Note: Descriptions are shown in the official language in which they were submitted.
` 10739Zl ~OE 75/~ 804
:.
Limiting as far as possible the detrimental influence
of heat and light on synthetic polymers requires the addition
of stabilizers and stabilizing additives to the polymers so
as to prevent degradation. It is also known that synergistic
effects may he achieved by combined a~dition of stabilizers
and stabilizing additives. Usually applied stabilizing
additives are, for example, epoxy compounds, antioxidants,
compounds absorbing ultra-violet radiation, and organic phos-
phites.
However, the stabilizing additives are very often not
entirely satisfactory, some havin~ even multiple shortcomings
at the same time. An insufficient resis*ance to hydrolytic
influence and a relatively high degree of volatility plague,
,
for e~ample, a séries of known organic phosphites which are
used for stabilization purposes. Moreo~er, among these phos-
phites are some not entirely unobjectionable in the physio-
logical field.
The object of present invention was thereforeto provide
~tabilizers based on organic phosphites which do not have-
said disadvantages and which show a highly stabilizing effect.
It has been found now that phosphites of the generalformula
.. \
B - O / P
wherein A, B and C are identical or different organic radicals
and wherein at least one of the radicals has the structure
R - C ~CI - Rt or H - C -Cl - H
OH ~
'
- 1073921 HOE 75/i` 804
R and R' may be identical or different ~nd represent a hydro-
gen atom, an aryl group or a cycloalkyl group or an alkyl
group and wherein the sum of the carbon atoms included in R
and R~ does not exceed 60, and wherein X is a straight-chain
saturated or unsaturated alkylene radical, whilst possible
residual radicals B and C are either aryl group~ or cyclo-
alkyl groups or alkyl groups and wherein the total number of
carbon atoms included in the radicals A, B and C is at least
10 - do surprisingly display to a large sxtent the advan-
tageous properties sought after.
Th0 present invention ls being rela~ed, therefore, theabove mentioned organic phosphites which were not known be-
fore, their use as stabili~ers for organic polymers, stabi-
- lizer composit~ons containing these phosphites and organic
polymers being stabilized by means of these phosphites.
A special advantags of the phosp~ites according to the
invention is their resistance to hydrolytic influence which
is substantially increased in comparison to many other phos-
ph~te stabilizers, a fact which improves the weathering
properties of the molding compositions which are stabilized
with the phosphites of the invention.
The fact that those among the novel phosphites occurring
a~ subYtances which are solid at room tenperature, impart an
dimension stability under heat to the plastic better
articles processed by means of these phosphites than
by using known liquid phosphites - i$ to be considered a
further advantage. Finally, the use of the phosphites as per
the in~ention reduces substantially the formation of tarnish
29 on the processing machines and of groove~ on the shaped
-- 3 ~
... . ..... .
107392.1 HOE 75/F 804
articles being produced. Additional valuable properties are
the lnodorousness, the practically absent ~olatility and the
lacking tendency to exudation.
The ph4sphitesas per the invention are obtained according
to known methods by transesterification of tri-low alkyl-
phosphites or Or triphenyl phosphites with the corresponding
hydroxy compounds. Some are still liquid at room temperature;
generally and preferably, however, the novel phosphites re-
present solid white products - part of them having wax-like
characteristics. Most interesting are the latter having flow-
drop-points of from about 35 to 100C, since in addition to
their stabilization effect they influence fa~orably the pro-
perties of the products made of polymer molding compositions
containing such ~-ax-like phosphites.
In the phosphites of the general formula
A - O \
B - O P
'., C - 0/
A, ~ and C are identical or different organic radicals at
least one of these radicals has to be of a structure as per
the formula
R - C - C - R~ H - C - C - H
I I or ¦
OH OH
I II
In case that only radical A has one of these structures,
B and C may be a.lkyl groups having from 1 to 60, preferably
from 1 to 30 carbon atoms and/or aryl groups and/or cyclo-
- -- 4 --
' ' ~ ' '
.
~07392~ HOE 7~tF 804
alkyl grotlps having each from 5 to 12, preforably 5 or 6
carbon atoms. The aryl group may be optionally substituted by
alkyl radicals or alkoxyl radicals having preferably from 1 to
6 carbon atoms. If A and B have structure I and/or II, C is
one of the afors mentioned radic~ls.
Preference is given to one or two only of radicals A, B,
C having either structure I or II.
The letters R and R~ being employed in the general formu-
la I stand for identical or different radicals, namely hydro-
gen, an aryl group having from 6 to 15 carbon atoms which may
be substituted optionally by alXyl groups or alkoxyl groups
having preferably from 1 to 6 carbon atoms, by chlorine or
hydroxyl groups, such as a phenyl group, a tolyl group, a
xylyl group, a tert.-butylphenyl group, a nonylphenyl group,
a chlorophenyl group or a hydroxyphenyl group. Furthermore,
R and Rl represent a saturated or unsaturated substituted or
unsubstituted cycloalkyl radical having from 5 to 12 carbon
atoms, such as a cyclopentyl radical, a cyclohexyl radical, a
cycloheptyl radical, a cyclooctyl radical, or a cyclododecyl
radical, or as well a straight-chain or branched alkyl radical
having from 1 to 60, preferably from 8 to 40 and especially
from 8 to 20 carbon atoms, such as, for example, the ethyl
- radical, butyl radical, hexyl radical, octyl radical, decyl
radical, dodecyl radical, tetradecyl radical, hexadecyl radical,
octadecyl radical, eicosyl radical, docosyl radical, tetra-
cosyl radical, hexacosyl radical, octacosyl radical, tria-
contyl radical, dotriacontyl radical, tetratriacontyl radical,
hexatriacontyl radical, octatriacontyl radical, tetracontyl
29 radical or dotetracontyl radical. The sum of the carbon atoms
~ 5 --
,
'
.
'
` 1073921 HOE I~/F 804
contained in R and K: sh~ld not exceed a maximum of 60,
preferably of about 40.
If Rl in structure I is hydrogen, methyl or ethyl, a
straight-chain alkyl radical is preferred for R, having from
6 to 58, preferably from 18 to 40 and especially from 20 to 36
carbon atoms. Structures I of this kind, wherein R' is hydro-
gen, are suitable for being incorporated into the phosphite
through the corresponding 1,2 diols, these latter may be pre-
pared for example from the corresponding epoxides by adding
water.
If use is made of epoxide mixtures such as they are ob-
tained e.g. by epoxidizing mixtures of commercially available
long-chain ~-olefins, products are obtained the structure of
which is characterized by designations such as
C20/24 alkyl- ~ C18/22~37/45-"~ ~lC30~-alkyl_ll; cf.table
page 12, footnotes 3,4 and 5.
In formula II "X" represents a straight~chain saturated or
unsaturated alkylene radical having from 3 to 10, preferably
from 5 to 7 carbon atoms. A group of structure II is e.g. the
~-hydro~y-cyclohexyl radical.
A further characteristic quality of the phosphites is
that the total number of carbon atoms contained in the radicals
A, B and C amount~ to at least 10, preferably to at least 16.
Some particularly representati~e novel phosphites may be
cited thereaf~er, though the inYention is not to be limited
to said substances:
- 6 -
,
- 1073921 HOE 7 5/~ 804
tris(2-hyd-oxydodecyl)phosphite (CloH21 ~H-CH2 o)3p
ethyl-bis(2-hydroxyhexadecyl)phosphite(C14H29-CH-CH2-0)2P OC2H,~;
OH
(2-h-yd-rny-~vh~x~ yl )phQ~ 4~Z~ H-r'HZ n)
OH
diethyl(2-hydroxyoctadecyl)phosphite C16H33~H-CH2-O P(OC2H5)2
OH
. . .
:.; ethyl-bis(2-hydroxyoctadecyl)phosphite(cl6H33lcH-cH2-o)2p OC2H5
OH
, phenyl-bis(2-hydroxyoctadecyl)phosphite(C16H337H-CH2-0)2P OC6H5
OH
tris(2-hydroxyoctadecyl)pho~phite(C16H33-lCH-CH20)3P
OH
diethyl ( 2-hyd~oxy-c2o/24-alky~
.', phosphite 18~22H37/4s-1H-CH2--P (OC2H5)2
,. H
"~ phenyl-bis(2-hydroxy-C20J24-
alkyl)phosphite / ( 18/22 37/45~ClH~cH2~o)2p OC6~5
OH
tris-(2-hydroxy-C20/24-alkyl ~
phosphite (C18/22H37~45-ClH CH2 )3
, OH
'i diethyl(2-hydroxy-C24/28-alkyl~
pho phite 22/26H45/s3-~CH-CH2-O P(oc2H5)2
OH
ethyl-bi s ( 2-hydroxy-C24/28,,~
. alkyl)phosphite (C22/z6H45/s3-~CH^cH20)2P OC2H5
OH
,' .
-- 7 --
, ' ' , .
;' ' ~ ' ' . :
., - . -.
1073921 HOE 7~/F 804
, ` .
tris(2-hydroxy-c2ll~2g-alkyl)phosphite(c22/26H4s/53 ~H C 2 )3
OH
diethyl(2-hydroxy-c3o+-alky~ 30H61 1 2 2 5 2
phosphite OH
ethyl-bis(2-hydroxy-C30+-alkyl)phosphite (~C30H6llH-cH20)2P
OH
OCzH5
diphenyl(2-hydroxy-c3o~alkyl ~
phosphite C30H61-pH-CH20 P(OC6H5)2
OH
- phenyl-bis(2-hydroxy-c3o+-alkyl)~
phosphite (~ C30H6l-lH-cH2-o)2p C6 5
OH
triS(2-hydroxy-c3o~-alkyl)phosphite (~ C30H61-~H-CH20)3P
I H
The novel phosphites may be used also in admixture to each
other, optionally combined with different, generally known
~tabilizers, stabilizing auxiliaries, antioxidanta and ultra-
violet-stabilizing compounds.
Upon processing chlorinated polymers, such as chloropoly-
ethylene, rigid and soft polyvinyl chloride, polyvinylidene
- chloride, polyvinylchloroacetate and vinyl chloride-O~-ole-
fin-copolymers a substantially improved stability under heat
and to light is achieved by adding the novel phosphites
claimed herewith, in the presence of compounds known as stabi-
lizers, such as metal compounds, indoles substituted in 2-
' ,~ . ', .'' " ' ,
.' . ~
10739Zl HOE 7~/~ 804
position, preferably 2-phenylindole, epoxide stabilizers and
possibly polyhydric alcohols.
By metal compounds ~nown as stabilizers are to be under-
stood: Ca, Ba, Sr, Zn, Cd, Mg, ~1 and Pb soaps of aliphatic
carboxylic acids or oxyca.boxylic aclds ha~ing from about ~ to
32 carbon atoms, preferably from 8 to 24 carbon atoms, salts
of these metals with aromatic carboxylic acids of preferably
from 7 to 12 carbon atoms, such as benzoates, salicylates as
well as (alkyl)phenolates of these metals, the alkyl radical
having from 1 to 12, preferably from 1 to 6 carbon atoms. This
range of compounds also includes organotin compounds such as
dialkyl-tin-thioglycolates and carboxylates as well as -
; optionally - neutral and basic lead salts of inorganic acids
; such as sulfuric acid and phosphorous acid.
Known epoxide stabilizers are, for example, higher
s ~ epoxidized fatty acids such as epoxidized soybean oil, tall
; oil or linseed oil, epoxidized butyloleate and higher epoxy-
alkanes.
Polyhydric alcohols are e.g. pentaerythritej trimethylol
. 20 propane, sorbitol or mannitol, i.e. preferably alcohols having
from 5 to 6 carbon atoms and from 3 to 6 OH groups. I
!
Stabilizers of this kind such as metal compounds,
epoxides and polyhydric alcohols are described, for example,
in J.Voigt "Stabilisierung der Kunststoffe gegen Licht und
Warme", Springer-Verlag, Berlin-Heidelberg-New York (1966).
A ~ery efficient stabilizer composition for processing
halogenated polymer molding compositionsconsists, for example,
; of from 0.01 to 10 parts by weight of a phosphite according
29 to the in~ention, 0.1 to 10 parts by weight of metal compounds
- 9 _
'
- 10739Zl H0~ 7 5/F 804
known as stabilizers, 0.1 to 10 parts by weight of a known
epoxide stabilizer and 0 to 1 part by weight of a polyhydric
alcohol.
The novel phosphites display also an excellent efficiency
- 5 for stabilizing polymers or copolymers of olefins free from
halogen. The stability of e.g. polypropylene under heat and
to light is considerably improved by the addition of the novel
phosphites, especially in admixture to phenolic and/or sul-
i~ fidic stabilizers.
By phenolic and sulfidic stabilizers are to be understood
the generally known stabilizers against heat und to light
which are used in the processing of plastics, such as 3.5-
ditertiarybutyl-4-hydroxyphenyl-propionic acid-ester, 2.6-di-
tertiarybutyl-p-cresol, alkylidene-bis-alkyl-phenols, esters
~- 15 of bis-(4~-hydroxy-3t-tertiary-butylphenyl)-butyric acid,
thiodipropionic acid ester of fat alcohols as well as diocta-
decyl sulfide or dioctadecyl disulfide; cf. - J.Voigt,
"Stabilisierung der Kunststoffe gegen Licht und Warme",
~ Springer-Verlag, Berlin-Heidelberg-New York (1966).
-~ 2~ A synergistically efficient stabilizer composition for
j; polymers or copolymers of olefins free from halogen consists,
for example, of from 0.05 to 5 parts by weight of a phosphite
according to the invention, from 0.05 to 3 parts by weight of
a known phenolic stabilizer and/or of from 0.1 to 3 parts by
weight of a known sulfidic stabilizer. Special stabilizers
against ultra-violet rays may also be added to the stabilizer
composition at a rate of from 0.1 to 3 parts by weight, if
deemed necessary. Known ultra-violet absorbers are e.g. al-
29 koxy-hydroxybenzophenones, hydroxyphenylbenzotriazoles,
-- 10 --
,
' ~
' ' ' - '
' , ' .
` 10739Zl HOE 75/F ~04
~alicilic acid phenolic ester, benzoic acid hydroxyphenolic
ester, benzylidene malonic acid mononitrile ester as well as
so-called "quenchers" such as nickel chelates, hexamethyl-
phosphoric acid triamide or - as recently made known - pi-
peridine stabilizers.
Stabilizer compositions of the phosphites according to
the invention and known stabilizers not only do improve the
stability of polyolefins, chloropolyolefins and chlorinated
vinylpolymers, but impart also an improved stability to poly-
esters, polyamides, polyacrylonitrile, polycarbonates, poly-
i` siloxanes, polyethers~poly urethanes and others.
; The following Examples illustrate the invention and specify the advantages of the novel phosphltes:
E X A M P L E 1:
A 1 liter-four-necked flask being equipped with an agi-
tating device, an internal thermometer, gas inlet and descen-
ding cooler i9 rinsed with nitrogen and subsequently charged
with 42~ g (1.5 mole) of octadecanediol-1.2 and 83 g ~0.5 mole)
of newly distilled triethyl phosphite. During 20 - 30 minutes
the content of the flaqk is heated to 115 - 120C in a weak
nitrogen current, while stirring, ethanol is then starting to
separate at an internal temperature of about 110 C. Within
rurther 3 - 5 hours, while stirring is continued, the tempera-
ture of the reaction mixture is slowly increased from 120C
to a final temperature of 160C. 66.2 g of ethanol are
distilled off during this period of time. Agitation is then
continued for another hour in a water jet vacuum of 10 - 20 mm
at the unaltered temperature of 160 C, in order to remove
29 possible volatlle components. In a cooling trap set up
-- 11 --
10739Zl HOE 75/F 804
.
between the described apparatus and the water jet pump there
are found after this period of time 3.1 g of a liquid clear
as water consisting of 1. 2 g of triethyl phosphite and further
1.9 g of ethanol.
Thus a total quantity of 68.1 g = 98.6 % of the theo-
retical yield of ethanol was separated.
After cooling down the limpid, slightly yellowish melt
438 g z 98.8 % of the theoretical yield of tris-(2-hydroxy-
octadecyl)phosphite are obtained as a white wax having a
flow-drop-point of 59.5 - 61 C (being determined according to
DGF M III 3 (57) ), containing 3.3 % of phosphorus of the
molecular weight of 854. Theory for the compound of a
: summation formula C54H11106P of 3.5 % P and a molecular
. weight of 886.
. 15 E X A M P L E S 2 - 14s
.~ Further compounds among the no~el phosphites ha~e been
prepared by synthesis according to the method thoroughly
deJcribed by Example 1. The following table groups the special
- preparation characteristics and the analytical characteriza-
tion of the products obtained by the processes.
., '
_ 12 -
'
,
. . ' ' . '
'' ''
10739Zl
. _ ~
_ ~ ~o ~ U~
U~ . o CO U~ ;~ , , ,
ID h O \o u~
o~ ~ o I I I I ~ _
u~ . a) t~
~ _l ~ u~ u~ ~ ~ ~ r-
O ~ Pt
O . -
h In ~ 00 1!- oo C~l O U~ ~t ~ u
~,~ . :~ ~ ~ O ~ U~
,S ~ ~D ~ ~ ~ U~ ~o
,~:~' . ~ , ._ O I
. o ~ O O O oo " C)
~1 ~ O ;t O
<~ O t~ ~ ~ ~ N 0 u~ t~
~a ._.
~O W ~O O C~ _ I
11~ 0~ ;t C'~ ~ ~t
~ ~ ~ . 0
.~ ~ ~
o P~ :~ o~ o~ ~ ~ ~ o h
a~ 1~ ~ ~
~ --~ o--
.o a~ ~ ~ X
~ ~ ~ ~. ~:
,~ ~I o
,, ~0 ~ ~ ~ ~ O ~ 0 ~ _~
P~ O ~ IC X O ~ X ~-- N
O O O O o -I I ~.q ~1
~ h ~ I N O ~ ~ N 3 I :~ ID
o u. ~ ~a ---- I ~ ,Y -- N N ~ ~
ID ~ 1 0 N :~ _I U~ V -- --i ~-1
t6 T~ I ~I O ~ I~ 1 1
~ ~ N ~N O I --~ -- N 0 I X -- >- 0 U~
GD ~ _ O ~ I ~ N_I O ~ N O
~1 0 0 ~0 ~ ~ ~ ~ ,r
U~ O r1 a~1 x,~ o~D O rl;t ,1; ~ ,!~:
o ~ h o 5~ D ~ c~ h c~ rl N _I
. ~ ~ ~ V ~
=~ ~ ~ _~ ~
~1 ~1
~ ~ ~o - ~ ~
~ ~r~ o o~ ~ ~o
- ~ ~0 a~ ~ _ ~ ~ _
t,
;t
a~ ~ _ ~ _ ~ _ _
- ~ ~-~ o o o - o o
o p~ o o - -
-1 0-1 e e _ ~
P~ P~
D
~q .
o o o
~0 ~O O
h ~ ~: ~ ~ ~ O o
~ ~ ~~ ~ o~ _l
e ~ - c ~ O co N a:~ O O --
~D 0 0 ~ 3 ~ ~ ~ _ ,~ O
U~ O ~ ~ U~ U~ ~ O ~ ~ ~
E~ 1 ^ - - ^ X #) ao ~ P-
O ~ O O-- -- -- --C~l N ~l h O
~ ~ e ~ ~ ~ ~ ~ ~ ~ ~ ~ 4
0 Id N ~L 0 N ~O 00 X ;t ~ ~ 'a
I ~ -- -- -- -- N N N 11
u~ v - a~ ~ b.DV V V ~ V ~ V ~ O
_ ~
~ O _,_
li':l Z ~`I t'~ ~1~'\ ~ ~ 0 ~O
.
~ - 13 -
Image
- 13a -
` ~0739Zl HOE 75/F 804
E X A M_~ k~
.,, -- -- . .
; The following method was applied for determining the
' stability to hydrolysis of the novel phosphites in comparison
,- to the stability of four commercially available products:
5 g of phosphite were heated to the boiling noint in
; 100 ml of distilled wate~ after having boiled for 20 to 60
minutes, the reaction mixture is cooled and its content in
phosphorous acid determined in the aqueous solution by mean~
, of titration with aqueous 0.1 n-sodiumhydroxide solution. The
degree of hydrolysis Qf the phosphite submitted to the test
is randomly determined as a ratio of 100 x/y, x being th0
actually consumed volume of 0.1 n-NaOH and y being the theo-
retical volume of this reagent, calculation based on a
supposedly completed hydrolysis of the phosphite to yield
~- 15 phosphorous acid.
,. _ . .... .. . . _. _ _.
. Degree of hydrolysis
P h o 8 p h i t e. in % after a boiling¦
time of _l
~ 20 Min. 60 Min.
a) )Triphenylphosphite 84 100
b)1)Tris(nonylphenyl)phosphite 57 9Z
c)l)Diphenyl-isooctylphosphite 55 77
d)l)Di4tearyl-pentaerythrityl-diphosphite 52 68
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
e) Ethyl-bis~2-hydroxyoctadecyl)phosphite 33 42
f) Diethyl-(2-hydroxyoctadecyl~phosphite 21 3o
g) TriS(2-hydroxy-c24/28-alkyl)phosphite 35 51
h) Ethyl-bis~2-hydroxy-c24/28-alkyl)phosph . 31 41
i) Diethyl-(2-hydrOxy-c24/28-alkyl)phosph- 25 36
~- j) Ethyl-bis(2-hydroxy-c3o+-alkyl)phosph~ 11 13
k) Tris-(2-hydroxy-c3o+-alkyl)phosphite 16 23
1) Phenyl-bis(2-hydroxy-C~O+-alkyl)phosph. 12 13
1) Commercially a~ailable products as comparative substances
- 14 -
:
1073921 HOE 7~t~ 804
E X A M P L S S 16 to 39:
These Examples show the stabilizing effect of the phos-
phites according to the invention upon processing polyvinyl
chloride. The dynamic stability under heat (Example 16 to 27)
~d +h~ static st~h~1it~r unrl~ h~at (EY~mp1~s 28 t^ 39) ~e
determined. The specified parts are parts by weight.
1~0 Parts each of a mass-polyvinyl chloride having a
K-value of 60 were mixed thoroughly with 0.2 parts of 2
phenylindole, 3 parts of epoxidized soybean oil, 0.25 parts
of a c~mplex calcium/zinc stabilizer consisting of 42 weight ~
of ca~cium ~tearate, 30 weight % of zinc stearate, 22 weight %
of pentaerrthrite and 6 weight % of 2,6-di-t-butyl-4-methyl-
phenol, 0.2 part of a montanic acid ester (acid number 18,
saponification number 154~, 0.3 part of stearyl stearate,
-5 part of glycerolmonostearate, and 0.5 part of the phos-
phites.
In order to determine the dynamic stability under heat
the mi~tures were applied onto a laboratory-scale twin-roller
device heated to 180 C and rolled-out to a sheet (pelt) within
one miD~te at 20 rpm. In intervals of 10 minutes spot samples
were picked of the~e ~heets, and their color shades compared
with an internal color chart. The various tests were run each
until the rolled-out sheet had taken up a dark-brown to black
shade.
In order to determine the static stability under heat,
a rolled-out sheet was first prepared from the mixtures
according to the afore given description, and this sheet being
rolled-out on the twin-roller device at 180C for another 10
29 mimltes~ period. The sheet was then peeled off the roller
- 15 -
,
',
107392~ HOE 7~ 4
, . .
and flats of about 0.5 mm thickness and a diameter of 30 mm
blanked therefrom. The flats were wrapped in an alumin_um
sheet and tempered at 180~ in a heating cabinet with internal
air circulation. One flat was picked every 10 minutes and
5 its color sha'e cv...pa.ed w '.. ~ha co or cha;^t. The val-ue
figures employed in the color chart ha~e the following
.
- meaning:
1 = clear as water
2 = slightly yellowish
3 = distinctly yellow tint
4 = dark yellow-brown shade
5 = dark brown to black
A~ demonstrated by the following tables, the polyvinyl
; chloride being stabilized by organic phosphites according to
the present invention is clearly superior in comparison to
polyvinyl chlor$de being stabilized with known phosphites
and with mixtures free from phosphites as far as their dynamic
,: stability and their stability under heat are concerned.
r;
.;.
, . .
.,
.
..
.
- 16 _
,. .
~73921
1~1011
~d ~ ~ _ ____________'_____
o ~ ~,, ,, ;t
0 ~ o _ _ ~ _ _ _
~ ~ ~ _ ' ~ ' ' ' ' '_'____
~ _ h _ _ _ _ _ _ _ _ _ _ I
O o ~
_lIr~ h cr~ I I I
h _ O _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
O ~
t~ o_ _ o e~t N N C~
ID _ Il~ ~
O E3 O h I I I c~t C~l ~`l I I ~ I I c~ I
~ ~_ _ ~ ~I N N N C~
'.:, 0~ _ ~Oi ~.
~ O O N N N N ~1 ~ N ~ ~ ¦ N ~ C--
h I N U~ I I I ~ ~ I I
o ~ _ . ._ __ _ _ _------ ' ---- 1---------
. ~ h . _ ~ l
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, ~ . .. ~.
~ ~ bD . 1 ~0 .q
o ~1 c~ o~c~o ~ ....
n~ t~ ~
~ ~
E a I O O o
~ ~ .~o ~ 00 o~ o -- ~ ~ ~ ~ ~o
~ _ X O . -- - . N N C`l N N ¦ N ~ ~`1
_ 17 -
'~ .
; ` ~0739Z~
:
',':
~ ._ _ _ _ _ _ _ i _ _ _ _
~ '
, . ~ o U~
. ~ o _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
O ~ ~ ~ I
hl _ ~ _ _ _ _ _ _ _ _ _ _ _ _ I_ _ _ _ _
G~ _ ~
O ~ I I I I '~ t I I I I ~ I U~
~: ~ _ h cu c~ ~ N ~ N CU
rl ~ _ ~ t~ I
G~ O h I I I I I I I I I I ~ ~ I
e _ o ~ N C~ t N ~ ~ ~
,: . , .~q ~ _ t~ ~ t~
,.: ~ ~ O O ~ I
~3 ~ _ _ ,~ _ N ~ N N C~ N I IY N
o ~: _ h ~ .
O O td C~l N N N ~1 C~ ~1 N ¦ e~ l I
:; ~ ~ ~ e~- _ _ _ _ _ _ _ _ _ _ _ _l_ _ C~ _
.- ~ :J _ C~
o h O ~ c~l N
~ h _ _ _ _ _ _ _ _ _ _ _ I _ _ _ _ . .
.~ . Q~l O ________ I___
, ' ~ _ _ .
o ,
~: h a~bD I
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3 P4 h ~j, _ _
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~ ~Ll CU N '~
(.q .1
_ 18 -- .
~. I
1~739Z~ HOE 7~/~ 80~
E X A M P L E ~lO-
This example shows that the addition of the phosphites
according to the invention to polypropylene improves consider-
ably its stability to light and against alterations due to
heat.
A powdery mixture consisting of
100 parts by weight of unstabilized polypropylene
~ 5(230oc)about ~
0.15 part by weight of octadecyl-3-(3~,5~-di-tert.-
butyl-4~-hydroxyphenyl)-propionate
and
0.10 part by weight of the ethyl-bis(2-hydroxy-
C24/28-alkyl)phosphite prepared according
to Example 7
- 15 was injection-molded on an injection molding machine to yield
test plates measuring 60 x 60 x 1 mm. Test specimens were
blanked from these plate~.
The stability to light was determined by means of the
Xeno-test device, type 150, produced by Messrs. Hanau Quarz-
; 20 lampen GmbH with the filter combination 6 IR + 1 UV as per
DIN 53 387. (DIN = German Industrial Standard). The time of
exposure to light, i.e. the period of time after which the ab-
~i fiolute elongation at break had decreased to 10 % was measured
in hours. In the case of polypropylene being stabilized with
ethyl-bis(2-hydroxy-C24/28-alkyl)phosphite this time of ex-
posure amounted to 695 hours. Comparative secimens which had
been prepared according to the above specified recipe - but
~ without ethyl-bis(Z-hydroxy-C24/28-alkyl~phosphite - reached
29 only 540 hours for this time of exposure.
_ 19 _
~,. - , .
- ~IOE 75/F 804
1073921
The resistance to alterations under heat of in~ection
molding test samples which had been measured approximately to
the procedure described by DIN 53 383 at an airtemperature of
140 C, amounted to 40 days until total embrittlement of the
polypropylene being stabilized with ethyl-bis(2-hydroxy-
C24/28-alkyl)phosphite; the resistance to alterations under
heat of comparative sampleY reached 22 day~.
.
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