CA1081234A - 2,2,6,6-tetramethyl-4-hydroxy-7-carbamoyl piperidene compounds - Google Patents
2,2,6,6-tetramethyl-4-hydroxy-7-carbamoyl piperidene compoundsInfo
- Publication number
- CA1081234A CA1081234A CA270,242A CA270242A CA1081234A CA 1081234 A CA1081234 A CA 1081234A CA 270242 A CA270242 A CA 270242A CA 1081234 A CA1081234 A CA 1081234A
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- Prior art keywords
- compound
- hydroxy
- polymer
- tetramethyl
- acid
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/60—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D211/62—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals attached in position 4
- C07D211/66—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals attached in position 4 having a hetero atom as the second substituent in position 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Hydrogenated Pyridines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Piperidine hydroxyamides and their preparation Abstract of the disclosure:
Distinct 2,2, 6,6-tetramethyl-4-hydroxy-4-carbamoyl-piperidines are excellent stabilizers for polymeric materials against light and heat decomposition.
Distinct 2,2, 6,6-tetramethyl-4-hydroxy-4-carbamoyl-piperidines are excellent stabilizers for polymeric materials against light and heat decomposition.
Description
~ 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 ~ ..
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~
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
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
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:
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. .
. ~ . . _ _ 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.
-. -. -. - -: ~ . : .. ::. : . -;............ :
- ,. ~ . ::
~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:
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. .
. ~ . . _ _ 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.
-. -. -. - -: ~ . : .. ::. : . -;............ :
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A 2,2,6,6-tetramethyl-4-hydroxy-4-carbamoylpiperi-dine of the formula wherein R1 and R2 each represent methyl groups and H-X
represents phosphoric acid, phosphorous acid, an aliphatic or aromatic sulfonic acid or a phosphonic acid, an aliphatic mono-, di-or polycarboxylic acid or an aromatic mono- or dicarboxylic acid and m is 0 or 1.
represents phosphoric acid, phosphorous acid, an aliphatic or aromatic sulfonic acid or a phosphonic acid, an aliphatic mono-, di-or polycarboxylic acid or an aromatic mono- or dicarboxylic acid and m is 0 or 1.
2. A compound as claimed in Claim 1, wherein the compound is 2,2,6,6-tetramethyl-4-hydroxy-4-carbamoyl-piperidinium stearate.
3. A compound as claimed in Claim 1, wherein the compound is 2,2,6,6-tetramethyl-4-hydroxy-carbamoyl-piperidinium-p-tert-butyl benzoate.
4. A compound as claimed in Claim 1, wherein the compound is 2,2,6,6-tetramethyl-4-hydroxy-4-carbamoyl-piperidinium succinate.
5. A process for the preparation of a compound as claimed in Claim 1 in which a 2,2-dimethyl-6,6-dialkyl-piperidine cyanohydrin is saponified with a strong mineral acid and the resultant 2,2-dimethyl-6,6-dialkyl-4-hydroxy-4-carbamoylpiperidinium chloride is converted into a 2,2,6,6-tetramethyl-4-hydroxy-4-carbamoylpiperidine by means of a strong base or a suitable ion exchanger.
6. A process for the stabilization of a synthetic polymer against the detrimental action of light and heat in which 0.01 to 5 parts by weight, calculated on the polymer, of a compound as defined in Claim 1 is added to the polymer.
7. A process as claimed in Claim 6 in which the compound is added in an amount of 0.05 to 3 parts by weight.
8. A process as claimed in Claim 6 in which at least one other stabilizer selected from the group of heat and light stabilizers is added to the polymer.
9. A process as claimed in Claim 6, Claim 7 or Claim 8 in which the polymer is a polyolefin.
10. A process as claimed in Claim 6, Claim 7 or Claim 8 in which the polymer is a polymer containing halogen atoms.
11. A process as claimed in Claim 6, Claim 7 or Claim 8 in which the polymer is a homopolymer of vinyl chloride or vinylidene chloride, or a copolymer of said compounds with olefinically unsaturated monomers copoly-merizable therewith.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762602673 DE2602673C3 (en) | 1976-01-24 | 1976-01-24 | 2,2,6,6-Tetramethyl-4-hydroxy-4carbamoylpiperidine, its preparation and use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081234A true CA1081234A (en) | 1980-07-08 |
Family
ID=5968206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA270,242A Expired CA1081234A (en) | 1976-01-24 | 1977-01-21 | 2,2,6,6-tetramethyl-4-hydroxy-7-carbamoyl piperidene compounds |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS5291875A (en) |
| AT (1) | AT353013B (en) |
| BE (1) | BE850694A (en) |
| BR (1) | BR7700373A (en) |
| CA (1) | CA1081234A (en) |
| CH (1) | CH628331A5 (en) |
| DE (1) | DE2602673C3 (en) |
| DK (1) | DK25077A (en) |
| FR (1) | FR2338931A1 (en) |
| GB (1) | GB1561001A (en) |
| IT (1) | IT1076011B (en) |
| LU (1) | LU76617A1 (en) |
| NL (1) | NL7700520A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2742582A1 (en) * | 1977-09-22 | 1979-04-05 | Hoechst Ag | SUBSTITUTED PIPERIDINE HYDROXYAMIDES, THEIR PRODUCTION AND USE AS LIGHT PROTECTION AGENTS |
| DE4125440A1 (en) * | 1990-08-09 | 1992-02-13 | Sandoz Ag | MONO, BI OR TRI-CARBOCYCLIC PHOSPHINE OR PHOSPHONIC ACID COMPOUNDS |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1526656A (en) * | 1966-06-15 | 1968-05-24 | Sankyo Co | New compounds 2, 2-dimethyl-4, 4, 6, 6-tetrasubstituted-piperidine-1-oxides and process for their preparation |
| DE2719133A1 (en) * | 1976-05-11 | 1977-12-01 | Ciba Geigy Ag | NEW STABILIZERS |
-
1976
- 1976-01-24 DE DE19762602673 patent/DE2602673C3/en not_active Expired
-
1977
- 1977-01-19 NL NL7700520A patent/NL7700520A/en not_active Application Discontinuation
- 1977-01-19 BR BR7700373A patent/BR7700373A/en unknown
- 1977-01-20 CH CH68877A patent/CH628331A5/en not_active IP Right Cessation
- 1977-01-21 AT AT37677A patent/AT353013B/en not_active IP Right Cessation
- 1977-01-21 LU LU76617A patent/LU76617A1/xx unknown
- 1977-01-21 IT IT1953677A patent/IT1076011B/en active
- 1977-01-21 GB GB250377A patent/GB1561001A/en not_active Expired
- 1977-01-21 CA CA270,242A patent/CA1081234A/en not_active Expired
- 1977-01-21 JP JP501777A patent/JPS5291875A/en active Pending
- 1977-01-21 DK DK25077A patent/DK25077A/en not_active Application Discontinuation
- 1977-01-24 FR FR7701884A patent/FR2338931A1/en active Granted
- 1977-01-24 BE BE174332A patent/BE850694A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| LU76617A1 (en) | 1977-08-12 |
| NL7700520A (en) | 1977-07-26 |
| DE2602673C3 (en) | 1979-02-15 |
| JPS5291875A (en) | 1977-08-02 |
| DE2602673A1 (en) | 1977-07-28 |
| IT1076011B (en) | 1985-04-22 |
| DK25077A (en) | 1977-07-25 |
| CH628331A5 (en) | 1982-02-26 |
| FR2338931A1 (en) | 1977-08-19 |
| GB1561001A (en) | 1980-02-13 |
| BE850694A (en) | 1977-07-25 |
| AT353013B (en) | 1979-10-25 |
| BR7700373A (en) | 1977-09-20 |
| FR2338931B1 (en) | 1980-06-06 |
| DE2602673B2 (en) | 1978-06-15 |
| ATA37677A (en) | 1979-03-15 |
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