Note: Descriptions are shown in the official language in which they were submitted.
WO 94/06831 ~ 1 ~ 310 3 PCI/EP93/02419
Process for the ~ ion of olefin pol~,nners
The present i~ ,nlioll relates to a process for the preparation of olefin polymcrs in which
hydrot~lcites, 7eolites or metal oxides and optional st~bilicers are added during the
polymloric~tion, The invention also relates to the olefin polymers so oblained.
The low-~le~ polymeric~tion of olefins with o~ -olll~t~l1ir- comrl~PY catalysts (e.g.
Ziegler-Natta catalysts) usually results in a finely powdered polymer which is extruded in
an cxtruder before being shapcd by ~ce~ g. In this ~n~ tion, subst~nccs such as
st~hilic~rs, corrosion inhih-;tr~rs~ colour enh~ncers~ ~ntict~tic agents or other l,l~ccs~: ng
~l1Yili~ries However, this gr~nl1l~tion is not always desired or possible, inter alia, with
polymers of high molPcnl~r weight.
Recently, it has proved possible by using solid ~u~u-Led catalysts to ~a-~c spherical,
granular-type polymers that no longer have to be gr~nl1l~t~1 by extrusion, but can be
~lvcessed direct. Suitable suppor~s for these solid catalysts have been found to be in
particular sphPrir~l m~gnP,cil1m halides of specifir particle size as ~iccloseA inter alia, in
DE-A-2 641960. The anhydrous m~ .s;.JIll halide forms with TiCl4 andclc~luil donors
incoll1h1e compl~Y~s which are then activated with allln~ill;llln alkylene. The
stereo~e~-;ri~ity and activity are enh~nreA by using electron donors such as c&ll,o~ylic
acid esters or compounds cont~;nil~g Si~-C bonds as ~licclosed~ inter alia, in
EP-A-45 977.
As the polymers so obtained no longer have to be gram1l~tPd, it was then desired to add
mo-lifiers which are important for ~-ocescil~g and long-term stability during
polymPric~ti()n The addition of many conventional modifiers (e.g. st~bilicerc) illLelrcl~s
with the olefin polymeric~tion and causes discolouration of the polymers.
The m~rhinP.s used in further processing of the polymers, e.g. c~l~ndPrs, are subject to
corrosion. The corrosive action of the polymer on metal surfaces is generally attributed to
catalyst residues or degradation products of the catalyst system. Up to now it has been
Wo 94/06831 ,~ ,3 PCr/EP93/02419
.-rces.~h.y to add a corrosion inhibiting col~ ,und in a sep~ ces~ g step.
It is known (EP-A-192 987 or EP-A-0 350 4~14) that str.ri~lly hin~lf.~ amine st~hili~f~.
of the polyaLkyll.;l f ~ ine type do not illLc.r~ with the polymPri~tion and do not
subs~nti~lly discolour the polymer and effect good thf~rm~ id~ , stability.
It has further been p-o~osGd (EP-A-254 348) to add organic phoi,~l,;t~.s or phnsphnnites as
~ntjoYir1~nt~.
It is also known to add ste,ri~lly hindered amine st~bili~ers of the polyalkyll.;pc ;rline type
in colljullcLion with organic ~hnsl.l.i~s or phos~hh..;~,s during the polyrn~ri~tinn
(EP-A-0 351 360).
Surp i~ingly, it has now been found that the ~Mitinn of c~mpo~ of the series of the
hydrot~lçitf,s"~lil. s or metal oxides which do not release water under the ~ioncnn~litinn~, in conjul-cLion with optional st~bilisf~ s, does not illteL~ with the
~oly.~lf ~ tinn of olefins and ~ s~ lly prevents corrosion o~ ,.w~e oc~ g duringpolytn~ri~ti~ n, and that eyl~f~ nt long-term stability is achh,~,d by adding further
st~hili~f-rs
~rcnr~lingly~ the invention relates to a ~roccss for the ~ p~' Al jon of olefin polymers by
poly---~ l ;C~ n using 1- ~ ;I;n.~ metal catalysts, which compn~çs ca~rying out the
polymP-ri~tinn by adding at least one col~puulld of the series of the hydrot~1cites, 7~,olitçs
or metal oxides that do not release water under the reaction co~tlitinll~
The polyn Pris~tinn is preferably ca~ied out with a solid ~u~olt~d tr~n~itinn metal
catalyst which has been ~ al~,d by reacting an ~1.. ;.~;.. colll~oulld caTry~ng at least
one aLkyl group with a colllpoulld of a metal of the IVth subgroup of the Periodic Table.
The olefins poly~eri~hle by this process are ethylene and a-olefins such as propylene,
but-l~ne, ~methyll)ent-l-ene or 5-methylhex-l-ene, as well as Illib~luu~s of olefins,
typically ethylene-propylene or propylene in ~ with minor ~mo~1nt~ of higher
a-olefins. The process for the polym~ris~tion and copolymeris~tion of propylene is of
particular interest.
The polymPri~tinn catalysts are tr~nsitiQn metal catalysts. They typically consist of a
W O 94/06831 ~14 310 3 PC~r/EP93/02419
m~..eS;~ lih~ lP in active form and a tit~nillm compound. Catalysts with the other
metals of the IVth subgroup of the Periodic Table (Zr and Hf) are also suitable. By
m~gntoSillm tlih~ le in active form is meant one in whose X-ray ~e,cLlulll the line of
sngest reflc~;LiviLy is broader than the cull~;.yollding line in the S~CCLl ulll of the inactive
m~gnesillm halide.
It is yl~,rc~l~ d to use m~gn.q.Sillm (lirhlnsi~le or m~g..eS;-.... dibromide as m~ ..P.~; ~....
~lih~lirlr, The t;t~..hllll con~younds preferably contain at least one l;lnn;.l~n-halide bond. It
is particularly ylGr~l~d to use ~;lnn;lllll tetr~rhlnri~
The l;l~..;..l.. conll,ound can be used in conjunrtinn with an elecLIun donor, typically a
CLUbUAY1iC acid ester, as ~ closed in EP-A-45 977.
After reaction of the m~gn~ lm halide colll~ollellt with the I ;Inll;l --- comyound and,
where a~yru~liate, the clecllun donor, excess t;l~ co...pou-.d and excess elec~ndonor are con~.niclltly washed off with an inert solvent, typically with hexane or h ~ e.
The catalyst so yl~ d is a~;Liv~cd by reaction with an ~l.. l.. i.~;.. compound which
carries at least one aLkyl group and is used preferably as a solntion in an aLkane.
l~.Yrmpl~ry of suitable ~hl.. ,il.;.. alkyls are Al(C2Hs)3 or Al(C4Hg)3. It is pos~ib!e to use
an clec~un donor as co-acL-~Lor, con~ iently an organic silicon co..l~ound that co~ln;~
at least one Si-O-C bond, as ~ rlose~l in EP-A~5 977. Typical eY~mrlPs of such silicon
co..lyounds are phenyl 1. ;elhn~ysilane, phenyl 1. ;-..clh~y~ilane, diyhcnyl
flimethoxysilane, methyl triethoxysilane, dimethyl diethoxysilane or ethyl
trimethoxysilane.
Further tr~n~ition metal catalysts typically consist of a cLIullliulll co--lpound on a soli
support, e.g. ~lnmin~ or silica or mLLlulGs thereof. Examples of such catalysts, also called
Phillips catalysts, will be found in US-A-2 825 721.
The polymr,ri~tion with these catalysts can be carried out by known methods in liquid
phase or in the gas phase. The liquid phase may conveniently be an alipha*c hyd ucalbon
or the liquid monomer itself.
The col..~ou-lds of the series of the hydrot~lcites, zeolites or metal oxides that do not
release water under the reac*on cQ~lition~ are added to the polymeri~*( n meAillm at the
wo 94/06831 ~ 3 ~ 3 pcr/Ep93/o24l9
--4--
start, during, or towards the end of the polym~ tirm
Co~ oullds of the series of the hydrot~1~ites, 7ef-1ites or metal oxides are the n~t~l~lly
occ~ g mint~ as well as ~ ;r~11y p~ d colll~oullds.
~o---l-u---~ls of the series of the hydrot~l~ittos may be i~ t~cl by the general f~ rmn1
M2+~ M3+" -(OH)2 -(An~ mH20 ~I~
wl-~,.cil-
M2+ = Mg, Ca, Sr, Ba, Zn, Cd, Pb, Sn and/or Ni,
M3+ = Al, B or Bi,
An is an aniûn of valency n,
n is a number from l to 4,
x is a number from 0 to 0.5,
m is a number from 0 to 2, and
A = OH-, C~, Bf, I-, Cl04-, HCO3-, CH3COO-, C6H5COO-, co32-, so42-,
,COO~
COO-,(CHOHC00)22-,(CHOH)4CH20HCOO-.C2H4(CO0)22-,(CH2CO0)22-,
CH3CHOHCOO-, SiO32-, sio44-, Fe(CN)63~, Fe(CN)64~ or HPo42-.
Other hydrotalcites which may cûl~ iclllly be used in the ~r~cess Aes~nbe~l above are
cu---~uu--ds of the general form~ Ia
Mx+Al2(OH)2~+6nz(An~)2-mH2O (Ia)
wll~,lcill M2+ is at least one metal of the series of Mg and Zn, Mg being ~l~fc . c d, An- is an
~ C, 00~ 2-
anion of the series of co32-, ~ (~OO) , OH- and S2-, and n is the valency of the anions, m
is a posili~,e number, preferably from 0.5 to 5, and x and z are ~o~ , numbers, and x is
preferably 2 to 6 and z is smaller than 2.
E~cfe~d cG~Ilpû~ of the series of the hydrot~l-ites are those of the general formn1~ I
M2+l X M3+,~ (OH)2 (An-)" mH20 (I~
~ 21~3~3
WO 94/06831 PCI/EP93/02419
. . .
Wh~lll M2+ iS Mg or 11~PnotP~s a solid sol-ltir n of Mg and Zn, An- is co32-, x is a nnmber
from 0 to 0.5 and m is a nl-mber from 0 to 2.
Particularly ~iefe,l~d hydrotalcites are those of fonn~ P,
Al203-6MgO-C02- 12H2~
Mg4,sAl2(0H)l3 C03 3~5H20
4MgO-Al203-C02-9H2
4MgO-Al203-C02-6H20~
ZnO-3MgO-Al203-CO2-8-9H20 oder
ZnO-3MgO Al203 C02 5~6H20 -
In the practice of this i..~ Lion it is also possible to use 7eolites of the general ft~rm
M~ t(AlO2)~c(siO2)y] wH2o (X)
~Le.~ill n is the charge of the cation M,
M is an el~om~nt of the first or second main group of the Periodic Table,
y: x is a nnmber from 0.8 to 1.2, and
w is a number from 0.5 to 10.
The ~l-,Çell~d per se known 7~olitp~s which may be used in the above ~luce,ss have an
average pore r~i~mpter of 3-5 A, inclllrling those of the NaA type that have an average
effective pore fli~metP.r of 4 A, for which reason they are also called 4A 7P~litPS
Illustrative examples of snit~kle 7P~litPs are the colll~uullds:
Nal2r(Al02)l2(SiO2)l2] 12H2
Ca4~sNa3[(Alo2)l2(sio2)l2] 30H20
WO 94/06831 PCr/EP93/02419
L~3
K9Na3[(AlO2)l2(siO2)l2] 27H2o
Metal oxides can also be used in the process of this invention. Oxides of divalent metals
are ~-~f~ ~ Oxides of metals of the second main group or subgroup of the Periodic
Table are especially ~lefc,.-ed, and zinc or m~r.. rs:.. oxide is most ~-~,Çc.-~
The novel co.l.~ou.lds are dried to remove the unbound or only loosely bound water at
50-800C, preferably 80-400C, provided they are not already sllffici~r tly dry and have
been stored with exclllcion of moict~lre. Drying can be carried out under vacuulll or inert
gas. The ~. r~,cs of the s~lbsli~n~s can be treated with surface active re~g~ntc such as
CalbUAY1iC acids or linear ~l~oholc of 8 or more carbon atoms, con~ tly stearic acid.
The colllpuunds of the series of the hydrot~lrit~s~ 7P~littq-s or metal oxides or similar
sy~ lly ~-~Gd co-llpounds that do not release water under the reaction conAitinn~
are nnrm~lly added in an ~mollnt of 0.005 to 5.0 % by weight, preferably from 0.01 to 1 %
by weight, based on the polymer.
The process is preferably carried out using ~AAition~l stabilisers.
A particularly ~ -~,r~ d emboAiment of the invention co...~ s carrying out the above
~JCGSS by the further ~(lAition of a compound that csnt~inc at least one 2,2,6,6-tetra-
melllylpi~ idine radical and that has a mol~ r weight above 500, or by the further
~Mi*on of a phosphorus(III) compound. The use of such a 2,2,6,6-tetramelllyll.il,&. ;Ain~.
compound with a phnsphorus(m) compound is particularly pl~r~l~,d.
The st~rir~lly hindered ~min~s, preferably piperiAines, are known in particular as light
st~hilicers, but they act here also as antioxidants, i.e. they impart thPrm~l oxidative
stability to the polymer. These compounds contain one or more than one group of
formula I
H3C CH3 s
N~ (I),
H3C CH3
~ WO 94/06831 214 310 3 PCI/EP93/02419
They may be oligomeric or polymeric co~
Particularly Ul~Ollai)~ st~kilicers are the following classes of ~el~-,.rtl~y~ r,s
a) compounds of formula II
H C
3 ~H3
R _ N~ ~ O R (II),
H3C CH3 ~ n
wh~ n is a number from 1 to 4, preferably 1 or 2, Rl is hy~ cll, oxyl, Cl-Cl2alk~yl,
C3-C8~1kt~.nyi, C3-C8aLynyl, C7-Cl2araLlryl, Cl-C'8~lk~noyl~ C3-~s~lk~'nnyl~ glycidyl or a
group -CH2CH(OH)-Z, wl.c~ Z is hydrogen, methyl or phenyl, the ~er~l,Gd m~.~ninE Of
Rl being Cl-C4alkyl, allyl, benzyl, acetyl or acryloyl, and R2, if n is 1, is lly~O~
Cl-Cl8aLkyl which may be ilite~u~d by one or more than one oxygen atom, Cyal~O~ lhyl,
benzyl, gly~;dyl, a monovalent radical of an ~lirh~ti~ cy~lo~lirh~t;~ irh~ti~
..... c~ l .. 2. t~ .~1 0r aromatic cal1,0Aylic acid, c~ub~nic acid or or phosphorus cc l~t~h~ g aCid,
or is a monovalent silyl radical, preferably a radical of an ~lirh~tic C~I~AY1iC acid of 2 to
18 carbon atoms, of a cyclo~lirh~ti~ C~bOAY1iC acid of 7 to 15 carbon atoms, of an
~ nSaIU1~ted C&1bOAY1iC acid of 3 to 5 carbon atoms or of an ~oma~ic carboxylic acid
of 7 to 15 carbon atoms, and, if n is 2, is Cl-Cl2aLkylene, C4-Cl2aL~cenylene, xylylene, a
divalent radical of an ~liph~tir cycls~lirh~tir, ~r~lirh~tic or aromatic dic~l~,.ylic acid,
dicall,a,nic acid or phosphorus co t~; ; .g acid, or is a divalent silyl r~ l, preferably a
radical of an ~lirh~tic dicall,uAylic acid of 2 to 36 carbon atoms, of a cyc4 ~lirh~tic or
aromatic dicarboxylic acid of 8 to 14 carbon atoms, or of an ~lirh~ti~, cyrlo~lirh~tic or
aromatic dic~b~llic acid of 8 to 14 carbon atoms, and, if n is 3, is a trivalent radical of an
aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tric~l,~--ic acid or
of a phosphorus co~ i n; - ~g acid, or is a trivalent silyl radical, and, if n is 4, is a tetravalent
radical of an ~lirh~ti., cycloaliphatic or aromatic tetracarboxylic acid.
S~lbs~ enL.~ 51efin~ as Cl-Cl2alkyl may typically be 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 dar.
W O 94/06831 PC~r/EP93/02419
R2 as Cl-Cl8aL~yl may be the groups listed above and may ~ ition~lly be n-trideeyl,
n-te~decyl, n-heY~lecyl or n-octadecyl.
Rl as C3-C8aL~enyl may typieally be 1-~lu~enyl, allyl, methallyl, 2-butenyl, 2-~en~cnyl,
2-hexenyl, 2-oetenyl, 4-tert-butyl-2-butenyl.
Rl as C3-C8aLIcynyl is preferably ~lopa,~yl.
Rl as C7-Cl2aralkyl is preferably ph~nethyl and, most preferably, benzyl.
Rl as Cl-C8aLkanoyl is typieally formyl, propionyl, butyryl, octanoyl, but is preferably
aeetyl and, as C3-C',~lk~-noyl, is preferably aeryloyl.
R2 ~l~ofin~ as a monovalent radieal of a earboxylie aeid is typieally the radieal of aeetie
aeid, ca~lol~ic aeid, stearie aeid, aerylie aeid"l-clllaelylie acid, ben7~i~ aeid or B-(3,5-di-
tert-butyl-4-hyd.~"~y~hcnyl)propionic aeid.
R2 definç-l as a divalent radieal of a diearboxylic aeid is typieally the radieal of m~lonie
aeid, s~lccinic acid, glutaric aeid, adipie aeid, suberie aeid, sebacie acid, maleie acid,
phth~lic aeid, dibutylm~lnnic aeid, dibcll~yl.~.~lonic aeid, butyl-(3,5-di-tert-butyl~hy-
dn~ybcrlzyl)m~lonie aeid or bieyeloh~ptc u1ir~. l,o,.ylie aeid.
R2 fl~-finçd as a trivalent radical of a tric~l,(".ylic aeid is typically the radieal of trimt~.llitir.
acid or of nitrilotri~eti~ aeid.
R2 (l~ofin~A as a tetravalent radical of a tetracarboxylic acid is typieally the tetravalent
radieal of butane-1,2,3,4-tetraearbooxylie acid or of pyromellitic acid.
R2 ~ fin~ as a divalent radieal of a dic~ub~llic acid is typically the radieal of
hP.x~methyl~n~rlie~ b~llic acid or of 2,4-toluylenedicarbamie acid.
b) Compounds of formula (III)
W O 94/0683121~ 31 0 3 PC~r/EP93/02419
H3C CH
~3 3
Rl N ~--N--R4 (rlI)
H3C CH3 -1
W~ Gin n is 1 or 2, R1 is as ~3PfinP~ under a), R3 is hydrogen, Cl-C12aLcyl,
C2-Cshydlu~y~lkyl, Cs-C7cycloalkyl, C7-C8araLcyl, C2-ClgaLlcanoyl, C3-~s~lkpnoyl or
bcll~oyl and, R4, if n is 1, is hydrogen, Cl-Cl8alkyl, C3-C8aLcenyl, Cs-C7cycloalkyl,
Cl-C4alkyl which is substituted by a hyd~uxyl, cyano, alku,~yc~l,onyl or c&-lJa,l-ido group,
glycidyl, a group of ft rm~ -CH2-CH(OH)-Z or of formula -CONH-Z, wh~ Z is
hydrogen, methyl or phenyl; or, if n is 2, R4 is C2-Cl2alkylene, C6-Cl2arylcne, xylylene, a
-CH2-CH(OH)-CH2 group or a -CH2-CH(OH)-CH2-O-D-O- group, WhC,~ D is
C2-ClOalkylene, C6-Clsarylene, C6-Cl2cycloalkylene, or, with the ~rOi/iSo that R3 is not
aLcanoyl, aLcenoyl or benzoyl, R4 is also a divalent radical of an ~lirh~tir, cyclc~lirh~tir~
or aromatic dicarboxylic acid or dic~bal--ic acid or may also be the -CO- group, or R3 and
R4, when taken together, if n is 1, may be the divalent radical of an ~liph~tir cycl~liph~-
tic or aromatic 1,2- or 1,3-dicarboxylic acid.
Substit~lent~ defin~l as Cl-Cl2alkyl or Cl-Cl8alkyl have the me~nings already given
under a).
Substitu~Pnt~ d~PfinP~i as Cs-C7cycloalkyl are preferably cyclohexyl.
R3 as C7-C8aralkyl is preferably phenylethyl or, most preferably, benzyl. R3 as
C2-Cshydl(,xyalkyl is preferably 2-hydroxyethyl or 2-h-ydlu~y~lu~yl.
R3 as C2-Cl8aLcanoyl is typically propionyl, butyryl, octanoyl, ~ ec~noyl~ hPY~rlPr~
oct~flec~noyl, but is preferably acetyl and, as C3-Cs~lk~Pnoyl, is preferably acryloyl.
R4 as C2-C'8~1k~-nyl is typically allyl, methallyl, 2-butenyl, 2-pentenyl, 2-h~ ,nyl or
2-octenyl.
R4 as Cl-C4aLkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or ca,l,&---idO
group typically in~lu-lPs 2-hydroxyethyl, 2-hydro~y~,upyl, 2-cyanoethyl,
methoxycarbonylmethyl, 2-etho~yc~ l,onylethyl, 2-~ mi noc~rbonyll~l u~yl or
WO 94/06831 PCr/EP93/02419
3 ~ ~ 3
- 10-
2-(dimethylcarbamoyl)ethyl.
S~lbs~ r ~ tofin~A as C2-Cl2aL~ylene may typically be ethylene, propylene,
2,2-dime~}~ylylo~ylene, tetramethylene, ~ ...ell-ylene, oct~methylene, llrr~ Illylene or
l~ec~mPthylene.
Subsl ;l .,enl ~i d~fin~l as C6-Clsarylene may typically be o-, m- or p-phenylene,
1,4-naphthylene or 4,4'-diphenylene.
D as C6-Cl2cycloaL~ylene is preferably cyclohexylene.
Illu~LIati~,e ey~mples of polyaLkyll,;p . ;rline componn-lc of this class are the following
colllpc,unds:
N,N'-bis(2,2,6,6-tetrame~llyl~ , ;rlin4-yl)-N,N'-dibutyl~-lir~mide
N,N'-bis(2,2,6,6-tetramell-yll~ ;rlin-4-yl)-N,N'-dicyclohexyl-2-
hycllo~y~lu~ylene-1,3 ~ r.
the colllpound of formula
CH3 CH3 C4Hg
CH3 - N~} N-CH2-CH(OH)-CH2 0
CH3 CH3
CH3--C--CH3
CH3 CH3 ¢~
CH3 - N~ N-CH2-CH(OH)-CH2 0
C4Hg
CH3 CH3
c) Compounds of formula (IV)
WO 94/06831 ~ 1 4 3 ~ ~ 3 ` PCr/EP93/02419
H3C CH3 O
R1 N~< /R5 (IV),
H3C CH3 n
wl~e~l n is 1 or 2, Rl is as ~fin~ under a) and R5, if n is 1, is C2-C8alkylene or
C2-C8hy&u,~yaLlcylene or C4-C22acylûxyaL~cylene, and, if n is 2, is the (-CH2)2C(CH2-)2
group.
Rs as C2-C8aLIcylene or C2-C81-y&uAyaL~cylene may be ethylene, l-mell.yletllylene,
propylene, 2 e~yl~u~ylene or 2-e~yl-2-l-y~ y.nelllyl~r~ylene.
Rs as C4-C22acyloxyaL~cylene may be 2-ethyl-2-aceto~y...etl.ylpr~ylene.
d) Compounds of forrnnl~. VA, VB and VC
H3C CH3 IR
~ N--C=O
Rl--Nj~(C N R (VA)
H3C CH3 O n
H3C CH3 T1
~C, o C--T2
R1 _ N~ X I (VB)
k N C = O
H3C CH3 H
H3C CH3 1~
~C, o C--T2
R1 _ N X I (VC)
~ C N R7
H3C CH3 o - n
WO 94/06831 ~ ~i 31~3 PCr/EP93/02419
~l.c.~ n is 1 or 2, Rl is as d~ofin~l under a), R6 is hydrogen, Cl-Cl2aL~cyl, allyl, benzyl,
glycidyl or C2-C6~1koYyalkyl, and R7, if n is 1, is hydlug.,n, Cl-Cl2alkyl, C3-Cs~lk~nyl,
CrC9aralkyl, Cs-C7cycloaLIcyl, C2-C41-y~1-uAyalkyl, C2-c6~lknyyalkyL C6-ClOaryl,glycidyl or a group of f~rm~ -(CH2)p-COO-Q or of fnrrnlll~ -(CH2)p-O-CO-Q, ~L~ .~,n
p is 1 or 2 and Q is Cl-C4alkyl or phenyl, or if n is 2, is C2-Cl2alkylene, C4-Cl2alkenylene,
C6-Cl2arylene, a -CH2-CH(OH)-CHrO-D-O-CH2-CH(OH)-CH2- group, wl.e.~l D is
C2-ClOaLkylene, C6-Clsarylene, C6-Cl2cycloalkylene, or is a -CH2CH(OZ')CHr
(OCHrCH(OZ')CH2)r group, wLe~l Z' is hy~oge.l, Cl-C18alkyl, allyl, benzyl,
C2-Cl2alkanoyl or be-l~yl, Tl and T2 are each in~ pçnfl~n~ly of the other hy~u~ or
C6-ClOaryl or C7-C9araLlcyl which may be s~lbsl;l.JI~ by halogen or Cl-C4alkyl, or Tl and
T2, t~gc~l~,r with the linking carbon atom, form a Cs-Cl2cycln~1k~nto ring.
S~l 5l;l..~ lPfin~ as Cl-Cl2aL~cyl may typically be methyl, ethyl, n-propyl, n-butyl,
sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-u.ldc.;yl or
n-dodecyl.
S~lbsl;l- r ~ efin~l as Cl-Cl8aL~yl may be the groups cited above and may ~qflrliti~n~lly
be n-tridecyl, n-tetradecyl, n-h~Y~ yl or n-octadecyl.
Sub~ efinç~ as C2-C`G~lk xyaL~yl may typically be .~l Ih~ 1IY1~ CILUAY111Cl}IY1
~u~o~yllletllyL tert-bul~".y..lelllyl, etho~ lyl, GlLu~y~Jlu~Jyl~ n-bulo~ l.yl~
tert-l,ul~ hyl, isu~l~u~ tllyl or ~lopu~y~lupyl.
R7 as C3-Cs~lkPnyl may be l-~r~ yl, allyl, methallyl, 2-butenyl or 2-~c.l~,lyl.
R7, Tl and T2 as C7-C g~r~lkyl are preferably phenclllyl or, most preferably, benzyl. A
cycln~lk~ne ring formed by Tl and T2 together with the linking carbon atom may be a
cyclope~ cyclohtoY~n~, cyclooct~ne or cyclc~ c~nto ~ing.
R7 as C2-C4hydluxyaLkyl may be 2-hy~lruxytlllyl, 2-hyLuxylll~yl, 2-hy~lluxybulyl or
4-hydroxybutyl.
R7, Tl and T2 as C6-CIOaryl are preferably phenyl, a- or ~-naphthyl, which may be
sub~ u~l by halogen or Cl-C4aLkyl.
R7 as C2-Cl2alkylene may typically be ethylene, propylene, 2,2-diuletllyl~lul~ylene,
W O 94/06831 ~ 1 4 3 l D 3 PC~r/EP93/02419
- 13 -
~ elllylenc, hf Y~ ell.ylene, o~ llethylene~ dccd~llelllylene or ~odec~methylene.
R7 as C4-Cl2aLh,llylene is preferably 2-butenylene, 2-~enlenylene or 3-h~ ylene.
R7 as C6-Cl2arylene is typically o-, m- or p-phenylene, 1,4-naphthylene or
4,4'-diphenylene.
Z' as C2-Cl2alkanoyl may be propionyl, butyryl, octanoyl, flo~e~noyl, but is preferably
acetyl.
D as C2-ClOalkylen, C6-Clsarylene or C6-Cl2cycloalkylene is as tlefin~A under b).
Illu~l~aLi~ eY~mpl~'s of polyaL~lyiy~ ines of this class are the following co...~o...
2,2,4,~1 tet~ nethyl-7-oxa-3~2o-diaza-2l-oxo-dispiro[s. 1.1 1.2]-hf ~ `O~ f,
8 a~ctyl-3-dodecyl-1,3,8-triaza-7,7,9,9-~ f ~hylspiro[4,5]decane-2,~dione
or the colllpoullds of the following formulae:
CH3 CH3 CH3 CH3
NH-f=O O=C ~ N-CH
~ C - N - CH2cH(oH)cH2-[ocH2-cH(oH)cH2]2 N-C ~
CH3 CH3 oCH3 CH3
CH3 CH3 CH3 CH3
~ NH- C = O O = C - NH ~
CH3-N X l l X N-CH3
~ C N (Cll2)6 N - C ~
CH3 CH3 0 CH3 CH3
CH3 CH3 CH3 CH3
~kc _ N ~ CHz~ N--C~
Wo 94/06831 ~ L 3 ~ ~ 3 PCr/EP93/02419
- 14-
e) Compounds of formula VI
- R8 -
N J~ N
R9J~N~J R
wll~,r~ n is 1 or 2 and Rg is a group of formula
CH~CH3
-E-(A) {~N--R
C~7\CH3
wll~,~m Rl is as ~lefin~ under a), E is -O- or -NRll-, A is C2-C6aL~cylene or -(CH2)3-O-
and x is 0 or 1, R9 has the me~ning of R8 or is a group -NRllRl2, -oR~3, -NHCH2oRl3 or
-N(CH2oRl3)2, Rl, if n = 1, has the m~ning of R8 or R9, and, if n = 2, is a group
-E-B-E-, wlle-~,m B is C2-C6aL~ylene which may be i,lL.~u~t~,d by -N(Rll)-, Rll is
Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hy~ ~yaLkyl or a group of fcrrrn~
R~<CH2R
--~ N--R
CH3 CH2R
Rl2 is Cl-Cl2aLkyl, cyclohexyl, benzyl, Cl-C4hydlo~y~L~cyl, and Rl3 is hydrogen,Cl-Cl2aLlcyl or phenyl, or Rll and Rl2, when taken together, are C4-CsaL~cylene or
C4-CsoxaaL~cylene, typically
-CH2CH2 ~ -CH2CH2 ~
, or are a group of formula N - R1
-CH2CH2 ~ -CH2CH2 ~
WO 94/06831 21 4 310 3 PCT/EP93/02419
:: ,
or Rll and Rl2 are also each a group of formula
CH3 CH3
>~ Cl 4Hg N
HN>~--N ~ q--NH-A-
CH3 CH3
C4H9-N
CH3 >~CH3
CH3 N CH3
H
S~b~ el.f~ .ffnP~l as Cl-Cl2alkyl may typically be 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 dar.
Sl~b~ e..~ fin~(l as Cl-C41ly~u~yalkyl may typically be 2-l~yd~ yl,
2-l~y~u~y~r~yl, 3-1IY&~Y1J1~Y1~ 2-lly~llw~yllulyl or ~llydlo~ybulyl.
A as C2-C6alkylene may be ethylene, propylene, 2,2 dimetLylplu~yl~,nc, ~~ ylene or
k~ yl~llc,
Rll and Rl2 logell~ as C4-C5alkylene or oxaaLkylene may be ~ha~ ylene,
p~ edlylene or 3_o~t ~pe ~ ylellc.
Illu~ali~,v e~r~mples of polyaL~ylp;p.,. ;~lin~s of this class are thc coll.~ounds of the
following fr~rm~
N~C4Hg)2
3 >~3 N ~ N ~< 3
CH3 k~ C2H5 C2~<CH
W O 94/06831 21~ 3 10 3 PC~r/EP93/02419
- 16-
R H ~ CH3
N ~ N R c -NH-cH2cH2cH2-o ~H3
CH3 CH3
CH2-CH~ ~NH
NH CH3 CH3
CH ~--CHz-CH~NII ~ NH-CH2-CH~ ~NH
CH3 CH3 C H3
W O 94/06831 .. PC~r/EP93/~2419
~ I I
~)--Z
Z \~Z YZ I
~z ~7<
Z ~ ~
j--~7<Z I
Z
Z =< I c~
~<
z z_~ Z~I
\7
~ ~)
Z \~--Z ~(Z I
~=Z I
~ Z
I /\
~Z~ <~
~ I I
W O 94/0683t PC~r/EP93/02419 -
~143~L~3
- 18-
R R
75~ R-NH-(CH2)3-N--(CH2)Z N-(CH2)3-NH-R
R = CH3 CH3
N ~<NH
N ~N CH3 CH3
C4Hg-N
CH3 ~J~CH3
CH3 NH CH3
R R
76)R-NH-(CH2)3-N--(CH2)2 N-(CH2)3-NH-R
R = CH3 CH3
C4Hg ~<
N N ~<N-CH3
~/ CH3 CH3
C4Hg-N
CH3 ~<CH3
CH3 N CH3
CH3
CH3 R R CH3
77)
R-N--(CH2)3--N--(CH2)2--N--(CH2)3--N R
~ W O 94/06831 2 1 4 31~ 3 PC~r/EP93/02419
- 19-
R = N C4H~C~H3
C4H9 N
CH3 ~J~CH3
CH3 N CH3
CH3
CH3 CH3
C8H17 - N ~NH
CH3 CH3
78) C8H17 _ N 1N 1NH(CH2,
CH3>~<CH3
CH3 HN CH3 _ 2
CH2CH20H
CH3 N CH3
CH3~<CH3
N-C4H9
CH3~3 N ~ N C~<CH3
HO-CH2CH2-N\ ~ N N N--< N-CH2CH2-OH
~ C4H9 C4Hg 7~
C~3 CH3 CH3 CH3
WO 94/06831 ~ 1 ~ 3 ~ ~ 3 PCr/EP93/02419
- 20 -
CH2-CH=CH2
H3C N CH3
H3C>~CH3
N-C4Hg
80)
H3C~H3 N~N CH~CH3
H2C-HC-H2C- k~ N lN~ N ~N-CH2-CH~cH2
H3C CH3 CH3 CH3
f) Oli~m .ri~ or polymeric co~ ou,lds whose SLIuClul~ c~l;n~ unit conl~;nc one or
more than one 2~2~6~6-tetraal~ylp;~ ;tlint~ radical of ~orm~ (I), preferably polyesters,
pO~ e.~, poly~mirles~ po~ n~;nPs, polyul~tll~nes~ polyureas, polyAln;nn1l;~7~nrs~
poly(meth)acrylates, polysilny~n~s~ poly(meth)acryl~mi~s and ~eir copolymers which
contain such radicals.
nl~ ", eY ~ plP.s of 2~2~6~polyalkyll-;l-... ;~in-o 1ight st~hili~P-rs of this class are the
ccl.o~le of the following formnl~e, wl~ m is a mlmb~r from 2 to about 200.
CH3 CH3
O O ~
81) r C-CH2-CH2--C-O-CH2-CH2--N - ~m
CH3 CH3
82)
--FCH2-CH2 N~ O--C-(CHz)4--C--O ~N-cH2 cH2-o- C-(CH2)~- c
CH3 3 CH3 CH3
W O 94/06831 214 ~10 3 PC~r/EP93/02419
83)
CH3\~_H5 0 o CH3~,,C2H5 o
~ a CH ~ H2)dNII C ~ C
CH3 C2H5 CH3 C2Hs
ICH3 CH3
NH C - CH2- C CH3
~ CH3 CH3
84) ~ N ~ (CH2)6 ] m
CH3 ~ CH3 CH3 ~ / CH3
CH3 N CH3 CH3 N ~ CH
[ CH2-CH(OH)-CH~ ] m
85) CH3 ~ CH3
CH3 H CH3
86)
r O ~ -CH2-CH=CH-CH2--~ C,,H9
CH3 CH3 CH3 CH3
WO 94/06831 PCI'/EP93/02419
~1~3~03 22
87)
[ N~`N N (CH2)6 ]m
~N J CH3` ~ CH3 CH3 ~ CH3
1 C4H9 CH N CH3 CHa H ~ CH3
CH3 ~ ~ CH3
CH3 N CH3
CH3\ CH3 CH3 CH3 0 0
88) - O{~N CH2~3CH2 N~c--(CH2)4-a_
CH3 CH3 CH3 CH3 ~m
O C2H5 0 \~
89) ~C--C -- 8 o cH2-N3~m
C2H5 CH ~CH
CH3
[ C CH~ lm
90) 0 = C C~<CH3
O ~ N-CH3
CH3 CH3
W O 94/06831 214 310 3 PC~r/EP93/02419
- 23-
CH3
[ 1 CH ~ m
91) o C C~<CH3
C6H13-N ~ N-CH3
CH3 CH3
~N~
N~N
92) ~I~N ~I N (CH2)~ N ~ m
CH3 >~<CH3 CH3 '>~<CH3
CH3 HN CH3 CH3 'H CH3
[ N (CH2)o N CH2-CH~
93) CH3>~ <CH3 CH3 >~ CH3
CH3 N CH3 CH3 N CH3
O O
[ N(CH2)6 N C CH2 C ~m
cH3>~cH3 CH3 ~<CH3
CH3 N CH3 CH3 NH CH3
WO 94/0683t æ ~ 4 3 ~ ~ 3 PCI'/EP93/02419
- 24 -
Cl H3
si--o
--m
(CHI 2)3
95) 0
CH3 ~k CH3
CH3 CH3
HsC4(R)N N ~N(R)c4H9
N~N
NH
(CH2)3
96) HsC4(R)N ~ ~rN--(CH2)2--N R'
NH -- 2-3
N(R)C4Hs
N~N
HgC4(R)N J~NJl~N(R)c4H9
wl~ R= H3C ~CH3
H3C CH3
and R'= N I or H
HgC4(R)N J~N1N(R)C4H9
Among these classes of light st~hili~ , classes e) and f) are esper~ y suit~hl~., in
WO 94/06831 214 310 3 PCI/EP93/02419
particular those tetraalkyl~ nPs which contain s-triazine groups. Other particularly
sllit~ble co~ oullds are co l l~o~ 74, 76, 84, 87, 92 und 95.
The ~mollnt of lc~ e!1 ylpipe~ c added will depend on the desired degree of
st~hili~tinn Normally 0.0l to 5 % by weight, preferably 0.05 to 1 % by weight, based on
the polymer, will be added. It is ~.~Çc,ll~id that the molar ratio of ~-h .~ y~ inP, and
;. alkyl should not be subst~nti~lly greater then l.
The phosphs)rustIII) coln~ounds added as optional ~d-liSion~l s~ilicers to the
polymP,ri~tion may be phnspl;;l s, phosphnnitP,s or phosphinites They may contain one or
more than one phQsrhnrir ester group. It is y-~ d to use a phos~h' us(m) co ~1 (1 of
formnl~ A, B, C orD
R~ lR2 ~R2
P--OR3 R30--P--R4--P--OR3
R2
A B
Rp/ ~ P--R,7 ~P R
C D
wherein Rl and R2 are each in~lepçn~l.o.ntly of the other Cl-Cl2aLlcyl, Cs-C8cycloaLlcyl,
phenyl, phenyl which is snb ,l;~ ~A by one to three C1-C12aLkyl groups, or are a radical
-OR3,
R3 is C6-C20aLkyl, Cs-C8cycloalkyl, phenyl or phenyl which is snb~l;l, Icd by one to three
C1-C12aLkyl groups, and
R4 is nn~ubs! i l JI~ ~ phenylene or naphthylene or phenylene or naphthylene which are
substihlte 1 by C1-C12aLkyl, or is a radical-O-Rs-O-, wll~ l~ihl
Rs is nn~ub~ l phenylene or naphthylene or phenylene or naphthylene which are
substih1te~1 by Cl-Cl2aL~yl, or is a radical -Phen-R6-Phen-, wL~ Phen is phenylene,
R6 iS -O-, -S-, -SO2-, -CH2-, or-C(CH3)2-,
R7 and R8 are each in~lepçn~ently of the other phenyl or phenyl which is snbst tute~ by
one to three C1-C12aLkyl groups, and the two snbsli~.,e~-t~ R7 and R8 may also be linked
WO 94/0683t PCr/EP93/02419
- 26 -
by a Cl-Cl2aLIcylene group, and
R9 is F, Cl, Br or I, preferably F.
Among the compounds of formula A it is l~.Gf~li,d to use those colllyoullds WL~ ill Rl
and R2 are a radical -OR3 and R3 is C6-C20alkyl, phenyl or phenyl which is substitnt~A by
one to three Cl-Cl2aLIcyl groups.
Among the colll~,ounds of fonn~ B it is l..cÇe.lGd to use those compounds ~L~"Gh~ R2 is
a radical -OR3, R3 is phenyl or phenyl which is S~lb~ A by one to three Cl-Cl2aLtcyl
groups, and R4 is a diphenylene radical.
Among the colllpounds of form~ C it is ~lGÇc.l~d to use those con~ounds wL~ Rl is
a radical -OR3, R3 is phenyl or phenyl which is s.lbsl ;~ "1. rl by one to three Cl-Cl2aLkyl
groups.
It is ~ ,Çtl-.,d to use a ph- sphorus~[I) collll)ound which cont~in~ at least one P-O-Ar
group, and Ar is a mono-, di- or triaLlcylphenyl radical.
Illustrative ex~mples of eligible phosphorus(m) cGIll~ounds are:
L.;~hellyl phosphite, decyl di~henyl phnsphite, phenyl didecyl pho~ ;;, tris(nonylphenyl)
phosFhite, trilauryl phos~h;~:, trioct~decyl phGs~ distearyl pentae.y~ irhosphite"
tris(2,4-di-tert-butylphenyl) phosphit~, r~ o~1ecyl pent~.yLl~;~ol ~iphosphite, bis(2,4-di-
tert-buLylphenyl) pentac.yLluiLol diphos~hite, tristearyl sorbitol 1l ;l.ho ,~hit~
tetrakis(2,4-di-tert-bu~ylp}~l~yl~-4,4'-bi~hellylene ~liphosphonit~o, bis(2,~di-tert-butyl-4-
meLhylphe.lyl) pentaelyLlll;Lol .1irhosphit~-
The amount of phosphorusaII) coll.~oulld will depend on the amount of piperidinecolll~oulld added. Normally 0.0l to 1 % by weight, preferably 0.05 to 0.5 % by weight, is
added, based on the polymer.
Besides the phosphorus(III) compound, it is possible to add further co-st~bili~ers and
mo~lifiers that do not h~te-r~.G with the polym~ri~tinn It is ~-efe.-~d at add antioxidants
of the sterically hindered phenol type to the polym~.ri~tion. These phenols are standard
~ntioX~ nt~ for organic m~teri~l~ and are frequently used for st~b~ ng polymers.Illustrative examples of such phenolic antioxidants are:
WO94/06831 214 31 0 3 PCr/EP93/02419
- 27 -
1. AL~lated monophenols, for ey~mrle 2,6 di-tert-butyl~melllyll~hu ~nl~ 2-tert-butyl-
4,6 dimethylphf nnl, 2,6~i-tert-butyl ~ edlyll-hP.nnl 2,~di-tert-butyl-~n-buLyll-hf .~nl,
2,6-di-tert-butyl~isobulyll.h.-..nl, 2,~dicyclopentyl-~mclllyll.hf .~nl, 2-(a-methylcyclo-
hexyl)-4,6-dilllelllyllJh~nol~ 2,6--lioct~-~fecyl~lllPthyll.hP.~ol, 2,4,6-tdcycloh~"~yll.h~ ol,
2,6-di-tert-butyl-4-methnYymf thyll~hf )nl~ 2~6~inonyl-4-lllelllylllhf- ~nl~ 2,4-di~ llyl-6-
(l'-,l.cthylundec-l'-yl)phenol, 2,~dilllcll,yl-~(1'-methylheptadec-1'-yl)phenol, 2,~di-
methyl-6-(1'-1ncll,yll,idec-l'-yl)phenol and Il~L~lul~s thereof.
2. AL~cylthiolnell~yl~ .hf.nol~ for eY~mple 2,4-dioctylthin...elhyl-~tert-bulyll.he-~nl, 2,4-di-
octylthis~ Pll.yl-6-n~fIhyll)hf ~ 2,4 dioctylthin~lelllyl-6 elllyll~hr~ol and2,~ ode~
thi~methyl~nor~yll.h. ..~ol,
3. IIydl~llil-ol-f s and aL~cYlated hydro~l;,-o.~rs, for eY~mrlf 2,~di-tert-butyl-4-,~etl..,~y-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,~ henyl~octa-
decyloAyyhGllol~ 2,6-di-tert-butylhy(L~uil,ol~, 2,5-di-tert-butyl-4-hyd,uAy,...;~ol~P., 3,5-
di-tert-butyl-4-hy~Ayi~ ole, 3,5-di-tert-butyl-4-hydluAyyhenyl ~ le and bis-(3,5-
di-tert-butyl~hy~uAY~henyl) ~ir~t~
4. IIyd~uAylated thin~irhenyl ethers. for ey~mpl~- 2,2'-thiobis(6-tert-butyl~melllyl~hG-
nol), 2~2~-thiobis(4-octylrhtonnl)~ 4,4'-thiobis(6-tert-butyl-3-ll,cll,yll~hr-~-nl), 4,4'-thiobis-
(6-tert-butyl-2-mclhyll-h--~-ol), 4,4'-thiobis(3,6-di-sec-amylph~-nol) and 4,4'-bis-(2,6-di-
methyl-~hyd~,Ayyh~nyl) ~ nlfi~e~
5. AL~lidene bi~k~- ol~, for eY~mpl~ 2,2'-methylenebis(~tert-butyl-4-m(,ll,yll-h~.~-ol),
2,2'-methylenebis(6-tert-butyl-4~1hyll.h~- ~ol)~ 2,2'-methylenebis[4-methyl-6-(a-methyl-
cyclohexyl)phenol], 2,2'-methyl~n~bi~(4-methyl-6-cyclohexylrh~--nol), 2,2'-methylenebis-
(6-nonyl-4-1"~,Lllylyhenol), 2,2'-methylenebis(4,6-di-tert-buLyli-hf--ol), 2,2'-ethylidenebis-
(4,6-di-tert-butylphenol), 2,2'-ethylitlen~.b;~(6-tert- butyl~isobutylrhenol), 2,2'-methy-
lenebis[6-(a-methylbenzyl)-4-nonylrhl~-nol], 2,2'-methylenebis[6-(a,oc-dhl,ell,ylbenzyl)-
4-nollylphel~ol], 4,4'-methylenebis(2,6-di-tert-butylrh~-nol), 4,4'-methylenebis(6-tert-bu-
tyl-2-methylrhP-nol), 1,1-bis(5-tert-butyl-4-hyd~Ay-2-,l,~ lllyl~henyl)butane, 2,6-bis(3-
tert-butyl-5-methyl-2-llyd-uAyl,e-i~yl)- 4-melhyll)h~ - nl, 1,1 ,3-tris(S-tert-butyl-4-lly~Ay-
2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-lly~L~Ay-2-"lelllyl~hcnyl)-3-n-dodecylmer-
captobutane, ethylene giycol bis[3,3-bis-(3'-tert-butyl-4'-hyd~Ayyhellyl)bulylate], bis(3-
tert-butyl-4-hyd,uAy-S-methylphenyl)dicyclopent~ ne, bis[2-(3'-tert-butyl-2'hy~LuAy-
W O 94/06831 PC~r/EP93/02419
2 L4~1a~
5'-methylbenzyl)-6-tert-butyl4-me~ylphenyl] t~.e~h~ tP~, 1,1-bis(3,5-dimethyl-2-hy-
d~o,~yl,hellyl)butane, 2,2-bis(3,5~i-tert-butyl-4hyLuAy~henyl)~lupalle, 2,2-bis(5-tert-
butyl-4-hy lLoAy-2-methylphenyl)-4-n-dodecylrrlcrca~obut~c and 1,1,5,5-tetra(5-tert-
butyl-4-hy~LuAy-2-methylphenyl)pent~ne.
6. O-, N- and S-Benzyl comPounds. for ey~mI~le 3,5,3',5'-tetra-tert-butyl-4,4'-dil.y~LuAydi-
benzyl ether, octadecyl 4-hyd-~Ay-3,5-dimethylbenzyl-m~c~l~to~cet~t~, tris(3,5{ii-tert-
butyl-4-hy~uAyb~ Lyl)amine~ bis(4-tert-butyl-3-hy~uAy-2.6-dimethylbenzyl)-dithio-
tercFhth~l~te, bis(3,5-di-tert-butyl-4-}-ydlu~y~e.-zyl) sulfide and isooctyl 3,5-di-tert-
bUtyl--4-1ly~llUAy~ lLyL~ a~o?(cets~te.
7. Hy~ u~ ,nzylated m~k)n~tto,s, for eY~mplP tlioct~d~P~yl 2,2-bis(3,5-di-tert-butyl-2-
hydl`uAy~ lLyl)m~lon~te~ nct~decyl 2(3-tert-butyl-4-hydLuAy-S-methylbenzyl)m~lnn~te,
od~yl---t,.- a~k,ctl.yl 2,2-bis(3,5-di-tert-butyl-4-llydluAyl,ellLyl)m~lnn~tc and bis[4-
(1,1,3,3-te,tramcthylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hy~lluAybel~zyl)m~lo~
8. Aromatic l-ydl~u~ybenLyl comPounds. for example 1,3,5-tris(3,5-di-tert-butyl-4-
lly~ A~ lLyl)-2~4~6~ tllylhe~ 1,4-bis(3,5-di-tert-butyl-4-hy~l.uAyl,c,.lLyl)-
2,3,5,6 h h ~ hylbcl-L~ .~e and 2,4,6-tris(3,5-di-tert-but-yl-4-llydluAyb~,.-Lyl)phenol.
9. Triazine co-.,~-ounds~ for eY~mplt~ 2,4-bis(ocLyl.--el~lo)-6-(3,5-di-tert-butyl-4-hy-
dl`oAyal~ilino)-l~3~s-tri~7inlo~ 2-octylmcreapl~4,6-bis(3,5-di-tert-butyl-4-1-y~oAy~lilino)-
1,3,5-tri~7.in~, 2-ocLyl~c~ Lu-4,6-bis(3,5~i-tert-butyl-4-llydloAyyhel~oxy)-1,3,5-~.;~,.;..~.,
2,4,~tris(3,5-di-tert-butyl-4-hy~lr~yl,henoxy)-1,2,3-tri~7ine, 1.3,5-tris(3,5-di-tert-butyl-
4-hyd uAybG.-zyl) iSooyi-n~ t~ 1,3,5-tris(4-tert-butyl-3-hyd~uxy-2,6-dimethylbenzyl) iso-
cy~n~lr~te, 2~4~6-tris(3~5-di-tert-butyl-4-llyd~u~y~henylethyl)-l~3~s-tn~7ine~ 1,3,5-tris(3,5-
di-tert-butyl~-hy~ùxy~hel,ylylu~ionyl)hexahydro-1,3,5-triazine and 1,3,5-tris(3,5-di-
cyclohexyl-4-hy~u~cybenzyl) isocy~nllr~qte
10. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hyd~cybel,~,ylrhospho-
nate, diethyl 3,5-di-tert-butyl-4-hydroxyl.~,n~ylphosphonate. (1ioct~decyl 3,5-di-tert-butyl-
4-hydluAy~cnzylphosphonate, ~iioct~flecyl ~-tert-butyl-4-hy~l,uAy-3-methylbellzyl~hos-
phonate and the c~lcillm salt of monoethyl 3,5-di-tert-butyl-4-hyd,u,~yl,enzylphosphonate.
11. AcYlaminoPhenols. for example 4-hydroxylauranilide, 4-hydr~Ay~lr~ nilirl~o. and octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carb~m~t~.
WO 94/06831 ~14 3 ~ 0 3 PCI/EP93/02419
~. j
- 29 -
12. Esters of ~-(3,5~i-tert-butyl-4-hyd.oxy~,henyl)propionic acid with mono- or polyhy-
dric ~lcohol~, for example with meth~nol~ eth~nnl, oct~dec~nol, 1,6-h~Y~n~iol, 1,9-no-
n~nlo.flinl, ethylene glycol, 1~2-plupAn~AiQl~ neû~e.llyl glycol, thi~li~thylene glycol, di-
ethylene glycol, tliethylene glycol, pell~yLIuiLol, tlis(hydlux~.eLllyl) isocyanluate~ N,N'-
bis(hydlox~ethyl)rY~mi~le, 3-thi~llnfl~c~nnl 3-thi~rent~ rAnol, trimethylh~ PA;ol~ tri-
methylolpropane and 4- hydluxylllcthyl-1-phnsph~-2,6,7-trioxabicyclo[2.2.2]octane.
13. Esters of ~-(S-tert-butyl-4-hydloxy-3-methylphenYl)Propionic acid with mono- or
polyhydric ~l~ohol~ for eY~mrlP with mP.th~nol, eth~nol, oct~(1ec~nol, 1,6-k~ .Y A~fA;ol,
1,9-non~ntoAiol, ethylene glycol, 1,2-~lup~netliol, neopentyl glycol, thio liethylene glycol,
diethylene glycol, triethylene glycol, pentae~yL~u;tol, tris(hy&ukyelllyl) iso~iy~ r~
N,N'-bis-(hy~lluxy-ethyl)rY~mitlt~., 3_thi~nn(1~nl)1, 3_thi~re.ntA~1P~c~nol~ tIimethylh~A~
diol, tlimethylol~r~a~le and4-hydluxylllethyl-1-phospha-2,6,7-trioY~bi~yclo-
[2.2.yoctane.
14. Esters of ~-(3.5-dicYclohexYl-4-hYdr~xY~)henyl)propionic acid with mono- or polyhy-
dric ~l~ohol~, for eYAmple with me~h~nol, eth~nol, oct~tlecAnol, 1,6-hP~ l, 1,9-no-
n~ne~ l, ethylene glycol, 1,2-~u~ r~liol, neopentyl glycol, thiodiethylene glycol, di-
ethylene glycol, triethylene glycol, ~cn~clyllu;Lol~ tris(hydrû"yelllyl) iso;yA~.-..At~ N,N'-
bis-(hydlux~el~lyl)5)y~mi~le~ 3-thi~ nnl~ 3-thi~pent~flçc~nnl, L~ lylh~ l;nl, tri-
methylol~r~ e and 4-11yd~uxymethyl-l-phospha-2,6,7-trioY~bicyclo-[2.2~2]-octane.
15. Esters of 3,5-di-tert-butYl-4-lly~lluxy~,h~,nYlacetic acid with mono- or polyhydric
~lcohol.~, for ex~mrle with meth~nol, eth~n~l, oct~de~nol, 1,~hçx~nP,cliol, 1,9-nonane-
diol, ethylene glycol, 1,2-~ r~liol, lleopcntyl glycol, thi~i~thylene glycol, diethylene
glycol, triethylene glycol, yC.l~ll~ylhlilOl, tris(hydr~x~ yl) isocyanurate, N,N'-bis-
(hydroxyethyl)ox~mi(lto., 3-thi~lln-lec~nol, 3-thi~pent~lec~nol~ trimethylhtox~ne~liol,
trimethylolpropane and 4-hydloxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
16. Amides of ~-(3,5-di-tert-butYl-4-hydroxYPhenYl)propionic acid, for example N,N'-bis-
(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hçY~methylençfli~mine, N,N'-bis(3,5-di-
tert-butyl-4-hydroxyphenylpropionyl)trimethylP-n~li~minç and N,N'-bis(3,5-di-tert-butyl-
4-hydroxyphenylpropionyl)hy~r~7inç
Preferred antinxi-l~nt~ are those listed in 6, 8, 9, 12, 13, 14 and 16, espe~i~lly 6, 8, 9 and
Wo 94/06831 PCr/EP93/02419
~3~ 03
- 30 -
12. Particularly suitable ~ntioy~ nt~ are octadecyl ~(3,5-di-tert-butyl~lly&u~-y~he.-yl)-
propionate and 1,3,5-tris(3,5-di-tert-butyl-4-hy&u~yl ~,n~yl)-2,4,~~ ell.ylbe~.~f -~r
The amount of ~ntioYiA~nt added will depend on the amount of phG~ph~lus(m)
co.llyoulld. Normally 0.005 to 0.5 % by weight, preferably 0.01 to 0.2 % by weight, based
on the polymer, is added.
The invention is ill~ t~ A in more detail by the following non-lh~ e FY 7..r.~1cs in
which, and also in the dcs~ ion and claims, parts and p~ çs are by weight, unless
otherwise stated.
FY~mple 1: Prep~r~tion of the catalyst
25 g of anhy~uu~ m~ ;.. chl~iAe and 5 g of ~ .. ;-.. t~otr~hloriA~e-ethyl ~e~ Alf;
cQmrleY are milled in in a ball mill with st~inko-s~ steel balls for 24 hours at room
t~ , (c. 22C) under argon. The solid catalyst cclllyonent so o~ ;llpA conl~ c 2 %
!;1~..;...~
Polymtori~tic-n of propylene
The polymP-ri~tinn is carried out in a 3 litre stirred and thermost~t~ y controlled
st~inlP-~ steel autoclave which is ev~ tçrl before the start of the polymPri~tion for
30 . -i ..~l~ s at 110C (13 Pa) and is ~.~al ls fl-l~h~A for 30 ..-i~ s with propylene gas
at 110C. The autoclave is cooled to 20C and 300 mg of S-1, 300 mg of H-1 and 300 mg
of P-1 are added to the autoclave as solid or as 5-10 % sol~ltion in hP~y~ne Then 25 mg of
the solid catalyst component are ~;~ tc d for 10 ..;..~JI~ s with half of a snllltinn of 4 mmol
of triethyl ~ ..ii ;,.... and 1.6 mmol of tri~Pthoxyphenylsilane in 25 ml of hexane and
sn~p~nrled in the autoclave under argon. The autoclave is flushed with the second half of
the hexane sol--tinn The autoclave is closed and charged with hydlog.,n (6 kPa) and 600 g
of liquid propylene. With stin ing, the content~ of the autoclave are heated to 70C and
kept at this ~ ul~ for 4 hours. Excess propylene is then discharged and the resl-lt~nt
polymer is treated with 10 ml of isù~ropallol at 70C to deactivate the catalyst and then
dried under v~eculll for 1 hour at 70C.
The following tests are carried out on ~e polymer:
For the corrosion test, the polymer is cc"ll~rc;,~ion moulded on a hot press for 30 ~ nl~s
at 280C between carefully cle~n~l iron plates. The iron plates are then stored for
\
WO 94/06831 PCI/EP93/02419
~1~3103
24 hours at 100 % hnm~ ty at room ~el~aLu~, (c. 22C). Corrosion is ~csessed visually.
The colour of the polymer is ch~r~ct~ri~ by the Yellowness Index (Y~ according to
ASTM D 1925-70.
The polymer corrodes the iron plates only in~ignifit~ntly, It has a YI of 2.3.
Co,.ll~aLi~,~ ExamPle 2:
The procedure of F.Y~mpl~. 1 is repe~t~3, but wiLhouL using 300 mg of S-l, to give a
polymer which, with the same catalyst yicld, severely corrodes the iron plates and has a YI
of 2.5.
F.Y~mnles 3 and 4:
The ~ UlC of Fy~mrle 1 is l~e~ , reFl~ing S-1 with 300 mg of S-2/300 mg of S-5,
to give a polymer that corrodes the iron plates in~i~ifi~ntly/slightly and has a YI of 2.3/
2.2.
Example 5:
Poly~ylene powder, ~lc~cd as in P~mrle 3, is ~vcessed in a Rr~hentl~-r plastograph
for 10 ...;.~ s at 230C. The melt is taken from the kn~ r and co~ lesscd to a c. S mm
board. In the corrosion test, the iron plates exhibit no corrosion after the melt ~oCçc~ g
C~ , Example 6:
The polymer ~ JdL~d accc,lding to com~ti~,~, Example 2 is ~luCeSS~ as ~es~ibed in
F.Y~mpllo 5. The iron plates are severely corroded after the melt ~l~)cG~ g
Examples 7 and 8:
The stability to oxidative degr~l~tion is measured by the time taken until m~rkPd
emhrittll~:m~.nt of the polymer occurs in oven ageing at elevated t~ ly~l~dlulc. This test is
carried out with boards which are obtained by colll~lcssion moulding poly~r~,~ylelle
powder obL~ined as described in FY~mple 1 by adding 300 mg of S-1, 300 mg of H-l and
300 mg of P-1 and 300 mg of S-5, 300 mg of H-l and 300 mg of P-l at 230C. The time
taken until emhrittllomtont is 11 days for both polymers at an oven L~-llp~ ture of 135C.
Comparative Example 9:
A polymer ~ d and tested in accoldal-ce with the particulars of Examples 7 and 8, but
Wo 94/06831 214 3 ~ ~ 3 PCr/EP93/02419
- 32 -
without the ~dfiition of S-l and S-5, also becomes brittle after 11 days. This finding means
that ~e ~ iition of S-1 and S-5 does not affect the stability of the polymer to oxidative
degr~tinn
Co""~ iv~, Example 10:
A polymer prepared and tested in acco~ ce with the particulars of FY~mplP.s 7 and 8, but
without the ~itinn of S-1 and S-5 as well as H-1 and P-1, b~o. ~S brittle after 1 day.
Examples 11-14:
Polym~ri~tion is carned out as ~escrihe~l in FY~mrle 1, but using 44 mg of solid catalyst
co~ ,ollelll, 6.4 mmol of triethyl ~ .. i";.. and 2.4 mmol of trietho~y~hellylsilane. The
following co.n~ullds are used instead of comrol-n-l~ S-1 and lEI-1:
Example Additi~e Corrosion YI
11 H-1 + S-3 slight 2.3
12 H-1 + S-4 slight 2.5
13 H-2 + S-3 slight 2.5
14 H-3 + S-3 slight 2.8
The following additives are used in the F~i....l)l~5,
S-1: [Mg4,5Al2(0H)l3C03-3,5H20] (this cc-mpo-ln~l is sold by by Kyowa (~h~mir~
Japan, under the h~ n~mP. DHT-4A). The colll~oul~d is V~;UUlll dried over phosphorus
pentoxide at 95C for 24 hours.
S-2: [Mg4,SAl2(0H)l3C03-3,5H20] c~lrin~ (this compound is sold by by Kyowa
Ch~o.mir~ , Japan, under the tr~len~me DHT~C).
S-3: zink oxide (dried)
S-4: molecnl~r sieve 4A (dried)
S-S: m~n~sjllm oxide (dried)
WO 94/06831 ~ 4 3 1 ~3 PCI /EP93/02419
- 33 -
HNR _ (CH2)6--NR~ r NR--(CH2)6- NR--H
N~N
H-l NH --n, where
tert. C8H17
Mn ~ 2500
~CH3
R iS ~H,
CH3
CH3
R R
H-2: R-NH-(CH2)3-N--(CH2)i~ N-(CH2)3-NH-R
R = CH3 CH3
~N~ ~r ~N-CH3
y CH3 CH3
C4Hg-N
CH3 ~CH3
CH3 N CH3
CH3
WO94/06831 2 ~43~:û3 PCI/EP93/02419
- 34-
CH3
si--o -
--m
(CHI 2)3
H-3: 0 Ml,>1500
CH3 ~kCH3
CH3 CH3
C~CH3)3
P-l p- o~C(CH3)3
