Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ HOE 76/F ~00
The i.nventi.on relates to piperidine hydroxyamides, more
~ 6- 7L~c~m~c//
precisely to ~ 7~h~i~h~ 4-hy~roxy-~-carbamoyl- - :
piper.idlnes and salts thereof, to the prepaxation of these com-
pounds and to th~ir use as stabilizers ~or organi.c materials.
The novel compounds o~ the formula -~
113C C~
~ ' ' ' .
~_/ CO~lI2 ~ ..
2 Pte~h l ~OC~5~S~ o ~ rne an : ~ .
in whi.ch R and R each mean~ide~tlcal or different straight
chained or branched alkyl readicals having from 1 to 12 carbon :
atoms or Rl and R2me~n together withthe associated carbon atom a
saturated homocylic rin~ haviny S or 6 members or a grouping
of the formula
H3C ~}t
~ C~12 ~ 3' ,;
C ~ ~ N~
3 3
.... ; ... . .
and H-X means phosphoric acid, phosphorous acid, an aliphatic ~::
or aromatic sulfonic acid or phosphon.ic acid, an aliphatic mono-, :
di- or polycarboxylic acid or an aromati.c mono- or dicarboxylic
acid and m is O or 1.
Representatives of the novel p1peridine hydroxyamides are,
~or example:
2,2,6,6~tetramethyl-4-hydroxy-4-carbamoylpiperidine, ~,,;
" " piperdinium stearate ?
:
" " i , piperidinium-p-tertio- ~.
butyl ben~oate ~
, - .
1~81~3~
EIO~ 76/F 800
2,2,6,6~etr~lmethyl-4-hydro~y--4~c;lrbamoylpiperidinium succinate
For the prepar~tion of the novel compounds 2,2~dimethyl-
6,6-dia~kylpipe.ridones, ~hlch may be prepared according to known
processes (Cf. for example, Beilst~sin, vo].ume 21, page 249,
Francis, J.Chem.Soc. 1927, page 2891; German Offenlegungsschr.ift
1 695 753), are used as starting compounds. The reac-tion o~ the
piperidones with cyanides yields cyanohydri~s~ which are sapo-
ni.fied to amides likewise in known manner, preferably with strong
mineral acids, for example concentrated hydrochloric acid. .The
~,2,6,6-tetraalkyl-4-hydroxy-carhamoylpiperidines are obtained ~ ;~
in the form of their salts, which may be converted into the free
bases by means of strong bases, for example alkali hydroxides
or by suitable ion exchangers. The desired salts may be p:repar-
ed from the bases obtained by the reaction with acids, preferab- :
ly in the presence of a solvent, for example an alcohol or of
water. Both the free bases and the salts may be purified by re-
crystallization from water or aleohols.
In the novel compounds of thé formula
H 3C ~ 3
\ 0
. (II-~)n~ IIN X
~ J 2 . :
R1 and R2, whieh may be identieal o:r different, eaeh mean a
straight ehained or branehed alkyl radieal having from 1 to 12,
preferably from 1 to 6, earbon atoms. Espeeially interesting
are eompounds, whieh are derived from the readily aeeessible
triaeetone-amine and in whieh R1 and R2 eaeh mean a methyl group. .~.~
Rl and R2 may also form a saturated homocylie ring having from ~.
5 to 6 members, togsther with the associated earbon atom, for
:,:
~ . . .
. - 3 - - ~
1081~3~ oE 7~/F 800
":
example a c~clohexane ring, or a ~rouping oE the formula
113C Cl{3
\ CII
~ C I ~II
- ~--c~I2 J
~ 113C C~13
H-X means phosphoric aeid, phosphorous acid, an aliphatie sul-
fonie acid or phosphonicacid haviny from 1 ~o 30, ~reerably ~`~
from 1 to 18 earbon atoms, an aromatie sulfonie or a phosphonie
aeid havin~ from 6 -to 25, preferably from 6 to 18 earbon atoms,
whieh may be alkylabed by from 1 to 3 alkyl groups having from
1 to 16 earbon atoms, H-X may further mean an aliphatie straight
ehained or branehed mono- or diearboxylic aeid having from 2 to
3~, preferably from 2 to 18, carbon atoms or optionally a poly-
carboxylic acid with up to 4 carboxyl yroups and a total of up
to 16 earbon atoms, or an aromatic optionally C1-C4-alkyl or -iso-
alkyl substituted mono- or diearboxylie aeid having from 7 to
25, preferably from 7 to 19 earbon atoms. There may be mentioned~
by way of example phenylphosphonie acid, camphorsulfonie aeid, `
dodeeylsulfonie aeid, p-toluene sulfonie acid, alkyl polyglyeol
ether sulfonie aeids, alkylarylpolyglyeol ether sulfonie aeid~
aeetie aeid, propionia aeid, n oetanoie aeid, 2-ethyl hexanoie
aeid, laurie aeid, stearie aeid, tallow fatty aeid, montanie aeid,
sueeinie aeid, adipie aeid, azelaie aeid, eitrie acid, triearb-
allylie acidj benzoie aeid, tolylie .aeid, p-tertio-butyl benzoie
aeid, phthalie aeid and terephthalie-aeid. .
In the above formula m" which may be O or 1, indieates that
the invention reLates both to the free bases and to the afaresaid
salts or in the ease of polybasie aeids optionally to aeid salts
- 4
~ .
iO8~'~3~
of the tetraalkyl-4-hydroxy-~-carbamoylpiperidines.
The 2,2,6,6-tetralkyl-4-hydroxy-4-carbamoylpiperidines and
their salts confer upon synthetic polymer compositions an exellent
stability to decomposition by the action of ultraviolet radiation
or heat. The color of the polymer compositions is not effected
detrimentally by the presence of the novel compounds. ;~
Synthetic polymer compositions, which are to be protected
against the action of light and heat include polyolefLns, for
example, polyisoprene, po~ybutadiene, polystyrene and especially
polypropylene and polyethylene of low and of high density,
furthermore copolymers of ethylene-propylene, ethylene-butene,
ethylene-vinyl acetate, styrene butadiene and acrylonitrile-
styrene-butadiene. "Polyvinyl chloride" and "polyvinylidene
chloride" include homopolymers ~f vinyl chloride or vinylidene
chloride, copolymers of vinyl chloride or vinylidene
chloride with vinyl acetate or other olefinically unsaturated
monomers. Further polyacetals, polyesters, for example poly-
ethylene terephthalate, polyamides, for example nylon-6, nylon-
6,6 and nylon-6,10, polyurethanes and epoxy resins are suitable.
The quantity of the novel compounds to be added to the syn- `-
thetic polymers depends on the nature, the properties and the
particular applications of the polymer to be stabilized and is
generally in the range of from 0.01 to 5, preferably of from
0u05 to 3 and especial~y from 0.01 to 1.5 parts by weight,
calculated on the quantity of the synthetic polymer. One
compound may be used as well as a mixture of several compounds.
The compounds are incorporated into the synthetic polymers
. . .
according to known-methods. The stabilizer may be mixed in the
form of a powder with the synthetic polymer or a solution,
suspension or emulsion
- 5 -
: . : : -
, . . .
- ,. ~ . ::
~IOE 76/F 800
~38~L23~ ~
o~ the st~bilizer may be incorporat~d lnto a solution, suspension
or emulsion of the synthetic polymer.
The stabilizers are eficient both when used sol~Y and when
associated to A mixture of usual ligh-t stabilizers (UV-stabilizers
and quenchers) anc1 heat stabilizers based on phenolic, sulfidic
and phosphor-containing anti-oxydants.
In ~his content conventional stabilizers comprise, Eor exam-
ple 2,6-di-tertio-butyl -p- kresol, 3,S-di-tertio-butyl -4-hydro
xy-phenylpropionic acid ester, alky]idene-bis-alkylphenols~ thio-
propionic acid ester of fatty alcohols as well as dioctadecyl-
sulfide and -disulfide. Examples of phosphorus-corltaining corn-
pounds are trisnonyl-phenylphosphite, disstearylpentaerythritol
diphosphite~esters of pentaerythritol phosphite and others.
Examples of UV-absorbers are benzotrisazole compounds, such as
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole and examples oE quen-
chers are metal chelates.
An efficient stabilizer combination suitable for poly-~ ole-
fine free from halogen, for example hicJh pressure, medium pressure
and low pressure polymers of C2-C4 olefine, espcially polyethylene
and polypropylene or of copolymers of such ~-olefins consists,
calculated on 100 parts by weight of polymer, for example, of
from 0.01 to 5 parts by weight of the compounds to be used accord- `
ing to the invention, 0.05 to 5 parts by weight of a phenolic sta-
bilizer, optionally o 0~01 to 5 parts by weight of a sulfur-con-
23 taining costabilizer, as well as optionally of 0.01 to 3 parts
by weight of a basic or neutral metal soap, for example calcium
s~earate or zinc stearate, as well as optionally of 0.1 to 5 parts
by weight of a phosphite and optionally of 0.01 to 5 parts ~y
~ ~ .
weight of a known UV-stabilizer selected from the group of alkoxy-
hydroxybenzophenones, hydroxyphenylbenzotriazoles9 salicylic acid
. .:. . . ~ ~ .
: - . , . . ~ ,
..
~ .
~081Z3~ __ E 76/F 800
phenol es~ers, benzoic acid hydroxyuhenol esters, benzylidene ~ :
malonic acid mononi-trile est~r~of qu~nchers, for example nickel
chelates or hexamethyl phosphoric acid tr.isamide.
An addition of the novel stabil:izers in ~he presence of
metal compounds known as stabilizers, of epoxy-stabilizers, phos-
phites and optionally polyvalent alcohols ln the s-tabilization
of chlorine-containing vinyl-homo- and copolymers, for example
polyvinyl chloride, polyvinylidene chloride, polyvinyl chloroace-
tate, vinyl chloride ~ -olefin copolymers ancl chlo.rinated poly-
olefins, for example chlorinated polyethylene and polypropylene
also improves the heat and light stabili.ty.
Metal compounds known as stabilizers in this context are:
calcium, barium, strontium, zinc, cadmium, alumi.nium, and lead
50~pS of aliphatic carboxylic acids or oxycarboxylic acids having
from about 12 to 40 carbon atolns, salts of the said metals with
aromatic carboxylic acids, for example benzoates or sallcylates
as well as (al~yl~ phenolates of these metals, moreover organotin
compounds, ~or example dialkyltinthioglycolates and carboxylates.
Known epoxystab.ilizers are, for example epoxidized higher
fatty acids as well as epoxidized soy bean oil, tall oil, lin-
seed oil or butyloleate as well as epoxides o~ long chained
ole:Eins.
Suitable phosphites are for ~xample, trisnonylphenyl phos-
ph.ite, trislauryl phosphite or esters of pentaerythritol phosphi-
2S te. :
Examples of polyvalent alcohols are pentaerythritol, txi-
methylol propane, sorbitol or mannite, preferably alcohols hav-
i.ng from 5 to 6 carbon atoms and from 3 to 6 O~ groups.
~i A suitable stabilizer combination fo.r the stabilization of .~;
halogen-containing polymers COnSlStS, calculated on 100 parts ~ ;
7 - . .
.. : .:: :. : :
:. : . : :
- . : ; .. ~ .. . . . .: .
108123~ ~IOE 76/F 800
by wei~ht of pol.ymer, for example of from 0.01 to 1Q parts by
wei~ht of metal co~npounds known as stabilizers, oE from 0.1 to
10 parts by wei~ht o a known epoxide stabilizer, of from 0.05
to 10 parts b~ weight of a phosphite, of from 0~1 to 10 parts
by wei~ht of a po.Zyvalent alcohol and oE from 0.01 to 5 part~ by
weicJht of one of the compounds to be used according to the inven-
tion.
The followinc~ examples illus-trate the invention:
E X A M P I E 1-
2,2,6,6 tetramethyl-4-hydroxy-carbamoylpi~ dine :-
To 180 g of concentrated sulfuric acid were added portion-
wise while stirring ~t a temperature o:E 20 to 25~ 60 g of -tria-
cetatoaminocyanohydrin. Stirring was continued until a clear so- :
lution was formed (for about 3 to 6 hours), whi.ch was either con-
centrated in vacuo until the chlorohydrate precipitated or neutra-
lized with a base, for example concentrated NH3 while cooling, :
in which pxocess the hydrochloride likewise precipit.ated. The
colorless salt obtairled decomposed at a:temperature hicJher than
. 307C. The free base having a melting point of 210C was obtain-
ed from the hydrochlorlde by a treatment with aqueous or prefer-
ably alcoholic alkali hydroxide or with alcoholic ammoniac. .
.Analysis:calculated: C 60.0 % .. H 10.0 ~ .-N 14.0 %
found: C 59.9 ~ H 10.2 % N 13.2
IR: ~ C-0: 1 60Q cm , 1 680 cm 1
E X A M P I. E 2:
2,2,6,6-tetramethyl-4-hydroxy-4-carbamoylpiperidinium stearate
5.5 g of stearic acid and 4 CJ of the 2,2,6,6-tetramethyl-4-
hydroxy-4-carbamoylpiperidine obtained in Exarnple 1 were boiled . :
in about 20 ml o~ ethanol and allowed to stand thereaftex. White
,
- ~ : , ., ......... -
., :
,: . ..... , :~
. . . . . . . . ..
HOE 7~/E~ ~00
1~8~23~
cristals were obt~ined having a mel-ti.ng point of from 151 to 154C.
E X A M P L ~ 3:
.
~.,2,6,6-tetramethyl-4-hydroxy-4-carbamoylpiperidinium-p-ter-tio-
butylbenzoa-t~
. The preparation was carried out in an analogous manner to
Example 2 by using instead of stearic acid 3.7 g of p-
butylbenzoic acid. Melting point oE the salt 240C.
E X A M P L E A:
,
2,2,6,6--tetramethyl 4-hydroxy-4-carbamoylpiper:idinium succina-te
The preparation was carried out in an analogous manner to
Example 2 using instead of stearic acid 1.2 g of succinic acid. ~:
Melting poin-t of the salt 230C. .
E X A M P L E 5
. ~ . . _ _
This example d~.. m.onstrated -the light-stab~ ing ac-tion of ~:
some of the compounds according -to the invention used iII a poly-
~-olefin.
100 parts by weight of polypropylene having a melt index
i5 of about 6 g/10 minutes (according to ASTM D 1238-62 T) and
a density of 0.96 g/cm3 were mixed with
0.l part by weight of a bis-(4'-hydroxy-3'-tertio-butylphenyl)
butanoic acid ester
0.2 part by weight oE calcium stearate and each time
0.3 part by weight of the stabiliæers according to the invention
to be examlned and homogeni~ed on a two ro:Ller mill at 200C for ~:
a period of 5 mintes. The plastics rnelt was rolled at 200C
to give a plate having a thickness of 1 mm. Test specimens were
punched from the cooLed plate according to German industrial
standard DIN 53 455.
29~; Comparative test specimens were prepared in analogous manner
~ .
_ 9 _
HOE ~ 00
~1~8~Z3~
b~lt withou~ the use o~tl~st~bilizer to be examined.
For determ.ininy the light s-tabi].ity the spec.imens were ex-
posed to light of varying intens.ity in a weatherorneter (Xenotest .
150) of Messrs. Original Hanau Quarzlampen GmbH. The radiation
S intensi-ty was varied by 6 infrared windows and 1 ultraviolet win-
dow (according to DI~ 53 387).
The ~ime of exp~sure in hours (- endurance) has measured,
after which the absolute elongation at rupture has dropped to ...
l0 %. The elongation at rupture was determined with a tension
test device of Messrs. Instron at a take-off speed of 5 cm/minute.
It was 850 ~ prior -to the beginning of the exposure test.
The resultats are summarized in the following table:
~Compound according t~ example ~ Time of ~xposure (hours)¦
1 > 3 000
2 > 700
3 ~ 700
4 > 700 . .
without a piperidine compound .
(comparison) 560
__ _
When using the base according to Example 1, the elongation
to brea]c was 580 % after 3.000 hours, whereas it was only 6 %
when using a commercial product (octoybenzovhenone) after 3.000
hours and 18 % when using a nickel chelate.
- 10 -
-. -. -. - -: ~ . : .. ::. : . -;............ :
