up to 3 parts by weight, based on 100
parts by weight of the composition, expediently up to 2 parts by weight and preferably
from 0.01 to 1 part by weight. Typical examples of polyols are pentaerythritol,
dipentaerythritol, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)
isocyanurate (THEIC), the latter being preferred, sorbitol, mannitol and inositol.
' ' , ': :
'
.
2~3~3~
- 36-
In addition to said stabilizers and costabilizers, it is also possible to use epoxy compounds,
such as 1,2-epoxides and oxLranes, in amounts of, for example, up to 10 parts by weight,
based on 100 parts by weight of the composition, expediently up to 5 parts by weight and
preferably from 0.01 to 2 parts by weight. ~xamples of these are epoxidized
polybutadienf~, epoxiclized soybean oil, epoxidized linseed oil, epoxidized fish oil,
epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl)
isocyanurate, epoxidized castor oil, epoxidized sunflower oil,
3-(2-xenoxy)-1,2-epoxypropane, bisphenol ~ polyglycidyl ether, vinylcyclohexene
diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl
3,4-epoxycyclohexane carboxylate.
The compositions according to the invention may furthermore contain conventionalantioxidants, light stabilizers and UV adsorbers. Examples of these are:
1. Antioxidants
1.1. Alkvlated 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-dioctndccyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
~,6-di-tcrt-butyl-4-methoxymethylphenol and 2,6-dinonyl-4-methylphenol.
1.2. Alkylate(l hvdroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol,
2,S-di-tcrt-butylhydroqllinone, 2,5-di-tert-amylhydroquinone and
2,6-diphcnyl-4-octadecyloxyphenol.
1.3. ~IYdroxylatèd diphenyl thioethers, for example
2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol) and 4,4'-thiobis(6-tert-butyl-2-methylphenol).
1.4. Alkvlidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(a-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 ~ 3 ~
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2 '-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(~-methylbenzyl)-4-nonylphenol],
2~2~-methylenebis[6-(a~-dimethylbenzyl)-4-nonylyhenol]~
4,4'-methylenebis(2,6-di-tert-butylphenol~,
4,4 '-methylenebis(6-tert-butyl-2-methylphenol),
1,1-bis(5-tert-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,
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene
glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)bicyclopentadiene and
bis[2-(3 ' -tert-butyl-2 '-hydroxy-5 '-methylbenzyl)-6-tert-butyl-4-methylphenyl]
terephthalate.
1.5 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) dithioterephthalate,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris(4-tert-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,S-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
1.6 ~cYlaminophenols, for cxample 4-hydroxylauranilide, 4-hydroxystearanilide,
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine and octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamale.
1.7. Esters of ~-(3.5-di-tert-butYI-4-hYdroxYphenYl)propionic acid with monohydric or
polyhydric alcohols, eg. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate or N,N'-bis(hydroxyethyl)oxalamide.
1.8. Esters of ~-(S-tert-butYI-4-hYdroxY-3-methYlphenvl)propionic acid with monohydric
.
.: .. . . . .
20~ ~3~
- 38 -
or polyhydric alcohols, e~. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxy)ethyl isocyamlrate or N,N'-bis(hydroxyethyl)oxalamide.
1.9. Esters of ~-(3,5-dicyclohexYI-4-hYdroxYphenYl)yropionic acid with monohydric or
polyhydric alcohols, eg. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxy)ethyl isocyanurate or N,N'-bis(hydroxyethyl)oxalamide.
1.10. Amides of ~-(3,5-di-tert-butyl-4-hvdroxYphenvl)propionic acid, forexample
N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and
N,N '-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
2. UV absorbers and light screens
2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example the 5'-methyl, 3',5'-di-tert-butyl,
S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl,
S-chloro-3'-tert-butyl-S'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl
and 3',5'-bis(~,a-dimethylbenzyl) derivatives.
2.2. 2-~1YdroxYbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy,
4-dccyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and
2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted or llnsubstitllted benzoic acids, for example 4-tert-butylphenyl
snlicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrvlates, for example ethyl and isooctyl a-cyano-~,p-diphenylacrylate, methyl
a-carbomethoxycinnamate, methyl and butyl a-cyano-p-methyl-p-methoxycinnamate~
methyl a-carbomethoxy-p-methoxycinnamate and
N-(p-carbomethoxy-p-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of
. -,
.
: ;:.
2~3~3~
- 39 -
2,2'-~hiobis[4-(1,1,3,3-tetramcthylbutyl)phenol], such as the 1:1 or 1:2 complex, if desired
with additional ligands, such as n-butylamine, triethanolamine or
N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl
4-hydroxy-3,5-di-tert-butylbenzylphosphonates, such as of the methyl or ethyl esters,
nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecylketoxime,
and nickel complexes of 1-phenyl-4-lauroyl-S-hydroxypyrazole7 if desired with additional
ligands.
2.6. Oxalamides, 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-tert-butyl-2'-ethyloxanilide and rnixtures thereof with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, and rnixtures of o- and p-methoxy- and of o-
and p-ethoxy-di-substituted oxanilides.
2.7. 2-(2-Hydroxvphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)- 1 ,3,5-triazine and
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Depending on the intended use, the compositions according to the invention may also
contain other customary additives, for example
fillcrs and rcinforcing agents, eg. calcium carbonate, silicates, glass ~lbres, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite;
lubricants, pigments, flameproofing agents, antistatics, processing aids, impact modifiers
(polyacrylates) or biocides.
The compositions may also contain a compound from the series comprising the
hydrotalcites, in particular compounds having the general formula I
M2~ -M3+x-(OH)2-(An-)xln-mH2o (I),
:
,
: . : . : ,
. . .
.,
3 ~
- 40 -
where M2+ is Mg" Ca, Sr, Ba, Zn, Cd, Pb, Sn and~or Ni, M3+ is Al, B or Bi, An is an
n-valent anion, n is a number from 1 to 4, x is a number from O to û.5, m is a number from
O to 2, and
COO~
A is OH-, Cl-, Br~, I-, C104-, HC03-, (:H3COO-, C6EI5COO-, co32--, S042-, COO~
(CHOHCO0)22-,(CHOH)4CH20HCOO-.C2H4(coo)22-~(CH2C00)22--
CH3CHOHCOO-, SiO32-, sio44-, Fe(CN)~;3~, Fe(CN)64- or HPo42-.
Other hydrotalcites which can be employed are compounds having the general formula Ia
M2+xAI2(0H)2X+6nz(An-)2 mH20 (la)
where M2 ~ is at least one metal from the series comprising Mg and Zn, preferably Mg, An-
is an anion, for example from the series comprising co32-, ( l 0~ , OH- and S2-, where
CO
n is the valency of the anion, m is a positive number, preferably from 0.5 to 5, and x and z
are positive numbers, where x is preferably from 2 to 6 and z is less than 2.
Prefcrred polymer compositions are those as described above which contain at least one
cornpound from tlle series comprising the hydrotalcites, of the general formula Ib
M2~l~X Alx (OH)2 tAn~)xl2 H~O~ (Ib),
wherc M2 ~ is Mg or a solid solution of Mg and Zn, An- is co32-, x is a number from O to
0.5 and rn is a number from O to 2.
Examples of hydrotalcites of this type are the compounds of the formulae
4MgO Al203 CO2 9H20~
4MgO Al203 C02 6H20.
ZnO 3MgO Al203 CO2-8-9H20 or
. ' ' ' . . '
.
'
~,~3~ ~3~
- 41 -
ZnO 3MgO Al2O3 CO2 5-6H2O.
Expedient ranges for the amounts of hydrotalcite as mentioned above are from 0.1 to 3
parts by weight, preferably from 0.3 to 2 parts by weight, in particular from 0.4 to I part
by weight, in each case based on 100 parts by weight of the composition.
The present invention also relates to foarned articles obtainable by expanding acomposition according to the invention, as described above.
The articles may be, ~or example, amongst many further applications, tubes or profiles,
such as door frames, shutter boxes, window sills and furniture parts, sealing profiles,
furtherrnore shoe soles, buffers, shock absorbers, mats, webs, furs, blocks, carpeting,
foamed leathercloth, wall and floor coverings, cushioning materials and the like.
Examples of foamed articles which can be obtained according to the invendon are a) a
closed-cell soft PVC foam hnving a density d of from 0.05 to 1.0 glem3, which ean be
used as a highly elastic material in gymnastie mats, as an impact-protecting insert in
helmets, for absorbing machine vibrations and as a wall and floor covering, b) an
open cell soft PVC foam having a density d of from 0.07 to 0.33 g/cm3, which can be used
as n materi;ll in soundproofing technology and for breathable cushioning, e) a hard PVC
struetllral foam having a density d of from 0.5 to 1.0 g/cm3, which ean be used as a light
~hermoforrnable interior or exterior construetion material, or d) a elosed-cell hard PVC
foam hnving a density d of from 0.04 to 0.13 g/em3, which ean be used as a sandwich core
material, for net floats and life rafts or for low-temperature eontainers for liquid gases.
Example 1:
The following mixture is prepared for a hard foam:
Parts by weight~
Suspension PVC having a K value of ~8 100
PYC proeessing aid based on polymethyl
methaerylate 8
Chalk 2
Titanium dioxide pigment 2
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- 42 -
Diisodecylphenyl phosphite 0.5
Epoxidized soybean oil 0.8
Polyethylene wax (external lubricant) 0.3
Glycerol monooleate (internal lubricant) 1.0
Azodicarbonamide (chemical blowing agent
for foaming 0.5
~alcium stearate 0.8
Zinc stearate 2.0
Sterically hindered amine (Example 84
froM the description) 0.4
The mixture is subjected to the Brabender test, at a test temperature of 175C and a speed
of 35 rpm. The yellowness index (YI) is determined on the sheeted-out compound as a
function of time.
Table
Time . 5' 10' 15' 20'
YI 16.6 23.1 40.1 65.1
Example 2:
The following mixture was prepared for a sof~ foam:
Parts by weight:
Fincly divided emulsion homopolymer
having n K value of 67 100
9,11-Phthalate plasticizer B0
Potassium 2-ethylhexanoate 0.35
Basic zinc 2-ethylhexanoate 0.9
Aromatic hydrocarbons (solvent) 0.5
Tripropylene glycol monomethyl ether 0.25
Sterically hindered amine (Example 84
from the description) 0.1
Azodicarbonamide (chemical blowing agent
for foaming) 4
The mixture was subjected to the following test methods:
~3~3~
- 43 -
I'he Mathis test, in which the mixture is cast onto a substrate and gelled at 160C for 30
seconds. The sheeted-out compound produced is heat-treated at 200C, a fully expanded
material having a good foam structure being obtained after 60 seconds.
In another test using the Mathis ThermoSakter, ~he gelled mixture is loaded statically at
190C, the foam material produced exhibiting a clear colour change to brown after heating
for 28 minutes.
Example 3: A mixture is prepared as in Example 2, the 0.1 part by weight being replaced
by 0.3 part by weight of sterically hindered amine. In the same test method, a fully
expanded material having a good foam structure is obtained after 60 seconds, and the clear
colour change to brown on heating takes place after 32 minutes.
.
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