Note: Descriptions are shown in the official language in which they were submitted.
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Stabilisation of polyolefin-recvclates
The invention relates to a procass for sl~h;'~ ,g polyolefin recyclates, to a stabilizer mixture,
and to the recycled polyolefins oblail,able by the process.
The stabili~ation of recycled plastics for processing and re-use gives rise to specific
problems as a result of prior damage and associated structural alteration of the polymer
chains, and as a result of the impurities often present. The resulting dif~alcnces from virgin
plastics have necessitated the development of stabilizers for recyclates. From WO-A-
94/07946J WO-A-94/07950, WO-A-94/07951 and WO-A-94/2~377 it is known that
col. ~ in~lic,ns of phenolic antioxidants, phosphites and e,ooxides are suitable for stabilizing
previously damaged thermoplastics. With these systems, howev~r, it is necess~r~r to use at
least three components.
So that the concentrations in which they are used can be kept low, epoxides of high
epoxide c~ntent are expedient. However, commercially available epoxides of high epoxide
content are often liquid or low-melting products, whereas the abovementioned phosphitas
and phenolic antioxidants are solids. The addition of both liquid and solid products at the
same time in the course of processing may, however, cause proble",s, or may necessit~te
extensive technical e~uipment. Yet as a result of the low use concentrations of liquid
epoxides and their overall low price, there are economic ad~"lr,lages.
The object of the present invention was therefore to provide a st~hili'Ation system whic
has very good stabilizing properties and consists as far as possible of liquid,
homogene!ously miscible components. Furthermore, the stabilizer system should beeconomically acceptable for use in recyclates, i.e. it should either be effective in low
conce,.,l,~li3ns or consist of inexpensive co",ponents.
It has now surprisingly been found that a mixture comprising a secondary aromatic amine
and a polylunctional epoxide is particularly suitable for stabilizing polyolefin recyclates in
accordance with the requirements set out above.
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The present invention therefore provides a process for stabilizing a polyolefin recyclate
against oxidative, thermal or light-induced degradation, which comprises adding thereto at
least one secondary aromatic amine and at least one polyfunclional epoxide.
The invention is particularly important in connection with polyolefin recyclates as are
obtained from production waste, collections of recyclable material from households, in retail
outlets or through obligatory takeback schemes, for example in the automotive industry,
such as for old battery cases, or in the electrical sector. Examples of the products involved
are films, such as agricultural films, pouches, bottles and other containers. These polyolefin
recyclates may have suffered a wide variety of oxidative, thermal and/or light-induced
damage. Furthermore, these recyclates may also, in minor amounts, include admixed
plastics of different structure, for example styrene polymers (IPS, EPS, ABS, ASA),
polyesters (PET) or polyamides, and also customary impurities, for example paint residues,
traces of metal, fuel rcsidues ethylene glycol, isopropanol or else traces of water.
Polyolefin recyclates are derived from the following pure polyolefins:
1. Polymers of mono- and diolefins, for exa~ ,~'Q polypropylene, polyisobutylene, polybut-1-
ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also polymers of
cycloolefins, for example of cyclopentene or norbornene; furthermore polyethylene ~which
can be crosslinked), for example high-density polyethylene (HDPE), high-density
polyethylene of high molar mass (HDPE-HMW), high-density polyethylene of ultra high
molar mass (HDPE-UHMW), medium-density polyethylene (MDPE), low-density
polyethylene (LDPE), linear low-density polyethylene (LLDPE) and branched low-density
polyethylene (VLDPE).
Polyolefins, i.e. polymers of monoolefins exemplified in the preceding paragraph, especially
polyethylene and polypropylene, can be prepared by different, and especially by the
~;,.g, methods:
a) free-radically (no-"lally under high pressure and at a high temperature)
b) by means of a catalyst, the catalyst normally containing one or more metals of
group IVb, Vb, Vlb or Vlll. These metals usually have one or more ligands, such as
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o~cides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls
that may be either 7~- or ~-coordinated. These metal complexes may be in free form
or fixed on substrates, for example on activated magnesium chloride, titanium (Ill)
chloride alumina or silica. These catalysts may be soluble or insoluble in the
polymerization medium. The catalysts can be active as such in the polymerizationor further activators may be used, for example metal alkyls, metal hydrides, metal
alkyl halides, metal alkyl oxides or metal alkyloxanes. The metals being elements
of groups la, lla and/or Illa. The activators may be modified, for example, withfulther ester, ether, amine or silyl ether groups. These catalysts are usually termed
Phlillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), me'-"Deene or single
site catalysts (SSC).
2. Mixtures of the polymers mentloned under 1), for example mixtures of polypropylene
with polyisobutylene, polypropylene and polyethylene (e.g. PP/HDPE, PP/LI:~PE) and
mixtures of different types of polyethylene (e.g. LDPE/HDPE).
3. Copolynners of monoolefins and diolefins with each other or with other vinyl monomers,
for example ethylene-propylene copolymers, linear low-density polyethylene (LDPE) and
mixtures thereof with low-density polyethylene (LDPE), propylene-but-1-ene copolymers,
propyl~ene-isobutylene copolymers, ethylene-but-1-ene copolymers, ethylene-hexene
copolymers;, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-
octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers,
ethylene-all~yl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl
~et~te cop~olymers and copolymers thereof with carbon monoxide, or ethylene-acrylic acid
copolymers and salts thereof (ionomers), and also terpolymers of ethylene with propylene
and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbornene; furthermore,
mixturers of such copolymers with each other and with polymers mentioned under 1), for
example polypropylene~ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetate
copolymers, LLDPE/ethylene-acrylic acid copolymers and alternating or random
polyalkylene-carbon monoxide copolymers and mixtures thereof with other polymers, for
example polyamides.
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The polyolefin recyclate is preferably a copolymer recyclate of mono- and diolefins,
especially a polypropylene copolymer recyclate from battery cases or a polyethylene
copolymer recyclate.
Polyethylene recyclates or polypropylene recyclates are also particularly prefer. ed.
Preference is given to the novel process for stabilizing a polyolefin recyclate against
oxidative, thermal and/or light-induced degradation wherein both the secondary aromatic
amine and the polyf~ ,lional epoxide are in liquid form.
Secondary aromatic amines are, for the purposes of this invention, pre~erably compounds
of the formula I
R3~ ~RT
R4 R8
in which
Rl is hydrogen or C,-C25alkyl,
R2 is hydrogen, C1-C25alkyl or benzyl,
R3 is hydrogen, C~-C2salkyl, Cs-c12cycloalkyl~ benzyl, a-methyll,en~l or a,oc-dimethylben~yl;
or R2 and R3 together form a divalent group R
R4 is hydrogen, C,-C25alkyl or benzyl,
R5 is hydrogen or C,-C25alkyl,
R,3 ;s hydrogen, C,-C25alkyl or benzyl,
R~ is hydrogen, C~-C25alkyl, Cs-c12cycloalkyl~ benzyl, a-methylbenzyl, a,a-dimethylbenzyl
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or --N~ ; or R6 and R7 together form a divalent group Rg
R8 is hydrogen, Cl-C25alkyl or benzyl,
P~g is hydrogen or C,-C25alkyl, and
R-o is C5-C,2cycloalkyl, ~13~9 or ~Rg .
Alkyl of up to 25 carbon atoms is a branched or unbranched radicai such as, for example,
methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,
isopentyl, 11-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,
1,1,3,3-tetr~methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trime-
thylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, t-methylundecyl, dodecyl,
1,1,3,3,5,5 hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa-
decyl, eicosyl or docosyl. One of the preferred detinilions of R1, R2, R4, Rs, R6 and R8 is for
axample C1-C18alkyl, eSpeoiRlly C,-C12alkyl, for instance C,-C8alkyl. A preferred definition of
R3 and R, is for example C,-C,8alkyl, especially C,-C,2alkyl, for instance C4-C,2alkyl. A parti-
cularly preferred definition of R3 and R, is C4-C,Oalkyl, especially C4-C8alkyl, for in~ nce
tert-butyl or tert-octyl.
C5-C,2cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl
or cyclododecyl. A preferred derillilion of R3, R~ and R10 is for example C5-C8cycloalkyl, es-
pecially C5-t"cycloalkyl, for instance cyclohexyl.
Particularly preferred compounds of the formula I are those in which
R, and R2 independe,-lly of one another are hydrogen or C~-C~8alkyl,
R3 is hydrogen, C,-C,8alkyl, C5-C8cycloalkyl, benzyl, a-methylbenzyl or a,a-dimethylbenzyl;
or R2 and R3 together form a divalent group R9~
R4, R5 and R~ inde~l~el-dently of one another are hydrogen or C,-C,8aîkyl,
R7 is hydrogen, C~-C18alkyl, C5-C8cycloalkyl, benzyl, a-methylbenzyl, a,a-dimethylbenzyl
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or --N~ : or R~ and R7 together form a divalent group R~
R8 and R9 independently of one another are hydrogen or C,-C18alkyl, and
R10 iS C5-c8cycloalkyl~ ~3Rg or ~ ~R~ -
Of particular interest are the secondary aromatic amines of the formula I in which R1, R4, R5,
R6 and R8 are hydrogen.
Of specific i"terest are the compounds of the formula I in which
R1 and R2 are hydrogen,
R3 is hydrogen, C4-C12alkyl, cyclohexyl, benzyl, a-methylbenzyl or a,a-dimethylbenzyl; or R2
and R3 together form a divalent group R~
R4, R5 and R6 are hydrogen,
R7 is hydrogen, C4-C,2alkyl, cyclohexyl, benzyl, a-methylbenzyl, a,a-dimethylbenzyl or
Rlo
R8 and R~ are hydrogen, and
Rlo is cyclohexyl, phenyl or ,B-naphthyl.
Very particular preference is given to the secondary ar~ri,atic amines of the formulae la, Ib,
Ic, Id, le and If.
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--7--
,~,N ~ ~, ,~,N~ ~
W~N~J ~ W' IN~J (Ib)
H H
H
C'~CJ3~ ~C~3 R~ ~R' (Id)
H3C CH3 H3C CH3 R' = n-butyl or n-octyl
(CH3)3C ~c~N~[~3~C~ C(CH3)3
H3C CH3 H3C CH3
~N~[3
H
As secor..lary aro,..~llic amines, speGifiG ple~erence is given to the compounds of the
formulae le [4,4'-di-tert-octyldiphenylamine, Irganox~ 5057 (Ciba-Geigy~l and If [N,N'-
diphenyl-p-phenylenediamine~ and to the compounds of the formula I in which
R1, R2, R4, Rs, R6 and R8 are hydrogen,
R3 is hydrogen or C8altcyl,
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~H
R7 is C8alkyl or --N~ and
Rlo
R10 is phenyl.
The compounds of the formula I are known; some of them are available commercially and
some can be prepared as described in R. Gachter and H. Muller, Hanser Verlag, "Plastlcs
Additives Handbook, 3rd Ed.", page 44 to 45 (1990), in analogy to the literature references
cited therein.
For the purposes of this invention, polyfunctional epoxides can have an aliphatic, aromatic,
cycloaliphatic, araliphatic or heterocyclic structure; they include epoxide groups as side
groups, or these groups form part of an alicyclic or heterocyclic ring system. The epoxide
groups are preferably attached as glycidyl groups to the remainder of the molecule by way
of ether or ester linlcages, or the compounds involved are N-glycidyl derivatives of hetero-
cyclic amines, amides or imides. Epoxides of these types are generally known and commer-
cially available.
The polyfu"~ional epoxides cor"prise two epoxide radicals, for example those of the formu-
la 11
I H--(CH2)n Cl _ I H
R.1 R'2 R'3
which are attached directly to carbon, oxygen, nitrogen or sulfur atoms, in which Rll and R,3
are both hydrogen, R12 is hydrogen or methyl and n is 0; or in which R11 and R,~ together
are -CH2CI 12- or -CH2CH2CHz-, R12 is then hydrogen, and n is 0 or 1.
Examples of epoxides are:
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1. Diglycidyl and di(l3-methylglycidyl) esters obtainable by reacting a compound with two
carboxyl groups in the molecule and epicl,lGrol,ydrin and/or glycerol dichlorohydrin and/or
f3-methylepichlorohydrin. The reaction is expediently carried out in the presence of bases.
.
As compounds of two carboxyl groups in the molecule, aliphatic dicarboxylic acids can be
used. Examples of these dicarboxylic acids are glutaric acid, adipic acid, pimelic acid, sube-
ric acid, azelaic acid, seb~cic acid or dimerized or trimerized linoleic acid.
It is however also possible to employ cycloaliphatic dicarboxylic acids for example tetrahy-
drophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-m~thylhexa-
hy~llophll,alic acid.
I~urthermor~, aromatic dicarboxylic acids, for example phthalic acid or isophthalic acid, can
be used.
2. Diglycidyl, or di(l3-methylglycidyl) ethers obtainable by reacting a compound with two free
alcoholic hydroxyl groups and/or phenolic hydroxyl groups and a suitable sl~hstihlted epi-
chlorohydrin under alkaline conditions, or in the presence of an acidic catalyst with subse-
quent alkali treatment.
Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol,
diethylene glycol and higher poly(oxyethylene3 glycols, propane-1,2-diol,or poly(oxypropy-
lene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane-
1,5-diol, hexane-1,6-diol, sorbitol, and from Poly~F ~h'Drohydrins.
However, they are also derived, for example, from cycloaliphatic alcohols such as 1,3- or
1,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclo-hexyl)-
propane or 1 ,1-bis(hydroxymethyl)cyclohex-3-ene, or they possess aromatic nuclei, such as
N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino~diphenylmethane.
The epoxides can also be derived from l-,onor,uclear phenols, for example from resor~;;.,ol,
pyrocatecha,l or hydroquinone; or they are based on polynuclcar phenols such as, for
example, on 4,4'-dihydroxybiphenyl, bis(4-hydroxphenyl)methane, 2,2-bis(4-hydroxy-phe-
nyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3,5-dibromo-4-hydroxy-
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phenyl)propane, 4,4'-dihydroxybiphenyl sulfone, 9,9'-bis(4-hydroxyphenyl)fluorene, or on a
condensate of phenols with formaldehyde obtained under acidic conditions, such as phenol
novolaks.
3. Di(N-glycidyl) compounds are obtainable, for example, by dehydrochlorination of the
reaction products of epichlorohydrin with amines containing two amino hydrogen atoms.
Examples of these amines are aniline, toluidine, n-butylamine, bis(4-aminophenyl)methane,
m-xylylenediamine or bis(4-methylaminophenyl)methane.
Also included among the di(N-glycidyl) compounds, however, are N,N'-diglycidyl derivatives
of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and N,N'-diglycidyl deri-
vatives of hydantoins such as of ~,5-dimethylhydanl~,;.,.
4. Di(S-glycidyl) compounds, such as di-S-glycidyl derivatives derived from dithiols, for
ex~ ple ethane-1,2-dithiol orbis(4-mer~;ap~ "ethylphenyl) ether.
5. Froxides with a radical of the formula ll in which R11 and Rl3 together are -CH2CH2- and n
is û are, for example, bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl glycidyl ether or
1,2-bis(2,3-epoxycyclopentyloxy)ethane; examples of epoxides with a radical of the formula
Il in which R1, and Rl3 together are -CH2CH2- and n is 1 are (3',4'-epoxy-6'-methylcyclohe-
xyl)methyl 3,4-epoxy-6-methylcyclohexanecarboxylate and 3,4-epoxycyclohexylmethyl 3,4-
epoxycyclohexanecarboxylate .
Owing for example to the preparation process, the abovementioned difunctional epoxides
may include small amounts of mono- or trifunctional fractions.
Predon,i.)arllly, use is made of diglycidyl compounds having aromatic structures.
If desired, it is also possible to employ a mixture of epoxides of different structure.
Preference is given to the novel process for st~hi~ ng polyolefin recyclates against oxida-
tive, thermal and/or light-induced degradation wherein the polyfunctional epoxide is a di-
functional epoxide.
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Examples of s~ ~it~hlQ difunctional epoxides are:
a) liquid bisphenol A diglycidyl ethers, such as Araldit~9GY 240, Araldit~GY 250,
Araldit~GY 260, Araldit~GY 266, Araldit~GY 2600 or Ar~ldil~ 1Y 790;
b3 solid bisphenol A diglycidyl ethers, such as Araldit~GT 6071, Araldit~GT 7071,
Araldit~G T 7072, Araldit~9GT 6063, Araldit~GT 7203, Araldit~GT 6064, AraldiM9GT 7304,
Araldit~G T 7004, Araldit~GT 6084, Araldit~9GT 1999, Araldit~GT 7077, Araldit~9GT 6097,
Araldit~GT 7097, Araldit~GT 7008, Araldit(~GT 6099, Araldit~GT 6608, Araldit~GT 6609
or Araldit~GT 6610;
c) liquid bi~;phenol F diglycidyl ethers, such as Araldit~GY 281, Araldit~GY 282, Araldit(DPY
302, or Araldit~PY 306;
d) liquid glycidyl ethers o~ alcohols, such as Shell~9Glycidylether 162, Araldit~DY 0390 or
Araldit~D'I' 0391;
e) liquid glycidyl esters of carboxylic acids, such as Shell~9Cardura E lerepl,U,alic ester,
trimellitic e$ter, A~ liL~PY 284 or mixtures of al ~- "alic glycidyl esters, for eA~" ,~ 'e
A.~ldil~rT' 910;
f) liquid cyc:loaliphatic epoxy resins such as Araldit~CY t79.
On the other hand, tri- and polyfunctional epoxides can be employed supplementarily, in
order, If desired, to obtain branching sites. Examples thereof which are sl~it~hle are:
a) solid polyglycidyl ethers of tetraphenylethane, such as CG Epoxy Resin~D0163;
b) solid and liquid polyglycidyl ethers of phenol-formaldehyde novolak such as EPN 1138,
EPN 1139, GY 1180, PY 307;
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c~ solid and liquid polyglycidyl ethers of o-cresole-formaldehyde novolak, such as ECN
1235, ECN 1273, ECN 1280, ECN 1299;
d) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Ardldil~rT 810;
e) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldit~MY 0510;
f) tetraglycidyl-4-4'-methylenebenzamine or N,N,N',N'-tetraglycidyldia",i"oî~henylmethane,
such as Araldit~MY 720, Araldit~MY 721.
Particularly preferred difunctional epoxides are fiquid or low-melting diglycidyl ethers based
on bisphenols, for example on 2,2-bis-~4-hydroxyphenyl)propane ~bisphenol A) or mixtures
of bis(ortho/para-hydroxyphenyl)methane (bisphenol F).
Very particularly preferred epoxides are bisphenol A diglycidyl ethers, for example:
Araldit~GT 6071 or Araldit~GY 260; bisphenol F diglycidyl ethers, for example Araldit~
PY 306; liquid cycloal;~,halic epoxy resins, for example Araldit~CY 179; or phenol novolak
epoxy resins, e.g. Araldit~PY EPN 1139.
The process can be carried out in any vessels which can be heated and are fitted with a
stirring device. These may, for example, be closed apparatus from which atmospheric oxy-
gen is excluded, working for example under an inert gas atmosphere such as nitrogen. The
process is preferably conducted in an extruder.
The polyolefin recyclate to be heated and the mixture comprising a secondary aromatic
amine and a difunctional epoxide are nGr".ally charged to the apparatus at the beginning of
heating; however, subsequent metered addition of the novel mixture to the polyolefin re-
cyclate is a further option, it being possible to add the mixture as such or else to add the
individual coll,ponents in any desired sequence.
For addition, the secondary aromatic amine and the polyfunctional epoxide can, indepen-
dently of one another, be present in the form of a liquid, powder, granules or in compacted
form, or else on a carrier material such as silica gel, or together with a polymer powder or
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wax, for exllmple a polyethylene wax. In the present novel process, liquid addition is pre-
ferred.
For each 100 parts of polyolefin recyclate, it is preferred to employ from 0.01 to 5 parts of a
secondary aromatic amine and from 0.01 to 10 parts of a polyfunctional epoxide. In this
context, particular preference is given to the use of from 0.05 to 5 parts, especially from
0.05 to 2 parts, of a secondary aromatic amine, and from 0.05 to 5 parts, especially from
0.05 to 2 parts, of a polyfunctional epoxicle.
The novel process has the advantage that the polyolefin recyclate is sl~ ed in short reac-
tion times, and the additives, for example the secondary aromatic amine and the polyfunc-
tional epoxide, can be added in liquid form. The combination of secondary alulllalic amines
wilh polyfunctional epoxiclQs leads synery;slically to the :ilaL:';7~tion of polyolefin recyclates.
The presen~ invention also provides a mixture com~,ising a) a secondary aromatic amine
and b) a polyfunctional epoxide, the weight ratio of the cG,.~ponents a): b) being from 10:1
to 1:10, in particular from 5:1 to 1:5, for example from 2:1 to 1:2. Special preference is given
~ to a weight ratio of cG"~ponel-ts a): b) of from 1.5:1 to 1:1.5, in particular from 1.1:1 to 1:1.1,
for example 1:1.
The ,~ felenc~s regarding a) and b) correspond to those for the novel process.
In addilion k) the mixture of a secondary aro",alic arnine and a polyfunctional epoxi{le, addi-
tional stabilizers and additives can be added to the polyolefin recyclate. The following are
exa",ples of such additives:
1. Antioxidanl:j
1.1. Alkylated ",onopl,enols. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-
methylphenc)l, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu-
tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl-
phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-
methoxymel:hylphenol, nonylphenols which are linear or branched in the side chains, for
example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-di-
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methyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and
mixtures thereof.
1.2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc-
tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-
4-nonylphenol.
~.3. Hydroauinones and alkylated hvdroquinones, for exarnple 2,6-di-tert-butyl-4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-
cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-
butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-
hydroxyphenyl) adipate.
1.4. Toco~herols. for example a-tocopherol, ~-tocopherol, y-tocopherol, ~-tocopherol and
mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers. for example 2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-
2-methylphenol), 414'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphe-
nyl)rlic~ ~Ifjde
1.6. Alkylidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethyl,uhenol), 2,2'-methylenebTs[4-methyl-6-(a-methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexyl,~,hel-ol), 2,2'-methylenebis(6-nonyl-4-me-
thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl-
phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben-
zyl)-4-nonylphenol], 2,2'-methylenebis[6-(o~,a-dimethylbenzyl)-4-nonylphenol], 4,4'-rnethy-
lenebis(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-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-
butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadi-
ene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha-
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late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphe-
nyl)propane, 2,2-bis-~5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1, 1,5 ,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-. N- and S-benzyl compounds. for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-
benzyl eth~3r, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-
3,5-di-tert-l~utylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl~amine, bis~4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiotel ephll -alate, bis(3,5-di-tert-butyl-4-hydroxy-
benyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates. for example ~lioctedecyl-2,2-bis-(3,5-di-tert-butyl-2-hy-
droxybenzyl)-malonate, di-octadecyl-2-~3-tert-butyl-4-hydroxy-5-methylbenzyl~-malonate, di-
dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-te-
tramethylb~tyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)r"alonate.
1.9. Aromal:ic hydroxybenzvl compounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds. for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hy-
droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,6-
triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-
tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-
benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,~-di-tert-butyl-4-hydroxyphenylethyl~-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl4-hydroxyben-
zyl)isocyanurate.
1.11. Benzylphosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl~,hospho-
nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl~hos,uhonate, dioctadecyl3, 5-di-tert-butyl-4-hy-
droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate,
the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylpho~phon-G acid.
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1.12. Acylaminophenols. for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-
(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of ,~-(3,5-di-tert-butvl-4-hydroxyphenyl)~ro~ionic acid with mono- or polyhydric
alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-
lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy-
droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of ~,-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-
diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene gly-
col, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,
N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, I.i"lelllylhexanediol,
trlmethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo~2.2.2]octane.
1.15. Esters of ,~-(3.5-dicyclohexyl-4-hydroxy~henvl)proPionic acid with mono- or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, oct~dee~rlol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyi)ox-
amide, 3-thiaundecanol, 3-thiapentaclec~nol, trimethylhexanediol, trimethylolpropane, 4-hy-
droxymethyl-1-pl,ospl,a-2,6,7-llio ''. )~clQr~ octane.
1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco-
hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol"ropane, 4-hy-
droxymethyl-1 -phospha-2,6 ,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of ~-(3.5-di-tert-butyl-4-hydroxYphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-
butyl-4-hydroxyphenylpropionyl)hexamethylened;al" ~'a, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-
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phenylproF~ionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyipropionyl)-
hydrazide, N,N'-bis~2-(3-~3,5-di-tert-butyl-4-hydroxyphenyl3propionyloxy)ethyl30xamide
(Naugard~~L-1 supplied by Uniroyal).
.,
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants. for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-
butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl~-p-phenylenediamine, N,N'-bis(1-
ethyl-3-mel:hylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naph-
thyl)-p-phenylenediarlline, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-
N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclo-
hexyl-N'-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-
N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phe-
nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine,
4-n-butylarrlinophenol, 4-butyrylar.;nophenol, 4-nonanoylaminophenol, 4-dodecanoylan,i.,o-
phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dime-
thylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane,
1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis~4-(1',3'-dimethylbutyl)phenyllamine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-
octyldiphen'ylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of
mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro-
pylAsohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-ben~ i--e, phenothiazine, a mixture of mono- und dial-
kylated tert-butyl/tert-octylphenoll-ia~illes, a mixture of mono- und dialkylated tert-octyl-phe-
nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diarninobut-2-ene, N,N-bis-
(2,2,6,6-tetr~methyl-piperid-4-yl-hexamethylenedia~lli,le, bis(2,2,6,6-tetramethylpiperid-4-yl)-
seb~c~te, 21,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
~ UV absor~bers and light stabilisers
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2,1~ 2-(2'-Hvdroxyphenyl)benzotriazoles. for example 2-(2'-hydroxy-5'-methylphenyl)-benzO-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)ben~otriazote, 2-(5'-tert-butyl-2'-hydroxyphe-
nyl)ben~olliazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)~enzotriazole, 2-(3',5'-di-
tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole. 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphe-
nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-
(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotri-
azole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hy-
droxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hy-
droxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-
5'-(2-methoxycarbonylethyl)phenyl)ben~ol-ia~le, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy-
carbonylethyl)phenyl)bei~,lliazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-
hydroxyphenyl)ben~olriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis-
[4-(1,1,3,3-tetramethylbutyl)-6-bel-~ol,;A :le 2 yl,~het)ol~; the transesterification product of 2-
[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethy-
lene glycol 300; ~R--CH2CH2 COO-CHzC~2~ where R= 3'-tert-butyl-4'-hydroxy-5'-2H-
benzotriazol-2-ylphenyl, 2-~2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-
phenyl]benzotriazole; 2-l2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)-
phenyl]benzotriazole .
.2. 2-Hydroxybe"zophenones. for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids. as for example 4-tertbutyl-phenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-
zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-
ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy-
ben~ale, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxyben~oa(~.
2.4. Acrylates, for example ethyl a-cyano-~"~-diphenylacrylate, isooctyl a-cyano-,~"~-diphe-
nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-,B-methyl-p-methoxy-cinna-
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mate, butyl a-cyano-,~-methyl-p-methoxy-cinnamate, methyl o~-carbomethoxy-p-methoxycin-
namate and N-(,~-carbomethoxy-,B-cyanovinyl)-2-methylindoline.
.5~ Nickel compounds. for example nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetrame-
thylbutyl)phlenol~, such as the 1:1 or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-~yclohexyldiethanolamine, nickel dibutyldithiocarbamate,
nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel ¢omplexes of ketoximes, e.g. of 2-hydroxy-4-methylphe-
nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
2.6. Sterically hindered amines. for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)seba-
cate, bis(1-octyloxy-2,2,6,6-tetramelhyl-4-piperidyl)sebAc~te, bis(1,2,2,6,6-penl~r"ethyi-4-pi-
peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the concJensate of 1-(2-hydroxy-
ethyl)-2j2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic conden-
~ates of N,rl'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenedi~".;.,e and 4-tert-octylami-
no-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriAcet~te, tetrakis-
(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethanediyl)-bis-
(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-
2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-~2-hydroxy-3,5-
di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-t, i~ piro[4.5]decan-2,4-
dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sehAc~t~. bis(1-octyloxy-2,2,6,6-tetrame-
thylpiperidyl)succ;nale, linear or cyclic condens~les of N,N'-bis-(2,2,6,6-tetramethyl-4-piperi-
dyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,~i-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl )-1 ,3,5-triazine and 1 ,2-bis(3-
aminopropylamino)ethane, the cGndensale of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pen-
tamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis-(3-aminopropylarnino)ethane, 8-acetyl-3-dode-
cyl-7,7,9,9-tetramethyl-1,3,8-triA~-spiro[4.5~decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetrame-
thyl-4-piperidyl)pyrrolidin-2,5-dion~, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrroli-
dine-2,5-dione, a mixture of 4-hex~decyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine,
a condensakion product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine
and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, a condensatiGn product of 1 ,2-bis(3-ami-
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.
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nopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-te-
tramethylpiperidine (CAS Reg. No. ~136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-do-
decylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-
7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-
tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin,
1,1-bist1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-
formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-
methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-
3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleic acid anhydride-
a-olefin-copolymer with 2,2,6,6-tetrarnethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-
aminopiperidine .
2.7. Oxamides, for example 4,4'-dioctyloxyoxar, "~P, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani-
lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its
mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disub-
stituted oxanilides and mixtures of o- and p-ethoxy-~ Ihstituted oxanilides.
2.~. 2-(2-Hydroxyphenyl)-1 .3.5-triazines. for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-
1,3,5-triazine, 2-(2-hydroxy~-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-pro-
pyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-
(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphe-
nyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bls(2,4-dimethyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl~-1,3,5-
triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-
triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triaZine, 2,4,6-tris[2-hydroxy-4-
(3-butoxy-2-hydroxy-propoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl3-4-(4-methoxyphe-
nyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxylphe-
nyl}-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine.
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3. Metal deactivators. for example N,N'-diphenyloxar~ e, N ~-~i ,1al-N'-salicyloyl hydrazine,
N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenyl,~,r~,pionyl) hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl
dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl-
oyl30xalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites. for example triphenyl phosphite, diphenyl alkyl phosphi~es,
phenyl dialkyl phosphites, tris~nonylphenyl) phosphite, trilauryl phosphite, trioc~clecyl phos-
phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-
di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol di-
phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol dipho~phile, bis(2,4,6-tris(tert-
butylphenyl,'lpentaerythritol diphosphite, tristearyl sorbitol triphosphite, tel~kis(2,4-di-tert-bu-
tylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-
benzld,g]-1 ,3,2-dioxaphosphocin, 6-fluoro-2,4,8, 1 0-tetra-tert-butyl-1 2-methyl-dibenz[d,gl-
1 ,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-
tert-butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo~triethyltris(3,3',5,5'-tetra-tert-butyl-
1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-letra-tert-butyl-1,1'-biphenyl-2,2'-di-
yl)phosphite.
Especially preferred are the f~'low;.,g phosphites:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos~168, Ciba-Geigy), tris(nonylphenyl) phos-
phite,
(CH3)3C:~C(CH3)3 (CH3)3c~C(CH3)3
(A) H9C--C~ OrC(CHJ~ (CHD)~C--~ p_o--CH2cH2--N (B)
(CH3)3C - --3
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(CH3)3C ~C(CH3)3
~_ P O CHZCH(C~H8)CH2CH3
(CH3)3c--~
C(CH3)3
(CH3)3C ~'oXo' ~--C(CH3)3 (D
C(CH3)3 (CH3)3C
C(CH3)3 (CH3)3c
H3C ~ ~oXo~ ~CH3 (E)
C(CH3)3 (CH3)3C
-- ICH3
H3C--C--C~3
(F) H C--~--p' X _9 Cll, o--P--OCH~CH:~ (G)
Very particular preference is given to tris(2,4-di-tert-butylphenyl3 phosphite [Irgafos~168,
Ciba-Geigy], bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite [Irgafos~38, Ciba-Geigy,
formula (G)] and 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-t,1'-biphenyl-2,2'-diyl)-
phosphile [Irgafos~12, Ciba-Geigy, formula (B)].
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. Hydroxylamines. for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine,
N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,l~l-
dihexadacyihydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhy-
droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived
from hydrogenated tallow amine.
ff. Nitrones. lor example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc-
tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-
hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-
alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep-
tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhy-
droxylamine derived from hydrogenated tallow amine.
7. Thiosyneraists. for example, dilauryl thiodipropionate or distea~l thiodiprD~ ionate.
8. Peroxide s;cavenaers. for example esters of ~-thiodipropionic acid, for example the lauryl,
stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-
benzimidazole, zinc dibutyldill,iocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(,B-
dodecylmercapto)propionate.
~ Polyamide stabilisers, for example, copper salts in combination with iodides and/or phos-
phorus compounds and salts of divalent manganese.
10. Basic co-st~hi';sers. for example, melamine, polyvi.,ylpyrrolidone, dicyandial, ~6, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, al-
kali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stea-
rate, zlnc ste~lrate, magnesium behenate, magnesium stearate, sodium ricinoleate and po-
tassium pal",il~te, antimony pyrocatecholate or zink pyrocatecholate.
~1. Nucleatin~ aaents. for example, inorganic substances such as talcum, metal oxides
such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, pre-
ferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids
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and the satts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium
succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). t
12. Fillers and reinforcinq agents, for example, calcium carbonate, silicates, glass fibres,
glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-
bon black, graphite, wood ~lour and flours or fibers of other natural products, synthetic fi-
bers.
13. Other additives. for example, plasticisers, lubricants, emulsifiers, pigments, rheology
additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, anli~ldlic
agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863;
U.S. 4,338,244; U.S. 5,175,312; IJ.S. 5,216,0~2; U.S. 5,2~2,643; DE-A-4316611;
DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-
phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phe-
nyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-~4-[2-hydroxyethoxy]phenyl)benzofuran-2-
one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,~-dimethylphe-
nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-bu-
tyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-di-
methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
The addilional additives and/or st~hili7ers are preferably added to the novel mixture compri-
sing a) a secondary aromatic amine and b) a polyful,uliol)al epoxide.
With the exception of the fillers, reinforciog agents (item 12 in the list) and glass fibres, the
additional additives are added to the polyolefin recyclate in conce,lllations, for example, of
from 0.01 to 10 %, based on the overall weight of the polyolefin recyclate to be sl~ ed
The fillers and reinforcing agents (item 12 in the list) such as, for example, talc, calcium car-
bonate, mica or kaolin, are added to the polyolefin recyclate in concentrations, for example,
of from 0.01 to 40 %, based on the overall weight of the polyolefin recyclate to be s~
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The fillers and reinforcing agents (item 12 in the list) such as, for example, metal
hydroxides, especially aluminium hydroxide or magnesium hydroxide, are added to the
polyolefin recyclate in concentrations, for example, of from 0.01 to 60 %, based on the
overall weight of the polyolefin recyciate to be st~hi'i~er~
Carbon black as a filler is added to the polyolefin recyclate expediently in concentrations of
from 0.01 to 5 %, based on the overall weight of the polyolefin to be stabiiized.
Glass fibres as reinforcing agent are added to the poiyolefin recyclate expediently in con-
centrations of from 1 to 30 %, based on the overall weight of the polyolefin recyclate to be
stabilized.
Furt~er customary polyolefin additives can also be polymers which enhance the material
properties of the previously damaged polyolefin, such as elastomers (impact modifiers) or
co",patil~iliz~3rs (i.e. additives which improve comp~tihility).
Impact modifiers are homo- or copolymers which are able to modify brittle polyolefins in
~ such a way that they retain impact ~trength even in the cold. Suitable examples are EPM
polymers, El'DM polymers, ABR, BP~ or SBR graft polymers.
Examples ol possible comp~tihili'ers are copolymers, especially block copolymers, of sty-
rene with butadiene with or without acrylonitrile. Further co,-lp~ rs can be copolymers
of ethylene ~Ind propylene with or without a third monomer component, such as butadiene,
for example. Chlorinated polyethylene, or ethylene-vinyl acetate copolymers, are also sui
table as cornpatibilizers, a critical factor being of course the respective composition of the
recyclate. Further suitable co~palibilizers contain, in particular, polar groups, for example
maleic anhydride-styrene copolymers or graft polymers conkai.,i"g acrylic acid groups.
The co,.~p~ ers are preferably used in amounts of from 2 to 20 %, based on the overall
weight of the polyolefin recyclate to be sl~ ed.
J
Also of interest is the novel process for stabilizing polyolefin recyclates against oxidative,
thermal and/or light-induced degradation wherein further additives over and above at least
one secondary aromatic amine and at least one polyfunctional epoxide are addedl especial-
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Iy UV absorbers and light stabilizers (item 2 in the list); amides of ~-(3,5-di-tert-butyl-4-hy-
droxyphenyl)propionic acid (metal deactivators, item 1.17 in the list); nucleating agents (item
11 in the list); fillers and reinforcing agents (item t2 in the list); and/or comp~tihi';~ers.
Very special interest attaches to the novel process for stabilizing polyolefin recyclates
against oxidative, thermal and/or light induced degradation wherein at least one compati-
bilizer is added as a further additive in addition to at least one secondary aromatic amine
and at least one polyfunctional epoxide.
The incorporation of the secondary aromatic amine and the polyfunctional epoxide, and of
further additives if appropriate, into the polyolefin recyclate is accomplished by known
methods, for example prior to or during shaping or else by applying the liquid, dissolved or
dispersed ~l~bili~er mixture to the polyolefin recyclate, with or without subsequent evapora-
tion of the solvent. The stabilizer mixture can also be added in the form of a masterbatch,
containing said stabilizer mixture in a concentration, for example, of from 2.5 to 25 % by
weight, based on the weight of the polyolefin recyclate or virgin polyolefin material, to the
polyolefin recyclates which are to be s~hi'i~ed.
The novel stabilizer mixtures can be incorporated in pure form or encapsulated in waxes,
oils or polymers into the polyolefin recyclate which is to be st~hi~i7~ri
The novel stabilizers, such as the secondary aromatic amine and the polyfunctional epoxide
or mixtures thereof, can also be sprayed onto the polyolefin recyclate which is to be stabi-
lized. They are capable of diluting other additives (for example the customary additives in-
dicated above) and/or their melts, and consequently can also be sprayed together with
these additives onto the polyolefin recyclate whTch is to be st~hi~i~ed
The polyolefin recyclates thus st~hili~ed can be used for a very wide variety of purposes, for
example for pipes, profiles and panels, such as insulating panels, pallets, cable insulation,
sporting equipment, garden furniture, films, construction components, parts of vehicles and
machines, containers of all kinds, such as bottles, or packaging material.
The polyolefin recyclate can also be employed in a form mixed with virgin polyolefin material
or together with virgin material, fo example in a coextrusion iprocess.
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The invention additionally provides for the use of a mixture comprising a secondary aroma-
tic amine and a polyfunctional epoxide for ~ -~.'i71ng polyolefin recyclates against oxidative,
thermal and/or light-induced degradation. The preferences regarding the use correspond to
those for the process.
The inventiion also provides a cornposition comprising a) a polvolefin recyclate, b) a secon-
dary aromatic amine, and c) a polyfunctional epoxide. The preferences regarding the com-
position corlespond to those for the pr~Jcess.
The invention additionally provides polyolefin recyclates obtainable by the novel process.
The examples which follow illustrate the invention in more detail without limiting it thereto.
As in the remainder of the description, parts and percentages are by weight unless stated
otherwise.
Example 1: St~h~ g polypropylene copolymer recyclate from baKery cases.
In a Plasticorder from Brabender with a W ~0 mixing chamber, regrind from used battery
cases (polypropylene copolymer) is kneaded at a temperature of 210~C and at 40 revolu-
tions/minute for 60 minutes together with the additives indicated in Table 1. The torque of
the polymer is determined after 30, 45 and 60 minutes. The greater the number, the better
the stabiiization. After 60 minutes, lthe melt index (MFR) is messured (at 235~C under 2.16
kg in accordance with ISO 1133~. A large increase in the melt index denotes severe chain
degradation, and therefore poor ~ (;on. The results are cor, r-'~d in Table 1.
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Table 1:
Torque [Nm] after Melt
Example Additives index
30 min. 45 min. 60 min.[g/10 min.]
1 a~) 1.4 0.6 0.3 >150
1b~) 0 50 % Irganox~5057a) 5.8 5.4 4.6 5.1
lce) 0.50 % Araldit~GY 260b~ 2.1 1.0 0.5 ~150
1de) 0.50 % Araldit~PY 306C)2.3 1.0 0.5 >150
1e~) 0.50 % AraldirGT 6Q71d)1.9 0.9 0.4 >150
1ffl 0.25 % Irganox~5057a) 6.2 5.8 5.4 3.3
0.25 % Araldit'DGY 260b)
1gfl 0.25 % Irganox~5057a) 6.1 5.6 5.3 3.4
0.25 % Araldit~PY 306C)
1hf~ 0.25 % Irganox~5057a) 6.0 5.7 5.4 3.0
0.25 % Araldit~GT 6071d)
a) Irganox~5057 (Ciba-Geigy) is 4,4'-di-tert-octyldiphenylamine (see formula le).
b) Araldit~GY 260 (Ciba-Geigy) is a liquid epoxide of the bisphenol A diglycidyl ether type.
c) Araldit~PY 306 (Ciba-Geigy) is a liquid epoxi~e of the bisphenol F diglycidyi ether type
ldiglycidyl ether of bis~ortho/para-hydroxyphenyl)methane (Bisphenol F)].
d) Araldit~GT 6071 (Ciba-Geigy) is bisphenol A diglycidyl ether with an epoxide number of
2.15-2.22 Eq/kg and a softening range of 70-75~C.
e) Comparison examples.
f) Novel examples.
Example 2: St~hlli7irlg mixed polyolefin recyclates.
In a plasticorder from Brabender with a W 50 mixing chamber, a mixture of used plastics
consisting of about 80 % by weight of HD-polyethylene, about 15 % by weight of LD-poly-
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ethylene and about 5 % by weight of polypropylene is kneaded at a temperature of 190~C
, .
and at 40 revolutions/minute for 60 minutes together with the additives indicated in Table 2.
The torq~le of the polyolefin mixture is determined after 20, 40 and 60 minutes. The larger
the number, the better the st~hili7~tion. After 60 minutes, the melt index (MFR) is measured
(at 235~C under 2.16 kg in accordance with IS0 1133). A làrge increase in the melt index
denotes severe chain degradation, and thus poor stabilization. The results are compiled in
Table 2.
Table .':
Torque [Nm] after Melt
Example Additives index
20 min. 40 min. 60 min. ~9/10 min.]
2ad) -- 5.34.4 3.7 7.7
2b~) 0-25 % IrganOx~sos7~) 5.64.7 4.0 6.1
Q.25 % Araldit~CY 179b)
2c~) 0-25 % Irgan0x~sos7a) 4.2 6.3
0.25 % Araldit~EPN 11 39C)
a) Irganox~5057 (Ciba-Geigy) is 4,4'-di-tert-octyldiphenylamine (see formula le).
b) Araldit~'CY 179 (Ciba-Geigy) is liquid 3,4-epoxycyclohexylmethyl 3,4-epoxy-
cyclohexanecarboxylate, epoxide cor,lent 7.0-7.5 equivalents/kg.
c) Araldit~'EPN 1139 (Ciba-Geigy) is a liquid phenol novolak epoxy resin, epoxide content
5.6-6.8 equivalents/kg.
d) Comparison exampte.
e) Novel examples.
